JP2019209975A - Plastic container and composition for plastic container forming - Google Patents

Abstract

To provide a plastic container which enables effective control on transmission of ultraviolet in the long-wavelength from 380 to 420nm and short wavelength visible lights as well as favorable light transmission properties for the visible lights.SOLUTION: A plastic container contains at least one ultraviolet absorbing agent selected among the indole-based compounds shown in the general equation 1 below.SELECTED DRAWING: None

Description

  The present invention relates to a plastic container, and more specifically, a plastic container and a composition for forming a plastic container that have excellent transparency to visible light while efficiently suppressing transmission of ultraviolet rays and short-wavelength visible light of 380 to 420 nm. Related to things.

  Containers are used for storing medicines, cosmetics, food and drinks, and the like. However, since chemicals, cosmetics, foods and drinks and the like are easily changed by light, particularly ultraviolet rays, the container is required to suppress the transmission of ultraviolet rays. From the viewpoint of suppressing the transmission of ultraviolet rays, aluminum containers and colored containers are excellent, but it is difficult to visually confirm the amount and state of the contents of the aluminum containers and colored containers. Has the problem.

  On the other hand, plastic containers made of synthetic resin are widely used as containers because they are inexpensive and excellent in moldability and light weight. Although the plastic container is excellent in transparency (transmittance of visible light), it is inferior in the effect of suppressing the transmission of ultraviolet rays as compared with an aluminum container or a colored container. Therefore, in the past, ultraviolet absorbers have been used in plastic containers in order to suppress the transmission of ultraviolet rays (Cited documents 1, 2).

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

  Since the plastic container is transparent and easily transmits ultraviolet rays or the like, the ultraviolet absorber is required to have an excellent ultraviolet ray suppressing effect. However, the effect of the conventional ultraviolet absorber is not satisfactory, and there is still room for improvement even when a large amount of the ultraviolet absorber is used. In particular, the effect of suppressing the transmission of ultraviolet rays in the long wavelength region of 380 nm to 420 nm and visible light in the short wavelength region 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.

  In addition, in recent years. In order to reduce weight, plastic containers are being made thinner. A certain amount is required for the conventional ultraviolet absorber to exert its effect, but when used in a thin-walled container, the amount of addition to the container becomes relatively large, so that the mechanical properties of the plastic container are lowered. There was also.

  Therefore, the object of the present invention is to effectively suppress the transmission of ultraviolet rays, particularly ultraviolet rays in the long wavelength region of 380 to 420 nm and short wavelength visible rays, even with the use of an extremely small amount of the ultraviolet absorber. It is an object of the present invention to provide a plastic container having excellent transparency to visible light.

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

（一般式［１］中、Ｒ_１は直鎖、分岐または環状のアルキル基、アラルキル基、置換または非置換の芳香族基、−ＣＯＲ_３基を表し、Ｒ_２は置換または非置換の芳香族基を表す。Ｒ_３は、直鎖、分岐または環状のアルキル基、アラルキル基、置換または非置換の芳香族基を表す。Ｘ_１〜Ｘ_４はそれぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、ニトロ基、カルボキシル基、エステル基を表す。Ｙ_１およびＺ_１はそれぞれ同一でも異なっていてもよく、Ｒ_４−ＣＯ−基、Ｒ_５−ＯＣ（＝Ｏ）−基、Ｒ_６−基、またはＲ_７−ＳＯ_２−基を表す。Ｒ_４、Ｒ_５およびＲ_７は、直鎖、分岐または環状のアルキル基、アラルキル基、直鎖、分岐または環状のフルオロアルキル基、あるいは置換または非置換の芳香族基を表し、Ｒ_６は直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のフルオロアルキル基、ニトロ基あるいは置換または非置換の芳香族基を表す。Ｙ_１およびＺ_１が同時に−Ｒ₆基になることはない。式中の波線は二重結合に対してＥ体、Ｚ体、またはこれらの混合物であることを示す。）

（一般式［２］中、Ｒ_１、Ｒ_２およびＸ_１〜Ｘ_４は、一般式［１］と同じ意味を表し、Ｙ_２およびＺ_２のどちらか一方はＲ_７−ＣＯ−基、他方は水素原子を表し、Ｒ_７は置換または非置換の芳香族基を表す。式中の破線は二重結合に対してＥ体、Ｚ体、またはこれらの混合物であることを示す。）
［２］ 前記プラスチック容器内部において、波長５００ｎｍの光の透過率が８０％以上１００％以下であり、かつ、波長４２０ｎｍの光の透過率が０％以上４０％以下である［１］に記載のプラスチック容器。
［３］ 前記プラスチック容器は、樹脂容器本体からなる［１］または［２］に記載のプラスチック容器。
［４］ 前記プラスチック容器は、
樹脂容器本体と、
前記容器本体の内表面および外表面の少なくとも一方に形成された層と、
を備える、［１］または［２］に記載のプラスチック容器。
［５］ 前記紫外線吸収剤は、前記樹脂容器本体および前記層の少なくとも一方に含まれる、［４］に記載のプラスチック容器。
［６］ 前記層は、コーティング層および合成樹脂フィルムからなる層から選択される単層または２層以上の積層体である、［４］または［５］に記載のプラスチック容器。
［７］ ボトル形状である［１］〜［６］のいずれかに記載のプラスチック容器。
［８］ 薬品用である［１］〜［７］のいずれかに記載のプラスチック容器。
［９］ 化粧品用である［１］〜［７］のいずれかに記載のプラスチック容器。
［１０］ 飲料または食品用である［１］〜［７］のいずれかに記載のプラスチック容器。
［１１］ 下記一般式［１］および下記一般式［２］で表されるインドール系化合物から選択される少なくとも１種の紫外線吸収剤と、樹脂とを含むプラスチック容器形成用組成物。

（一般式［１］中、Ｒ_１は直鎖、分岐または環状のアルキル基、アラルキル基、置換または非置換の芳香族基、−ＣＯＲ_３基を表し、Ｒ_２は置換または非置換の芳香族基を表す。Ｒ_３は、直鎖、分岐または環状のアルキル基、アラルキル基、置換または非置換の芳香族基を表す。Ｘ_１〜Ｘ_４はそれぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、ニトロ基、カルボキシル基、エステル基を表す。Ｙ_１およびＺ_１はそれぞれ同一でも異なっていてもよく、Ｒ_４−ＣＯ−基、Ｒ_５−ＯＣ（＝Ｏ）−基、Ｒ_６−基、またはＲ_７−ＳＯ_２−基を表す。Ｒ_４、Ｒ_５およびＲ_７は、直鎖、分岐または環状のアルキル基、アラルキル基、直鎖、分岐または環状のフルオロアルキル基、あるいは置換または非置換の芳香族基を表し、Ｒ_６は直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のフルオロアルキル基、ニトロ基あるいは置換または非置換の芳香族基を表す。Ｙ_１およびＺ_１が同時に−Ｒ₆基になることはない。式中の波線は二重結合に対してＥ体、Ｚ体、またはこれらの混合物であることを示す。）

（一般式［２］中、Ｒ_１、Ｒ_２およびＸ_１〜Ｘ_４は、一般式［１］と同じ意味を表し、Ｙ_２およびＺ_２のどちらか一方はＲ_７−ＣＯ−基、他方は水素原子を表し、Ｒ_７は置換または非置換の芳香族基を表す。式中の破線は二重結合に対してＥ体、Ｚ体、またはこれらの混合物であることを示す。） That is, this invention can be shown below.
[1] A plastic container containing at least one ultraviolet absorber selected from indole compounds represented by the following general formula [1] and the following general formula [2].

(In the general formula [1], R ₁ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group or —COR ₃ group, and R ₂ represents a substituted or unsubstituted aromatic group. R ₃ represents a linear, branched or cyclic alkyl group, an aralkyl group, a substituted or unsubstituted aromatic group, X _{1 to} X ₄ may be the same or different and each represents a hydrogen atom, Represents a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a nitro group, a carboxyl group or an ester group, Y ₁ and Z ₁ may be the same or different, and R _{4 represents a} —CO— group, an R ₅ —OC (═O) — group, an R ₆ — group, or an R ₇ —SO ₂ — group, wherein R ₄ , R ₅ and R ₇ are linear, branched or cyclic Alkyl group, aralkyl group, straight chain, branched Other represents a cyclic fluoroalkyl group or a substituted or unsubstituted aromatic group,, R ₆ is a linear, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group or a substituted or unsubstituted Represents a substituted aromatic group, Y ₁ and Z ₁ are not simultaneously -R ₆ groups, and the wavy line in the formula indicates that they are E-form, Z-form, or a mixture thereof with respect to the double bond. Show.)

(In General Formula [2], R ₁ , R _2, and X _{1 to} X ₄ represent the same meaning as in General Formula [1], and either Y ₂ or Z ₂ is an R ₇ —CO— group, the other Represents a hydrogen atom, R ₇ represents a substituted or unsubstituted aromatic group, and a broken line in the formula indicates an E-form, a Z-form, or a mixture thereof with respect to a double bond.)
[2] In the plastic container, the transmittance of light having a wavelength of 500 nm is 80% or more and 100% or less, and the transmittance of light having a wavelength of 420 nm is 0% or more and 40% or less. Plastic container.
[3] The plastic container according to [1] or [2], wherein the plastic container includes a resin container body.
[4] The plastic container is:
A resin container body;
A layer formed on at least one of the inner surface and the outer surface of the container body;
A plastic container according to [1] or [2].
[5] The plastic container according to [4], wherein the ultraviolet absorber is included in at least one of the resin container body and the layer.
[6] The plastic container according to [4] or [5], wherein the layer is a single layer or a laminate of two or more layers selected from a layer comprising a coating layer and a synthetic resin film.
[7] The plastic container according to any one of [1] to [6], which has a bottle shape.
[8] The plastic container according to any one of [1] to [7], which is for chemicals.
[9] The plastic container according to any one of [1] to [7], which is for cosmetics.
[10] The plastic container according to any one of [1] to [7], which is for beverages or foods.
[11] A plastic container forming composition comprising at least one ultraviolet absorber selected from indole compounds represented by the following general formula [1] and the following general formula [2], and a resin.

(In the general formula [1], R ₁ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group or —COR ₃ group, and R ₂ represents a substituted or unsubstituted aromatic group. R ₃ represents a linear, branched or cyclic alkyl group, an aralkyl group, a substituted or unsubstituted aromatic group, X _{1 to} X ₄ may be the same or different and each represents a hydrogen atom, Represents a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a nitro group, a carboxyl group, or an ester group, Y ₁ and Z ₁ may be the same or different; _{4 represents a} —CO— group, an R ₅ —OC (═O) — group, an R ₆ — group, or an R ₇ —SO ₂ — group, wherein R ₄ , R ₅ and R ₇ are linear, branched or cyclic Alkyl group, aralkyl group, straight chain, branched Other represents a cyclic fluoroalkyl group or a substituted or unsubstituted aromatic group,, R ₆ is a linear, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group or a substituted or unsubstituted Represents a substituted aromatic group, and Y ₁ and Z ₁ are not simultaneously —R ₆ groups, and the wavy line in the formula indicates that they are E-form, Z-form, or a mixture thereof with respect to the double bond. Show.)

(In General Formula [2], R ₁ , R ₂ and X _{1 to} X ₄ represent the same meaning as in General Formula [1], and either Y ₂ or Z ₂ is an R ₇ —CO— group, and the other Represents a hydrogen atom, R ₇ represents a substituted or unsubstituted aromatic group, and a broken line in the formula indicates an E-form, a Z-form, or a mixture thereof with respect to a double bond.)

  ADVANTAGE OF THE INVENTION According to this invention, the plastic container which has the outstanding transmittance | permeability with respect to visible light can be provided, suppressing the transmission of the ultraviolet-ray of a 380-420 nm long wavelength region, and short wavelength visible light efficiently. Thereby, while being excellent in appearance, such as transparency, it is excellent in the effect which suppresses permeation | transmission of an ultraviolet-ray, Therefore The deterioration by the ultraviolet-ray of the content can be suppressed effectively.

2 is a ¹ H-NMR chart of an indole compound (Exemplary Compound 1-14) synthesized in Production Example 1. FIG. 2 is a ¹ H-NMR chart of an indole compound (Exemplary Compound 1-18) synthesized in Production Example 2. 2 is a ¹ H-NMR chart of an indole compound (Exemplary Compound 2-11) synthesized in Production Example 3. 7 is a ¹ H-NMR chart of an indole compound (Exemplary Compound 2-17) synthesized in Production Example 4. 2 is a ¹ H-NMR chart of an indole compound (Exemplary Compound 2-21) synthesized in Production Example 5.

The plastic container of the present invention contains at least one ultraviolet absorber (hereinafter, ultraviolet absorber (a)) selected from indole compounds represented by the general formula [1] and the general formula [2].
Hereinafter, the plastic container of this invention is demonstrated based on 1st Embodiment or 2nd Embodiment. In addition, description is abbreviate | omitted suitably about the same structure and component.

<First Embodiment>
The plastic container of the present embodiment is composed only of a resin container main body, and the container main body includes at least one ultraviolet absorber (a) selected from indole compounds represented by the general formula [1] and the general formula [2]. )including.

  Since the plastic container of this embodiment contains a specific ultraviolet absorber, it has excellent transmission with respect to visible light while efficiently suppressing transmission of ultraviolet light and short wavelength visible light in the long wavelength region of 380 to 420 nm. Have sex.

  That is, in the plastic container of the present embodiment, the transmittance of light having a wavelength of 500 nm is 80% or more and 100% or less, preferably 85% or more and 100% or less, more preferably 90% or more and 100% or less, In addition, the transmittance of light having a wavelength of 420 nm is 0% to 40%, preferably 0% to 30%, and more preferably 0% to 20%.

  In the plastic container of the present embodiment, the transmittance of 500 nm to 900 nm is 75% or more, preferably 80% or more, more preferably 85% or more. Furthermore, in this case, when the wavelength range of visible light is preferably 470 nm to 900 nm, more preferably 450 nm to 900 nm, it is more preferable that the respective transmittances are obtained.

  Thereby, since it is excellent in the visible light transmittance, it is excellent in appearance such as transparency, and since it is excellent in the effect of suppressing the transmission of ultraviolet rays, it is possible to effectively suppress the deterioration of the contents due to ultraviolet rays.

[Resin container body]
The resin container body includes a resin and an ultraviolet absorber.
The shape can adopt various shapes such as bottle shape, tank shape, ampoule shape, box shape, tube shape, infusion bag shape, etc., and from the viewpoint of handling and storage of the contents injected into the plastic container Therefore, the bottle shape is preferable.

The thickness of the resin container main body is about 0.1 to 2 mm, preferably about 0.2 to 1 mm, and can be as thin as about 1 mm or less. Since the plastic container of this embodiment contains the specific ultraviolet absorber mentioned later, it is excellent in mechanical characteristics even if it is thin.
Below, the component contained in the resin container main body is demonstrated.

(resin)
Examples of the resin constituting the resin container body include polyolefins such as polyethylene, polypropylene, and polystyrene; copolymers of polyethylene and cycloolefins such as norbornene; polyacrylic acid, polyacrylic ester, polyvinyl acetate, polyacrylonitrile, polychlorinated Vinyl compounds such as vinyl and polyvinyl fluoride, and addition polymers of vinyl compounds; polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, vinylidene polycyanide, vinylidene fluoride / trifluoroethylene copolymer, fluorine Vinyl compounds such as vinylidene chloride / tetrafluoroethylene copolymer and vinylidene cyanide / vinyl acetate copolymer, or copolymers of fluorine-based compounds; polytrifluoroethylene, polytetrafluoroethylene, Compounds containing fluorine such as hexafluoropropylene; polyamides such as nylon 6 and nylon 66; polyimides; polyurethanes; polypeptides; polybutylene terephthalate, polyethylene terephthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene terephthalate-tetramethylcyclobutylene diol Copolymer (Tritan), polyethylene terephthalate-cyclohexanedimethanol copolymer (PETG, PCTG), polycyclohexanedimethylene terephthalate-isophthalate copolymer (PCTA), polyethylene terephthalate-3,9-bis (1,1- Polyester such as dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane copolymer; Polymers; and polyvinyl butyral; polyoxymethylene, polyethylene oxide, polyethers such as polypropylene oxide, epoxy resins, polyvinyl alcohol.
Among these, polybutylene terephthalate, polyethylene terephthalate, polycyclohexane dimethylene terephthalate, polycyclohexane dimethylene terephthalate-tetramethylcyclobutylene diol copolymer (Tritan), polyethylene terephthalate-cyclohexane dimethanol copolymer (PETG, PCTG) , Polyesters such as polycyclohexanedimethylene terephthalate-isophthalate copolymer (PCTA), polycondensation polymers such as polycarbonate, and polyolefins such as polyethylene, polypropylene, and polystyrene are preferable. Polyethylene terephthalate, polycyclohexane dimethylene terephthalate, polycyclohexane dimethylene Terephthalate-tetramethylcyclobutylenediol copolymer (Tritan), polyester Terephthalate - cyclohexanedimethanol copolymer (PETG, PCTG), poly cyclohexane dimethylene terephthalate - isophthalate copolymer (PCTA) polyesters such as, the polycondensation polymer such as polycarbonate preferred.

(Ultraviolet absorber (a))
The ultraviolet absorber (a) contains at least one compound selected from indole compounds represented by the following general formula [1] and the following general formula [2].

(Compound represented by the general formula [1])

In the general formula [1], R ₁ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group, —COR ₃ group, and R ₂ represents a substituted or unsubstituted aromatic group. Represents. R ₃ represents a linear, branched or cyclic alkyl group, an aralkyl group, or a substituted or unsubstituted aromatic group. X _{1 to} X ₄ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a nitro group, a carboxyl group, or an ester group. Represent. Y ₁ and Z ₁ may be the same or different and each represents an R ₄ —CO— group, an R ₅ —OC (═O) — group, an R ₆ — group, or an R ₇ —SO ₂ — group. R _4, R ₅ and R ₇ is a linear, branched or cyclic alkyl group, an aralkyl group, a straight-chain, branched or cyclic fluoroalkyl group or a substituted or unsubstituted aromatic group,, R ₆ is a straight It represents a chain, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group or a substituted or unsubstituted aromatic group. Y ₁ and Z ₁ are not —R ₆ groups at the same time. The wavy line in the formula indicates the E-form, the Z-form, or a mixture thereof with respect to the double bond.

  The linear or branched alkyl group is a linear or branched alkyl group having 1 to 12 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group. Tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 2-methylpentyl group 4-methylpentyl group, 4-methyl-2-pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 3-methylhexyl group, 5- Methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,5- A dimethylhexyl group, and the like.

  The cyclic alkyl group is an optionally substituted cyclic alkyl group having 3 to 12 carbon atoms, specifically a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentanyl group. , Cyclodecanyl group, 2-hydroxycyclohexyl group, 2,3-dihydroxycyclohexyl group, 2-aminocyclohexyl group, 2,3-diaminocyclohexyl group, 2-mercaptocyclohexyl group, and the like.

  Examples of the aralkyl group include groups substituted with aromatic hydrocarbons or aromatic heterocycles. Examples of the aralkyl group substituted with aromatic hydrocarbons include benzyl group, 2-hydroxybenzyl group, 2,4-dihydroxybenzyl group, 2,4,6-trihydroxybenzyl group, 2-aminobenzyl group, 2 , 4-Diaminobenzyl group, 2,4,6-triaminobenzyl group, 2-mercaptobenzyl group, 2,4-dimercaptobenzyl group, 2,4,6-trimercaptobenzyl group, 2,4-difluorobenzyl Group, pentafluorophenylmethyl group, 4-vinylphenylmethyl group, phenethyl group, 2-naphthylmethyl group and the like. Examples of the aralkyl group substituted with an aromatic heterocycle include a 2-pyridylmethyl group, a 3-thiophenylmethyl group, and a 3-furylmethyl group.

  The aromatic group is an aromatic group having 6 to 30 carbon atoms, and specifically includes phenyl, naphthyl, biphenylyl, terphenylyl and the like.

  Examples of the substituent of the aromatic group include: hydroxyl group; amino group; cyano group; halogen atom which is fluorine, chlorine, iodine and bromine; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , Tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, etc. An alkyl group of 6; a haloalkyl group obtained by substituting one or more hydrogen atoms of the alkyl group with at least one halogen atom selected from fluorine, chlorine, iodine and bromine; a methoxy group, an ethoxy group, a methoxy group, i-propoxy group, n-propoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexylo group C1-C6 alkoxy groups, such as a xy group, etc. can be mentioned.

R _{3 in the} —COR ₃ group represents a linear, branched or cyclic alkyl group, an aralkyl group, or a substituted or unsubstituted aromatic group. These groups are the same as those exemplified for R ₁ .

In the present embodiment, from the viewpoint of the effects of the present invention, R ₁ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a substituted or non-substituted group having 6 to 30 carbon atoms. A substituted aromatic group is preferable, a linear or branched alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms is more preferable, and a linear or branched group having 1 to 6 carbon atoms. Or a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms is more preferable.

R ₂ represents a substituted or unsubstituted aromatic group.
The “substituted or unsubstituted aromatic group” is the same as the group exemplified for R ₁ .

In the present embodiment, from the viewpoint of the effects of the present invention, R ₂ is preferably a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, and more preferably a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms. .

X _{1 to} X ₄ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a nitro group, a carboxyl group, or an ester group. Represent.
Examples of the halogen atom include fluorine, chlorine, iodine and bromine.
The linear, branched or cyclic alkyl group is the same as the group exemplified for R ₁ .

  The linear or branched alkoxy group is an alkoxy group having 1 to 6 carbon atoms, and specifically includes a methoxy group, an ethoxy group, a methoxy group, an i-propoxy group, an n-propoxy group, an s-butoxy group, t- Examples include butoxy group, pentyloxy group, hexyloxy group and the like.

  The cyclic alkoxy group is a cyclic alkoxy group having 6 to 15 carbon atoms, and specific examples include a cyclopentyloxy group, a cyclohexyloxy group, a 2-methylcyclohexyloxy group, and a 2,4-dimethylcyclohexyloxy group. be able to.

In the present embodiment, from the viewpoint of the effects of the present invention, X _{1 to} X ₄ may be the same or different, and a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms is preferable.

Y ₁ and Z ₁ may be the same or different and each represents an R ₄ —CO— group, an R ₅ —OC (═O) — group, an R ₆ — group, or an R ₇ —SO ₂ — group.

R ₄ , R ₅ and R ₇ represent a linear, branched or cyclic alkyl group, an aralkyl group, a linear, branched or cyclic fluoroalkyl group or a substituted or unsubstituted aromatic group. R ₆ represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group, or a substituted or unsubstituted aromatic group.

R ₆ represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group, or a substituted or unsubstituted aromatic group. As described above, R ₆ does not contain a cyano group. Y ₁ and Z ₁ do not combine to form a ring.

The “linear, branched or cyclic alkyl group”, “aralkyl group” and “substituted or unsubstituted aromatic group” are the same as those exemplified for R ₁ .

The linear, branched or cyclic fluoroalkyl group is obtained by substituting one or more hydrogen atoms of the linear, branched or cyclic alkyl group exemplified by R ₁ with a fluorine atom.

In the present embodiment, from the viewpoint of the effect of the present invention, Y ₁ and Z ₁ are preferably R ₄ —CO— groups and R ₅ —OC (═O) — groups, and R ₄ and R ₅ are linear, A branched or cyclic alkyl group, an aralkyl group, a linear, branched or cyclic fluoroalkyl group is preferred.

  The wavy line in the formula indicates the E-form, the Z-form, or a mixture thereof with respect to the double bond. That is, the indole compound of this embodiment is a compound (E-form or Z-form) represented by the following general formula [1] and a mixture of the E-form and Z-form.

  Specific examples of the indole compound represented by the general formula [1] of the present embodiment are shown below, but are not limited to the following examples. Examples of the indole compounds represented by the general formula [1] of the present embodiment include Exemplified Compound Nos. The compound of 1-1 to 1-50 can be mentioned.

(Compound represented by the general formula [2])

In General Formula [2], R ₁ , R ₂ and X _{1 to} X ₄ represent the same meaning as in General Formula [1], and either Y ₂ or Z ₂ is an R ₇ —CO— group, and the other is Represents a hydrogen atom, and R ₇ represents a substituted or unsubstituted aromatic group. The broken line in a formula shows that it is E body, Z body, or these mixtures with respect to a double bond.

The “substituted or unsubstituted aromatic group” for R ₇ is the same as the group exemplified for R ₁ .

R ₇ is preferably a substituted aromatic group, more preferably an alkyl-substituted phenyl group, a chloro-substituted phenyl group, an alkoxy-substituted phenyl group, a trifluoromethyl-substituted phenyl group, a dialkylamino-substituted phenyl group, or a hydroxy-substituted phenyl group. And more preferably an alkyl-substituted phenyl group, an alkoxy-substituted phenyl group, a dialkylamino-substituted phenyl group, and a hydroxy-substituted phenyl group.

  Here, alkyl and alkoxy represent a lower alkyl group such as a methyl group, an ethyl group and a propyl group, and a lower alkyl group such as a methoxy group, an ethoxy group and a propoxy group.

  Specific examples of the indole compound represented by the general formula [2] of the present embodiment are shown below, but are not limited to the following examples. Examples of the indole compounds represented by the general formula [2] of the present embodiment include Exemplified Compound Nos. The compound of 2-1 to 2-50 can be mentioned.

  When the indole compound represented by the general formula [1] and the indole compound represented by the general formula [2] are used in combination, the ratio of the indole compound [2] to the indole compound [1] ([2] / [1] ) Is 5/95 to 95/5, preferably 10/90 to 90/10, more preferably 15/85 to 85/15.

(Method for producing indole compound)
In this embodiment, the indole compound represented by the general formula [1] can also be produced by a normal condensation reaction. For example, a so-called Kunefener gel condensation (knevenagel) condition (a method of condensing an aldehyde derivative and a compound represented by the general formula [IV] in a solvent such as toluene or ethanol using piperidine and / or acetic acid as a catalyst) ). However, in many cases, the compound cannot be obtained with good yield under normal condensation reaction conditions, and it is preferable to produce the compound by the production method of this embodiment.

  The method for producing an indole compound represented by the general formula [1] of the present embodiment includes the following steps.

Step 1: A Vilsmeier reagent is reacted with a compound represented by the following general formula [II] to prepare a compound represented by the following general formula [III].
Step 2: The compound represented by the general formula [III] is reacted with the compound represented by the following general formula [IV].

In the general formula _{[II], R 1, R} 2, X 1 ~X 4 have the same meanings as in formula [I].

In the general formula _{[III], R 1, R} 2 and _X 1 to X ₄ have the same meanings as in formula [I]. X ⁻ represents a halogen ion (fluorine ion, chlorine ion, iodine ion or bromine ion).

  In general formula [IV], Y and Z are synonymous with general formula [I].

(Process 1)

  The Vilsmeier reagent is prepared, for example, by reacting N, N-dimethylformamide with a halogenating agent such as phosphorus oxychloride, phosphorus oxybromide, oxalyl chloride, thionyl chloride, or benzoyl chloride. The conditions for the preparation are generally that the halogenating agent is added dropwise in the presence of N, N-formamide and, if necessary, a solvent (for example, a halogenated solvent such as dichloromethane or ethylene dichloride) under cooling at a temperature of about 0 to 5 ° C. After the reaction, the mixture is stirred for 30 minutes to 1 hour at room temperature. It is also possible to use a commercially available Vismeier reagent.

  When reacting the Vilsmeier reagent with the compound represented by the general formula [II], the Vilsmeier reagent may be added to the compound represented by the general formula [II] and reacted. You may make it react by adding the compound represented by general formula [II] to the Meyer (Vilsmeier) reagent. The reaction temperature is usually cooled (for example, 0 ° C. to 20 ° C.), the Vilsmeier reagent is brought into contact with the general formula [II], and then the reaction is performed at room temperature to about 100 ° C. The reaction temperature is preferably 40 ° C to 80 ° C. The reaction time varies depending on the reaction temperature, but is usually about 30 minutes to 1 hour at 60 ° C.

  The amount of the Vilsmeier reagent used relative to the compound represented by the general formula [II] is usually 1 to 1.5 times equivalent, preferably 1 to 1.2 times equivalent. Thereby, the compound represented by general formula [III] can be efficiently prepared.

  After the reaction, the compound represented by the general formula [III] can be obtained by cooling the reaction solution to room temperature. The compound represented by the general formula [III] can be taken out as crystals by cooling the reaction solution (for example, 5 ° C. to −10 ° C.), but it can be used in the next step without taking it out as it is. good.

(Process 2)
Next, the compound represented by the general formula [III] obtained in Step 1 is reacted with the compound represented by the general formula [IV].

  The reaction of the compound represented by the general formula [III] and the compound represented by the general formula [IV] is usually represented by the general formula [IV] in the reaction solution in which the compound represented by the general formula [III] is produced. And then a base (eg, an organic base such as triethylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, etc.) is usually added under cooling (eg, 0 ° C. to 10 ° C.), and then The reaction is performed at room temperature to about 120 ° C, preferably 60 to 100 ° C. While the reaction time varies depending on the reaction temperature, it is usually about 1 to 10 hours, preferably about 1 to 5 hours.

  The compound represented by the general formula [IV] can be reacted at 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, with respect to 1 mol of the compound represented by the general formula [III]. . The amount of the base used is generally 1.0 to 4.0 mol, preferably 1.0 to 3.0 mol, with respect to 1 mol of the compound represented by the general formula [III]. Can do.

  After the reaction, water is added, the hydrogen halide salt of the base produced in the reaction is removed by washing with water, the organic phase is concentrated, and then crystallized with a poor solvent (for example, methanol, ethanol, isopropanol, diethyl ether, diisopropyl ether). Indole compounds represented by the general formula [I] can be obtained. In some cases, the hydrogen halide salt of the base is removed by filtration, and the organic solvent is concentrated, followed by crystallization with a poor solvent. Furthermore, it can be purified by column chromatography or the like.

  The indole compound represented by the general formula [2] of the present embodiment is used instead of reacting the compound represented by the general formula [IV] in the method for producing an indole compound represented by the general formula [1]. Can be produced by reacting with an acetophenone derivative.

  Further, the indole compound represented by the general formula [2] is obtained by combining an aldehyde derivative represented by the general formula [V] and an acetophenone derivative under normal condensation conditions with a base (piperidine, triethylamine, diisopropylethylamine, pyridine, N , N-dimethylaminopyridine, etc.) in the presence of a solvent (for example, ethylene glycol, toluene, methyl cellosolve).

  The indole compound represented by the general formula [1] and / or the general formula [2] synthesized as described above generally has a maximum absorption at 350 to 410 nm. Accordingly, it is possible to effectively shield ultraviolet rays having a wavelength in this range.

  In the plastic container of this embodiment, from the viewpoint of the effect of the present invention, the blending amount of the ultraviolet absorber (a) is 0.001 to 1 part by mass with respect to 100 parts by mass of the resin constituting the container body, and is 0.00. It is preferably 002 to 1 part by mass, and more preferably 0.005 to 0.8 part by mass.

  The specific ultraviolet absorber (a) in the present embodiment is superior in the effect of suppressing ultraviolet rays as compared with the conventional ultraviolet absorber, and the amount added can be reduced. Therefore, the ultraviolet absorber (a) can be contained in the above-mentioned amount, and it has excellent transmission with respect to visible light while efficiently suppressing transmission of ultraviolet light and short wavelength visible light in the long wavelength region of 380 to 420 nm. In addition, the amount of addition is less than that of conventional UV absorbers, so that even when added to a thin plastic container, the mechanical properties are excellent.

(Other ingredients)
The composition which concerns on this embodiment can use various additives other than the said component. Additives include antioxidants, UV absorbers other than the UV absorber (a) of this embodiment, hindered amine light stabilizers, near infrared absorbers, antistatic agents, pigments, dyes, lubricants, processing aids, A plasticizer, a flame retardant, etc. can be mentioned.

[Plastic container manufacturing method]
The manufacturing method of the plastic container (resin container main body) of the present embodiment is different in processing temperature, processing conditions, etc. depending on the base resin to be used. Usually, the ultraviolet absorber (a) and other components as necessary are A molded product can be obtained by adjusting the composition by adding to a resin (powder or pellet), heating and dissolving at 150 to 350 ° C., and then molding.

  In the plastic container forming composition of the present embodiment, from the viewpoint of the effect of the present invention, the blending amount of the ultraviolet absorber (a) is 0.001 to 1 part by mass with respect to 100 parts by mass of the resin. It is preferably 002 to 1 part by mass, and more preferably 0.005 to 0.8 part by mass.

  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. Sheets, films, and the like are formed into a desired container shape.

  The plastic container (resin container body) of the present embodiment can be subjected to surface treatment as necessary. 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, ozone oxidation treatment, and the like.

  The plastic container (resin container body) of the present embodiment may have a coating layer on the surface thereof.

Second Embodiment
The plastic container of this embodiment includes a resin container body and a layer formed on at least one of the inner surface and the outer surface of the container body. The ultraviolet absorber (a) can be contained in at least one of the resin container main body and the layer.
The resin container main body in the present embodiment is the same as that in the first embodiment except that the resin container main body may not contain the ultraviolet absorber (a), and a description thereof will be omitted.

[layer]
In the present embodiment, the layer formed on the resin container body may be a coating layer or a layer made of a synthetic resin film, or a laminate of two or more layers combining these layers.

(Coating layer)
A coating layer is formed on a resin container main body, and the thickness of a coating layer is about 10-100 micrometers.
The method for forming the coating layer includes a method using a coating liquid (1) containing an ultraviolet absorber (a), a resin and an organic solvent, and an ultraviolet absorber (a), a water-soluble resin and an aqueous solvent. Examples include a method using the coating liquid (2).

  Examples of the resin contained in the coating liquid (1) include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, and polyvinyl resins. , Polyvinyl alcohol resins, polyvinyl modified resins (PVB, EVA, etc.), or copolymer resins thereof. Examples of the organic solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof.

  Examples of the water-soluble resin contained in the coating liquid (2) 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.

  These coating liquids can be obtained by stirring and mixing the above components by a known method.

In the plastic container of this embodiment, when the ultraviolet absorber (a) is included only in the coating layer, the blending amount of the ultraviolet absorber (a) is 100 parts by mass of the resin constituting the coating layer from the viewpoint of the effect of the present invention. Is 0.1 to 10 parts by mass, preferably 0.2 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass.
When a plastic container main body and a coating layer contain a ultraviolet absorber (a), the total amount is contained so that it may become the said range.

The coating solution contains dyes, pigments, or other UV absorbers for controlling the color tone in addition to additives such as near-infrared absorbers, antioxidants, and light stabilizers that are usually used in paints. Can do.
The coating layer is formed on the resin container body by applying the coating solution prepared by the above method to a bar coater, gravure coater, comma coater, lip coater, curtain coater, roll coater, blade coater, spin coater, reverse coater, die coater. It can be formed by coating with a CAP coater, R & R coater, spray or the like.

(Layer made of synthetic resin film)
A layer made of a synthetic resin film (hereinafter simply referred to as a synthetic resin film layer) is formed on the resin container body, and a single layer or two or more layers may be laminated. The thickness of the synthetic resin film layer is about 10 to 100 μm.

  As resins constituting the synthetic resin film, polyvinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polyamide resin such as MXD nylon (polymetaxylylene adipamide) and copolymers thereof; polyaramid resin; polycarbonate resin; polystyrene resin; polyacetal resin; fluororesin; , Thermoplastic polyurethanes such as polycarbonates; halogenated vinyl resins such as polyvinylidene chloride and polyvinyl chloride; polyacrylonitrile; α-olefin and vinyl acetate Copolymers with acrylic acid ester, methacrylic acid ester, etc., for example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, An ethylene-methacrylic acid copolymer; an acid obtained by modifying an α-olefin (co) polymer such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid Modified olefin resin; ionomer resin obtained by allowing Na ion, Zn ion or the like to act on a copolymer of ethylene and methacrylic acid; a mixture thereof; and the like, and at least one kind can be used.

In the plastic container of this embodiment, when the ultraviolet absorber (a) is included only in the synthetic resin film layer, the blending amount of the ultraviolet absorber (a) constitutes the synthetic resin film layer from the viewpoint of the effect of the present invention. It is 0.1-10 mass parts with respect to 100 mass parts of resin, it is preferable that it is 0.2-10 mass parts, and it is more preferable that it is 0.5-8 mass parts. When the synthetic resin film layer has a laminated structure, it may be in the above range as a whole.
When a plastic container main body and a synthetic resin film layer contain a ultraviolet absorber (a), the total amount is contained so that it may become the said range.

In this embodiment, an adhesive layer can be formed between the resin container main body and the synthetic resin film layer, or between the synthetic resin film layers that are multiple layers.
Adhesive layer is, for example, polyvinyl acetate adhesive, polyacrylate ester adhesive, cyanoacrylate adhesive, ethylene copolymer adhesive, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide It can be formed from a system adhesive, an amino resin adhesive, a phenol resin adhesive, an epoxy adhesive, a polyurethane adhesive, a rubber adhesive, a silicone adhesive, or the like. The coating method can be performed by a conventionally known method.

[Laminate]
In the present embodiment, a laminate of two or more layers combining a coating layer and a layer made of a synthetic resin film can be formed on the resin container body. The order of lamination of the coating layer and the layer composed of the synthetic resin film is not particularly limited. The thickness of the laminate is about 10 to 100 μm.

In the plastic container of this embodiment, when the ultraviolet absorber (a) is included only in the laminate, the blending amount of the ultraviolet absorber (a) is 100 parts by mass of the resin constituting the laminate from the viewpoint of the effect of the present invention. Is 0.1 to 10 parts by mass, preferably 0.2 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass. The ultraviolet absorber (a) may be contained in any layer constituting the laminate or may be contained in a plurality of layers.
When a plastic container main body and a laminated body contain a ultraviolet absorber (a), the total amount is contained so that it may become the said range.

[Usage]
The plastic container of the present embodiment includes pharmaceutical containers such as pharmaceuticals, vitamins, drinks and eye drops; cosmetic containers such as lotion, milky lotion and sunscreen; food containers; liquor, wine, beer, fruit juice, soft drinks, tea Can be used for beverage containers such as shampoo, rinse, gargle, toothpaste, disinfectant, etc. In particular, it can be preferably used for a container having transparency that can confirm the state of the contents.

  As mentioned above, although embodiment of this invention was described, these are the illustrations of this invention, In the range which does not impair the effect of this invention, various structures other than the above are employable.

  EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[Production Example 1]
(Production of Exemplified Compound 1-14)
Into a 1 L three-necked flask, 40.0 g of N, N-dimethylformamide and 130 g of 1,2-dichloroethane were inserted and cooled to 5 ° C. with an ice bath. Thereafter, 76.9 g of phosphorus oxychloride was added dropwise over 35 minutes, and the mixture was further stirred at room temperature for 25 minutes to prepare a Vilesmeier reagent. The solution was cooled to 5 ° C. with an ice bath, and 103.6 g of N-methyl-2-phenylindole was added in 10 portions over 60 minutes. Thereafter, the mixture was heated to 60 ° C. and heated and stirred for 40 minutes. To this was added 260 g of 1,2-dichloroethane and 67.0 g of ethyl acetoacetate, and then 152.5 g of triethylamine was added dropwise over 40 minutes. Thereafter, the mixture was heated to 80 ° C. and stirred for 20 minutes, and then stirred at 100 ° C. for 2 hours. After cooling the reaction mixture, it was discharged into 1 L of water and 1 L of chloroform and mixed vigorously, and then the aqueous phase was separated. After washing with water twice to separate the organic phase, chloroform and 1,2-dichloroethane were distilled off under reduced pressure. After adding 200 g of methanol to the residue, the crystallized solid was filtered off and recrystallized twice from ethanol to obtain 61.2 g of the desired product (Exemplary Compound 1-14) as pale yellow crystals.
The HPLC purity of this compound was 99.0 Area%, and the yield was 35%. The melting point was 143 ° C.
A ¹ H-NMR chart of this compound is shown in FIG. ^As apparent from the ¹ H-NMR chart, this compound was a mixture of E-form and Z-form.

[Production Example 2]
(Production of Exemplified Compound 1-18)
Into a 100 ml three-necked flask, 4.00 g of N, N-dimethylformamide and 13 g of 1,2-dichloroethane were inserted, and cooled to 5 ° C. with an ice bath. Thereafter, 7.69 g of phosphorus oxychloride was added dropwise over 35 minutes, and the mixture was further stirred at room temperature for 25 minutes to prepare a Vilesmeier reagent. The solution was cooled to 5 ° C. with an ice bath and 10.36 g of N-methyl-2-phenylindole was added in 5 portions over 10 minutes. Thereafter, the mixture was heated to 60 ° C. and heated and stirred for 40 minutes. After adding 26 g of 1,2-dichloroethane and 10.33 g of ethyl 4,4-difluoroacetoacetate, 15.25 g of triethylamine was added dropwise over 40 minutes. Thereafter, the mixture was heated to 80 ° C. and stirred for 20 minutes, and then stirred at 100 ° C. for 2 hours. After cooling the reaction mixture, it was discharged into 100 ml of water and 100 ml of chloroform and mixed vigorously, and then the aqueous phase was separated. After washing with water twice to separate the organic phase, chloroform and 1,2-dichloroethane were distilled off under reduced pressure. After adding 20 g of methanol to the residue, the crystallized solid was filtered off and recrystallized twice from ethanol to obtain 13.8 g of the desired product (Exemplary Compound 1-18) as pale yellow crystals.
The HPLC purity of this compound was 99.0 Area%, and the yield was 73%.
The melting point was 117 ° C.
A ¹ H-NMR chart of this compound is shown in FIG. ^As apparent from the ¹ H-NMR chart, this compound was a mixture of E-form and Z-form.

[Production Example 3]
(Production of Exemplary Compound 2-11)
1.7 g of piperidine was added to 4.7 g of N-methyl-2-phenylindole-3-carbaldehyde, 2.5 g of acetophenone and 10 g of ethylene glycol, followed by heating and stirring at 170 ° C. for 1 hour. After cooling the reaction mixture, 70 g of methanol was added, and the generated crystals were filtered off. This crystal was recrystallized from isopropanol to obtain 1.7 g of Exemplified Compound 2-11 as a pale yellow crystal.
The HPLC purity of this compound was 98.9 Area%, and the yield was 25%. The melting point was 165 ° C.
A ¹ H-NMR chart of this compound is shown in FIG. ^{As is} apparent from the ¹ H-NMR chart, this compound was in the trans form.

[Production Example 4]
(Production of Exemplified Compound 2-17)
Instead of using 2.5 g of acetophenone in Production Example 3, 2.7 g of Exemplified Compound 2-17 as pale yellow crystals was obtained according to the procedure described in Production Example 3 except that 3.0 g of 4-methoxyacetophenone was used. It was.
The HPLC purity of this compound was 98.7 Area%, and the yield was 36%. The melting point was 178 ° C.
A ¹ H-NMR chart of the compound is shown in FIG. ^{As is} apparent from the ¹ H-NMR chart, this compound was in the trans form.

[Production Example 5]
(Production of Exemplified Compound 2-21)
Instead of using 2.5 g of acetophenone in Production Example 3, according to the procedure described in Production Example 3 except that 2.8 g of 2-hydroxyacetophenone was used, 5.33 g of Exemplified Compound 2-21 was obtained as pale yellow crystals. .
The HPLC purity of this compound was 99.0 Area%, and the yield was 76%. The melting point was 229 ° C.
A ¹ H-NMR chart of the compound is shown in FIG. ^{As is} apparent from the ¹ H-NMR chart, this compound was in the trans form.

The materials and evaluation methods used in this example are as follows.
[1] Polyester resin-1: Polyethylene terephthalate, Mitsui PET J-125, manufactured by Mitsui Chemicals, Inc.
[2] Polyester resin-2: Tritan TX-2001 manufactured by Eastman Keimical
[3] Ultraviolet absorber-A (hereinafter sometimes abbreviated as UVA-A): Exemplified compound 1-14
[4] Ultraviolet absorber-B (hereinafter sometimes abbreviated as UVA-B): Exemplified compound 1-18
[5] Ultraviolet absorber-C (hereinafter sometimes abbreviated as UVA-C): Exemplified compound 2-11
[6] Ultraviolet absorber-D (hereinafter sometimes abbreviated as UVA-D): Exemplified compound 2-17
[7] Ultraviolet absorber-E (hereinafter sometimes abbreviated as UVA-E): Exemplified compound 2-21
[8] Ultraviolet absorber-F (hereinafter sometimes abbreviated as UVA-F): 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole [9] Processing Thermal stabilizer A: Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite: [Hostanox P-EPQ]
[10] Brewing agent A: 1-hydroxy-4- (p-tolylamino) anthracene-9,10-dione [macrolex violet B]

(Measurement of spectral transmittance)
The ultraviolet and visible light spectrum was measured with a spectrophotometer Multispec manufactured by Shimadzu Corporation.
[Measurement of YI value]
Measured with a color difference meter Cute-i manufactured by Suga Test Instruments Co., Ltd.
[Total light transmittance]
The measurement was performed in accordance with JIS K 7136 with NDH2000 manufactured by Nippon Denshoku Co., Ltd.

[Example 1]
100 parts by weight of polyester resin-1 and 0.080 parts by weight (800 ppm) of UVA-A were supplied to a biaxial extruder (TEM-35 manufactured by Toshiba Machine Co., Ltd., cylinder setting temperature 280 ° C.) by a quantitative feeder, and the filter After the foreign matter was filtered through, it was discharged from the die into a strand shape, cooled with water and solidified, and then pelletized with a rotary cutter to obtain a polyester resin composition. Thereafter, the polyester resin composition was dried in a clean oven at 120 ° C. for 5 hours.
The polyester resin composition was injection molded at a resin temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine [SE-180DU manufactured by Sumitomo Heavy Industries, Ltd.] to mold a preform (mouth outer diameter: 25 mm weight 25 g). Next, the obtained preform was biaxially stretch blow molded at a mold temperature of 130 ° C. to produce a plastic bottle having a volume of 500 ml and a thickness of 0.8 mm. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 2]
In Example 1, instead of using 0.080 parts by mass (800 ppm) of UVA-A, 0.035 parts by mass (350 ppm) of UVA-B was used according to the operation described in Example 1, and a volume of 500 ml, A plastic bottle with a thickness of 0.8 mm was prepared. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 3]
In Example 1, instead of using 0.080 parts by mass (800 ppm) of UVA-A, 0.010 parts by mass (100 ppm) of UVA-C was used according to the operation described in Example 1, and a volume of 500 ml, A plastic bottle with a thickness of 0.8 mm was prepared. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 4]
In Example 1, instead of using 0.080 parts by mass (800 ppm) of UVA-A, 0.037 parts by mass (370 ppm) of UVA-D was used, and a volume of 500 ml, A plastic bottle with a thickness of 0.8 mm was prepared. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 5]
In Example 1, instead of using 0.080 parts by mass (800 ppm) of UVA-A, 0.015 parts by mass (150 ppm) of UVA-E was used according to the operation described in Example 1, and a volume of 500 ml, A plastic bottle with a thickness of 0.8 mm was prepared. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 6]
In Example 1, a plastic bottle having a volume of 500 ml and a thickness of 0.8 mm was used in accordance with the operation described in Example 1, except that 100 parts by mass of polyester resin-2 was used instead of 100 parts by mass of polyester resin-1. It was created. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 7]
100 parts by weight of polyester resin-1, 0.035 parts by weight of UVB-B (350 ppm), processing heat stabilizer A 0.02 parts by weight and bluing agent A 5 ppm are biaxially extruded by a quantitative feeder [Toshiba Machine Co., Ltd. Manufactured TEM-35, cylinder set temperature 280 ° C.), filtered foreign matter through a filter, discharged into a strand from a die, water cooled, solidified, and then pelletized with a rotary cutter to obtain a polyester resin composition . Thereafter, the polyester resin composition was dried in a clean oven at 120 ° C. for 5 hours.
The polyester resin composition was injection molded at a resin temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine [SE-180DU manufactured by Sumitomo Heavy Industries, Ltd.] to mold a preform (mouth outer diameter: 25 mm weight 25 g). Next, the obtained preform was biaxially stretch blow molded at a mold temperature of 130 ° C. to produce a plastic bottle having a volume of 500 ml and a thickness of 0.8 mm. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Comparative Example 1]
In Example 1, polyester resin-1 was pelletized without adding 0.080 parts by mass of UVA-A, and then the polyester resin was dried in a clean oven at 120 ° C. for 5 hours.
The polyester resin composition was injection molded at a resin temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine [SE-180DU manufactured by Sumitomo Heavy Industries, Ltd.] to mold a preform (mouth outer diameter: 25 mm weight 25 g). Next, the obtained preform was biaxially stretch blow molded at a mold temperature of 130 ° C. to produce a plastic bottle having a volume of 500 ml and a thickness of 0.8 mm. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Comparative Example 2]
In Example 1, instead of using 0.080 parts by weight (800 ppm) of UVA-A, 6 parts by weight (60000 ppm) of UVA-F was used according to the procedure described in Example 1, and the volume was 500 ml. A 0.8 mm plastic bottle was created.
This plastic bottle had a powdery powder that appeared to be UVA-F on the surface. The obtained plastic bottle was measured for visible light transmittance at wavelengths of 500 nm and 420 nm, ultraviolet light transmittance at a wavelength of 400 nm, total light transmittance, and YI value, and are summarized in Table 1.

[Example 8]
A commercially available gargle (registered trademark: Listine, calculus-inhibiting disinfectant gargle) was placed in the plastic bottle obtained in Example 1 and the plastic bottle obtained in Comparative Example 1, and was cooled with a cold white fluorescent lamp (40 watts) for 2 days. Irradiation was performed. Two days later, the internal gargle was taken out, L *, a *, and b * were measured with a spectral colorimeter (COH7700) manufactured by Nippon Denshoku Industries Co., Ltd., and ΔE was determined by the following equation.
ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2
The smaller ΔE, the less discoloration.

Plastic bottle ΔE
Example 1 0.9
Comparative Example 1 1.3

  From the above results, it can be seen that the plastic bottle containing the ultraviolet absorbent of the present invention has less discoloration of the contents compared to the plastic bottle not containing the ultraviolet absorbent.

Claims (11)

A plastic container containing at least one ultraviolet absorber selected from indole compounds represented by the following general formula [1] and the following general formula [2].

(In the general formula [1], R ₁ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group or —COR ₃ group, and R ₂ represents a substituted or unsubstituted aromatic group. R ₃ represents a linear, branched or cyclic alkyl group, an aralkyl group, a substituted or unsubstituted aromatic group, X _{1 to} X ₄ may be the same or different and each represents a hydrogen atom, Represents a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a nitro group, a carboxyl group or an ester group, Y ₁ and Z ₁ may be the same or different, and R _{4 represents a} —CO— group, an R ₅ —OC (═O) — group, an R ₆ — group, or an R ₇ —SO ₂ — group, wherein R ₄ , R ₅ and R ₇ are linear, branched or cyclic Alkyl group, aralkyl group, straight chain, branched Other represents a cyclic fluoroalkyl group or a substituted or unsubstituted aromatic group,, R ₆ is a linear, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group or a substituted or unsubstituted Represents a substituted aromatic group, Y ₁ and Z ₁ are not simultaneously -R ₆ groups, and the wavy line in the formula indicates that they are E-form, Z-form, or a mixture thereof with respect to the double bond. Show.)

(In General Formula [2], R ₁ , R _2, and X _{1 to} X ₄ represent the same meaning as in General Formula [1], and either Y ₂ or Z ₂ is an R ₇ —CO— group, the other Represents a hydrogen atom, R ₇ represents a substituted or unsubstituted aromatic group, and a broken line in the formula indicates an E-form, a Z-form, or a mixture thereof with respect to a double bond.)   The plastic container according to claim 1, wherein the transmittance of light having a wavelength of 500 nm is 80% or more and 100% or less and the transmittance of light having a wavelength of 420 nm is 0% or more and 40% or less inside the plastic container.   The plastic container according to claim 1 or 2, wherein the plastic container comprises a resin container body. The plastic container is
A resin container body;
A layer formed on at least one of the inner surface and the outer surface of the container body;
The plastic container according to claim 1, comprising:   The plastic container according to claim 4, wherein the ultraviolet absorber is contained in at least one of the resin container main body and the layer.   The plastic container according to claim 4 or 5, wherein the layer is a single layer or a laminate of two or more layers selected from a layer comprising a coating layer and a synthetic resin film.   It is a bottle shape, The plastic container in any one of Claims 1-6.   The plastic container according to any one of claims 1 to 7, which is used for chemicals.   It is for cosmetics, The plastic container in any one of Claims 1-7.   The plastic container according to any one of claims 1 to 7, which is used for beverages or foods. A plastic container forming composition comprising at least one ultraviolet absorber selected from indole compounds represented by the following general formula [1] and the following general formula [2], and a resin.

(In the general formula [1], R ₁ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group or —COR ₃ group, and R ₂ represents a substituted or unsubstituted aromatic group. R ₃ represents a linear, branched or cyclic alkyl group, an aralkyl group, a substituted or unsubstituted aromatic group, X _{1 to} X ₄ may be the same or different and each represents a hydrogen atom, Represents a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a nitro group, a carboxyl group or an ester group, Y ₁ and Z ₁ may be the same or different, and R _{4 represents a} —CO— group, an R ₅ —OC (═O) — group, an R ₆ — group, or an R ₇ —SO ₂ — group, wherein R ₄ , R ₅ and R ₇ are linear, branched or cyclic Alkyl group, aralkyl group, straight chain, branched Other represents a cyclic fluoroalkyl group or a substituted or unsubstituted aromatic group,, R ₆ is a linear, branched or cyclic alkyl group, a linear, branched or cyclic fluoroalkyl group, a nitro group or a substituted or unsubstituted Represents a substituted aromatic group, Y ₁ and Z ₁ are not simultaneously -R ₆ groups, and the wavy line in the formula indicates that they are E-form, Z-form, or a mixture thereof with respect to the double bond. Show.)

(In General Formula [2], R ₁ , R _2, and X _{1 to} X ₄ represent the same meaning as in General Formula [1], and either Y ₂ or Z ₂ is an R ₇ —CO— group, the other Represents a hydrogen atom, R ₇ represents a substituted or unsubstituted aromatic group, and a broken line in the formula indicates an E-form, a Z-form, or a mixture thereof with respect to a double bond.)

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