JP7036671B2 - Plastic container and composition for forming plastic container - Google Patents

Description

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

Containers are used to store medicines, cosmetics, food and drink, etc. However, since chemicals, cosmetics, foods and drinks are easily changed by light, especially ultraviolet rays, the container is required to suppress the transmission of ultraviolet rays. Aluminum containers and colored containers are superior from the viewpoint of suppressing the transmission of ultraviolet rays, but it is difficult to visually recognize the amount and state of the contents in the aluminum container and colored container. Has the problem.

On the other hand, as a container, a plastic container made of synthetic resin is also widely used because it is inexpensive, has excellent moldability, and is lightweight. Although the plastic container is excellent in transparency (transparency of visible light), it is inferior in the effect of suppressing the transmission of ultraviolet rays as compared with the aluminum container and the colored container. Therefore, conventionally, in plastic containers, an ultraviolet absorber has been used in order to suppress the transmission of ultraviolet rays (Cited Documents 1 and 2).

Special Table 2003-522242A Japanese Unexamined Patent Publication No. 8-301363

Since the plastic container is transparent and easily transmits ultraviolet rays and the like, the ultraviolet absorber is required to have an excellent ultraviolet ray suppressing effect. However, the effect of the conventional UV absorber is not satisfactory, and there is still room for improvement even if a large amount of UV 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, the conventionally used ultraviolet absorber absorbs the visible light region (450 nm to 500 nm), so that the amount of visible light is attenuated and the amount and state of the contents are difficult to understand. Was there.

Furthermore, in recent years. Plastic containers are being made thinner to reduce weight. A certain amount is required for the conventional UV absorber to exert its effect, but when it is used for a thin-walled container, the amount added to the container is relatively large, so that the mechanical properties of the plastic container are deteriorated. Sometimes.

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

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

（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, the present invention can be shown below.
[1] A plastic container containing at least one ultraviolet absorber selected from the indole-based 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, an aralkyl group, a substituted or unsubstituted aromatic group, and -COR ₃ groups, and R ₂ is a substituted or unsubstituted aromatic group. Represents a group. R ₃ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group. X ₁ to X ₄ may be the same or different, respectively, and 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, an ester group. Y ₁ and Z ₁ may be the same or different, respectively. Represents a ₄ -CO-group, an R5 _- OC (= O) _-group , an R6 _- group, or an _{R7 -} SO2-group. _R4 , R5 and _R7 are linear, branched or cyclic. Represents an alkyl group, an aralkyl group, a linear, branched or cyclic fluoroalkyl group, or a substituted or unsubstituted aromatic group, where _R6 is a linear, branched or cyclic alkyl group, linear, branched or cyclic fluoro. Represents an alkyl group, a nitro group or a substituted or unsubstituted aromatic group. Y ₁ and Z ₁ cannot be -R ₆ groups at the same time. Wavy lines in the formula are E-form and Z-form for a double bond. , Or a mixture of these.)

(In the general formula [2], R ₁ , R ₂ and X ₁ to X ₄ have the same meaning as the general formula [1], and one of Y ₂ and Z ₂ has an R ₇ -CO- group and the other. Represents a hydrogen atom and R ₇ represents a substituted or unsubstituted aromatic group. The broken line in the formula indicates that the double bond is an E-form, a Z-form, or a mixture thereof.)
[2] The method according to [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. Plastic container.
[3] The plastic container according to [1] or [2], wherein the plastic container is made of a resin container main body.
[4] The plastic container is
With the 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 [1] or [2].
[5] The plastic container according to [4], wherein the ultraviolet absorber is contained 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 laminated body having two or more layers selected from a layer composed of 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] for chemicals.
[9] The plastic container according to any one of [1] to [7] for cosmetics.
[10] The plastic container according to any one of [1] to [7] for beverages or foods.
[11] A composition for forming a plastic container, which comprises at least one ultraviolet absorber selected from the indole-based 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, an aralkyl group, a substituted or unsubstituted aromatic group, and -COR ₃ groups, and R ₂ is a substituted or unsubstituted aromatic group. Represents a group. R ₃ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group. X ₁ to X ₄ may be the same or different, respectively, and 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, an ester group. Y ₁ and Z ₁ may be the same or different, respectively. Represents a ₄ -CO-group, an R5 _- OC (= O) _-group , an R6 _- group, or an _{R7 -} SO2-group. _R4 , R5 and _R7 are linear, branched or cyclic. Represents an alkyl group, an aralkyl group, a linear, branched or cyclic fluoroalkyl group, or a substituted or unsubstituted aromatic group, where _R6 is a linear, branched or cyclic alkyl group, linear, branched or cyclic fluoro. Represents an alkyl group, a nitro group or a substituted or unsubstituted aromatic group. Y ₁ and Z ₁ cannot be -R ₆ groups at the same time. Wavy lines in the formula are E-form and Z-form for a double bond. , Or a mixture of these.)

(In the general formula [2], R ₁ , R ₂ and X ₁ to X ₄ have the same meaning as the general formula [1], and one of Y ₂ and Z ₂ has an R ₇ -CO- group and the other. Represents a hydrogen atom and R ₇ represents a substituted or unsubstituted aromatic group. The broken line in the formula indicates that the double bond is an E-form, a Z-form, or a mixture thereof.)

According to the present invention, it is possible to provide a plastic container having excellent transparency to visible light while efficiently suppressing the transmission of ultraviolet rays and short wavelength visible light in a long wavelength region of 380 to 420 nm. As a result, the appearance such as transparency is excellent, and the effect of suppressing the transmission of ultraviolet rays is excellent, so that deterioration of the contents due to ultraviolet rays can be effectively suppressed.

6 is a ^{1 1} H-NMR chart of an indole compound (exemplified compound 1-14) synthesized in Production Example 1. 6 is a ^{1 1} H-NMR chart of an indole compound (exemplified compound 1-18) synthesized in Production Example 2. 6 is a ¹ H-NMR chart of an indole compound (exemplified compound 2-11) synthesized in Production Example 3. 6 is a ¹ H-NMR chart of the indole compound (exemplified compound 2-17) synthesized in Production Example 4. 6 is a ¹ H-NMR chart of an indole compound (exemplified 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 the indole-based compounds represented by the general formula [1] and the general formula [2].
Hereinafter, the plastic container of the present invention will be described based on the first embodiment or the second embodiment. The description of the same configuration and components will be omitted as appropriate.

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

Since the plastic container of the present embodiment contains a specific ultraviolet absorber, it efficiently suppresses the transmission of ultraviolet rays and short-wavelength visible light in the long wavelength region of 380 to 420 nm, and has excellent transmission to visible light. Has sex.

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

The plastic container of the present embodiment has a transmittance of 75% to 900 nm of 75% or more, preferably 80% or more, and more preferably 85% or more inside the plastic container. Further, 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 each of the above-mentioned transmittances is obtained.

As a result, the transparency of visible light is excellent, so that the appearance such as transparency is excellent, and the effect of suppressing the transmission of ultraviolet rays is excellent, so that deterioration of the contents due to ultraviolet rays can be effectively suppressed.

[Resin container body]
The resin container body contains a resin and an ultraviolet absorber.
The shape can be various shapes such as bottle shape, tank shape, ampoule shape, box shape, tube shape, infusion bag shape, etc., from the viewpoint of handleability and storage of the contents injected into the plastic container. Therefore, it is preferably in the shape of a bottle.

The thickness of the resin container 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 the present embodiment contains a specific ultraviolet absorber described later, it has excellent mechanical properties even if it is thin.
The components contained in the resin container body will be described below.

(resin)
Resins constituting the main body of the resin container include polyolefins such as polyethylene, polypropylene, and polystyrene; copolymers of polyethylene and cycloolefins such as norbornene; polyacrylic acid, polyacrylic acid ester, vinyl acetate, polyacrylonitrile, and polychloride. Vinyl compounds such as vinyl and polyvinyl fluoride and addition polymers of vinyl compounds; polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride, vinylidene fluoride, vinylidene silicate, vinylidene fluoride / trifluoroethylene copolymer, Vinyl compound / tetrafluoroethylene copolymer, vinyl compound such as vinylidene cyanide / vinyl acetate copolymer or polymer of fluorine-based compound; Fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, etc. Containing compounds; polyamides such as nylon 6, nylon 66; polyimide; polyurethane; polypeptides; polybutylene terephthalate, polyethylene terephthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene terephthalate-tetramethylcyclobutylenediol copolymer (Tritan), Polyethylene terephthalate-cyclohexanedimethanol copolymer (PETG, PCTG), polycyclohexanedimethylene terephthalate-isophthalate copolymer (PCTA), polyethylene terephthalate-3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-Polyester such as undecane copolymer [5,5] Polycondensate polymer such as polycarbonate; Polyether such as polyoxymethylene, polyethylene oxide, polypropylene oxide; Epoxy resin; Polyvinyl Alcohol; polyvinyl butyral and the like can be mentioned.
Among these, polybutylene terephthalate, polyethylene terephthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene terephthalate-tetramethylcyclobutylenediol copolymer (Tritan), polyethylene terephthalate-cyclohexanedimethanol copolymer (PETG, PCTG) , Polycyclohexanedimethylene terephthalate-isophthalate copolymer (PCTA) and other polyesters, polycondensate polymers such as polycarbonate or polyolefins such as polyethylene, polypropylene and polystyrene are preferred, with polyethylene terephthalate, polycyclohexanedimethylene terephthalate and polycyclohexanedimethylene. Polyethylene, polycarbonate, etc. such as terephthalate-tetramethylcyclobutylenediol copolymer (Tritan), polyethylene terephthalate-cyclohexanedimethanol copolymer (PETG, PCTG), polycyclohexanedimethylene terephthalate-isophthalate copolymer (PCTA), etc. Polycondensation polymers are more preferred.

(Ultraviolet absorber (a))
The ultraviolet absorber (a) contains at least one compound selected from the indole-based 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, an aralkyl group, a substituted or unsubstituted aromatic group, and -COR ₃ groups, and R ₂ is a substituted or unsubstituted aromatic group. Represents. R ₃ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group. X ₁ to X ₄ may be the same or different from each other, and may contain a hydrogen atom, a halogen atom, a linear group, a branched or cyclic alkyl group, a linear group, a branched or cyclic alkoxy group, a nitro group, a carboxyl group, or an ester group. show. Y ₁ and Z ₁ may be the same or different, respectively, and represent R ₄ -CO- group, R ₅ -OC (= O)-group, R _6- group, or R ₇ -SO _2- group, respectively. R ₄ , R ₅ and R ₇ represent linear, branched or cyclic alkyl groups, aralkyl groups, linear, branched or cyclic fluoroalkyl groups, or substituted or unsubstituted aromatic groups, where R ₆ is direct. Represents a chain, branched or cyclic alkyl group, linear, branched or cyclic fluoroalkyl group, nitro group or substituted or unsubstituted aromatic group. Y ₁ and Z ₁ cannot be -R ₆ at the same time. The wavy line in the equation indicates that it is an E-form, a Z-form, or a mixture thereof for a double bond.

The linear or branched alkyl group is a linear or branched alkyl group having 1 to 12 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. , Tart-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- Examples thereof include a methylhexyl group, a 2,4-dimethylpentyl group, an n-octyl group, a tert-octyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a 2,5-dimethylhexyl group and the like.

The cyclic alkyl group is a cyclic alkyl group having 3 to 12 carbon atoms which may have a substituent, and specifically, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or 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 aromatic hydrocarbons or groups substituted with aromatic heterocycles. Examples of the aralkyl group substituted with aromatic hydrocarbons include a benzyl group, a 2-hydroxybenzyl group, a 2,4-dihydroxybenzyl group, a 2,4,6-trihydroxybenzyl group, a 2-aminobenzyl group, and 2 , 4-Diaminobenzyl group, 2,4,6-triaminobenzyl group, 2-mercaptobenzyl group, 2,4-dimercaptobenzyl group, 2,4,6-trimercaptobenzyl group, 2,4-difluorobenzyl Examples thereof include a group, a pentafluorophenylmethyl group, a 4-vinylphenylmethyl group, a phenethyl group, a 2-naphthylmethyl group and the like. Examples of the aralkyl group substituted with the aromatic heterocycle include a 2-pyridylmethyl group, a 3-thiophenylmethyl group, a 3-furylmethyl group and the like.

The aromatic group is an aromatic group having 6 to 30 carbon atoms, and specific examples thereof include phenyl, naphthyl, biphenylyl, and turfenylyl.

Substituents of aromatic groups include hydroxyl groups; amino groups; cyano groups; halogen atoms such as fluorine, chlorine, iodine and bromine; methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups and isobutyl groups. , Tart-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. 6 alkyl groups; haloalkyl groups 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; methoxy group, ethoxy group, methoxy group, Examples thereof include an alkoxy group having 1 to 6 carbon atoms such as an i-propoxy group, an n-propoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group and an n-hexyloxy group.

-COR ₃ R _3s represent linear, branched or cyclic alkyl groups, aralkyl groups, substituted or unsubstituted aromatic groups. These groups are similar to the groups exemplified in _R1 .

In the present embodiment, from the viewpoint of the effect of the present invention, as R ₁ , 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 alkyl group having 6 to 30 carbon atoms. Substituted aromatic groups are preferred, linear or branched alkyl groups with 1-12 carbon atoms or substituted or unsubstituted aromatic groups with 6-20 carbon atoms are more preferred, linear or branched with 1-6 carbon atoms. Alkyl groups or substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms are more preferable.

R ₂ represents a substituted or unsubstituted aromatic group.
The "substituted or unsubstituted aromatic group" is the same as the group exemplified in _R1 .

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

X ₁ to X ₄ may be the same or different from each other, and may contain a hydrogen atom, a halogen atom, a linear group, a branched or cyclic alkyl group, a linear group, a branched or cyclic alkoxy group, a nitro group, a carboxyl group, or an ester group. show.
Examples of the halogen atom include fluorine, chlorine, iodine and bromine.
The linear, branched or cyclic alkyl group is similar to the group exemplified in _R1 .

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

The cyclic alkoxy group is a cyclic alkoxy group having 6 to 15 carbon atoms, and specific examples thereof 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 effect of the present invention, X ₁ to X ₄ may be the same or different from each other, and a hydrogen atom, a halogen atom, and a linear or branched alkyl group having 1 to 12 carbon atoms are preferable.

Y ₁ and Z ₁ may be the same or different, respectively, and represent R ₄ -CO- group, R ₅ -OC (= O)-group, R _6- group, or R ₇ -SO _2- group, respectively.

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. It should be noted that 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 similar to the groups exemplified in _R1 .

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 in _R1 with a fluorine atom.

In the present embodiment, from the viewpoint of the effect of the present invention, _R4 -CO-group and R5 _- OC ₍ = O) _-group are preferable as Y1 and Z1, and _linear chains are used as _R4 and R5. Branched or cyclic alkyl groups, aralkyl groups, linear, branched or cyclic fluoroalkyl groups are preferred.

The wavy line in the equation indicates that it is an E-form, a Z-form, or a mixture thereof for a double bond. That is, the indole-based compound of the present embodiment is a compound represented by the following general formula [1] (E-form or Z-form) and a mixture of the E-form and the Z-form.

Specific examples of the indole-based compound represented by the general formula [1] of the present embodiment are shown below, but the examples are not limited to the following. Examples of the indole-based compound represented by the general formula [1] of the present embodiment include Exemplified Compound No. Compounds 1-1 to 1-50 can be mentioned.

(Compound represented by the general formula [2])

In the general formula [2], R ₁ , R ₂ and X ₁ to X ₄ have the same meaning as the general formula [1], and one of Y ₂ and Z ₂ has an R ₇ -CO- group and the other has the same meaning. It represents a hydrogen atom and R ₇ represents a substituted or unsubstituted aromatic group. The dashed line in the formula indicates that it is an E-form, a Z-form, or a mixture thereof for a double bond.

The "substituted or unsubstituted aromatic group" of R ₇ is the same as the group exemplified in 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, a hydroxy substituted phenyl group. It is more preferably an alkyl-substituted phenyl group, an alkoxy-substituted phenyl group, a dialkylamino-substituted phenyl group, or a hydroxy-substituted phenyl group.

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

Specific examples of the indole-based 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-based compound represented by the general formula [2] of the present embodiment include Exemplified Compound No. 2-1 to 2-50 compounds 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, and more preferably 15/85 to 85/15.

(Manufacturing method of indole compound)
In the present embodiment, the indole compound represented by the general formula [1] can also be produced by a usual condensation reaction. For example, a method of condensing an aldehyde derivative with 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 under so-called Knoevenagel condensation conditions (knevenagel). ) Can also be manufactured. However, in many cases, the compound cannot be obtained in good yield under normal condensation reaction conditions, and it is preferable to produce the compound by the production method of the present embodiment.

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

Step 1: The Vilsmeier reagent is reacted with the compound represented by the following general formula [II] to prepare the 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 to X ₄ are synonymous with the general formula [I].

In the general formula [III], R ₁ , R ₂ and X ₁ to X ₄ are synonymous with the general formula [I]. X ^- represents a halogen ion (fluorine ion, chlorine ion, iodine ion or bromine ion).

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

(Step 1)

The Vilsmeier reagent is prepared by reacting, for example, N, N-dimethylformamide with a halogenating agent such as phosphorus oxychloride, phosphorus oxybromide, oxalyl chloride, thionyl chloride, and benzoyl chloride. The preparation conditions are such 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 normal cooling, and the temperature is about 0 to 5 ° C. After the reaction, the mixture is prepared by stirring at room temperature for about 30 minutes to 1 hour. It is also possible to use commercially available Vismeier reagents.

When the Vilsmeier reagent is reacted 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. A compound represented by the general formula [II] may be added to the Vilsmeier reagent and reacted. The reaction temperature is usually cooled (for example, 0 ° C. to 20 ° C.) to bring the Vilsmeier reagent into contact with the general formula [II], and then the reaction is carried out 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 for 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 the general formula [III] can be efficiently prepared.

After the reaction, the reaction solution is cooled to room temperature to obtain a compound represented by the general formula [III]. 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.

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

A compound represented by the general formula [IV] can be reacted with 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, with 1 mol of the compound represented by the general formula [III]. .. The amount of the base used is usually 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 be done.

After the reaction, water is added, the hydrohalide hydrogen salt of the base produced in the reaction is removed by washing with water, the organic phase is concentrated, and then crystals are crystallized from a poor solvent (for example, methanol, ethanol, isopropanol, diethyl ether, diisopropyl ether). It is possible to obtain an indole-based compound represented by the general formula [I]. In some cases, it is also possible to remove the halogenated hydrogen salt of the base by filtration, concentrate the organic solvent, and then crystallize with a poor solvent. Furthermore, it can be purified by column chromatography or the like.

The indole-based compound represented by the general formula [2] of the present embodiment is a substitute for reacting the compound represented by the general formula [IV] in the above-mentioned method for producing an indole compound represented by the general formula [1]. Can be produced by reacting with an acetophenone derivative.

Further, the indole-based compound represented by the general formula [2] is a base (piperidine, triethylamine, diisopropylethylamine, pyridine, N) of an aldehyde derivative represented by the general formula [V] and an acetphenone derivative under normal condensation conditions. , N-dimethylaminopyridine, etc.) and can be produced by dehydration condensation in a solvent (eg, ethylene glycol, toluene, methyl cellosolve).

The indole-based compounds represented by the general formula [1] and / or the general formula [2] synthesized as described above generally have a maximum absorption at 350 to 410 nm. Therefore, ultraviolet rays having a wavelength in this range can be effectively shielded from light.

In the plastic container 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 constituting the container body. 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 has an excellent ultraviolet ray suppressing effect as compared with the conventional ultraviolet absorber, and the addition amount can be reduced. Therefore, the ultraviolet absorber (a) can be contained in the above amount, and while efficiently suppressing the transmission of ultraviolet rays and short-wavelength visible light in the long wavelength region of 380 to 420 nm, it has excellent transmission to visible light. In addition to having properties, the amount added is smaller than that of conventional ultraviolet absorbers, so even if it is added to a thin-walled plastic container, it has excellent mechanical properties.

(Other ingredients)
In the composition according to this embodiment, various additives can be used in addition to the above-mentioned components. As additives, antioxidants, UV absorbers other than the UV absorber (a) of the present embodiment, hindered amine-based light stabilizers, near-infrared absorbers, antistatic agents, pigments, dyes, lubricants, processing aids, etc. Examples thereof include plasticizers and flame retardant agents.

[Manufacturing method of plastic container]
In the method for manufacturing a plastic container (resin container main body) of the present embodiment, the processing temperature, processing conditions, etc. differ depending on the base resin used, but usually, the ultraviolet absorber (a) and other components described above are used as necessary. A molded product can be obtained by adding to a resin (powder or pellet) to prepare a composition, heating and melting at 150 to 350 ° C., and then molding.

In the composition for forming a plastic container 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, and 0. It is preferably 002 to 1 part by mass, 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 molded bodies, sheets, films, and the like can be manufactured. Sheets, films and the like are molded into a desired container shape.

The plastic container (resin container main body) of the present embodiment can be surface-treated as needed. 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 main body) of the present embodiment may have a coating layer on its surface.

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

[layer]
In the present embodiment, the layer formed on the resin container body may be a coating layer, a layer made of a synthetic resin film, or a laminated body having two or more layers in which these layers are combined.

(Coating layer)
The coating layer is formed on the main body of the resin container, and the thickness of the coating layer is about 10 to 100 μm.
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 a method including an ultraviolet absorber (a), a water-soluble resin and an aqueous solvent. Examples thereof include a method using the coating liquid (2).

The resin contained in the coating liquid (1) includes an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, and a polyvinyl resin. , Polyvinyl alcohol resin, polyvinyl-based modified resin (PVB, EVA, etc.), or a copolymer resin 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, and the like. Examples of the aqueous solvent include water or water to which an alcohol such as methyl alcohol, a ketone such as acetone, or an ether such as methanol is added.

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

When the ultraviolet absorber (a) is contained only in the coating layer in the plastic container of the present embodiment, 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. On the other hand, it 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 the plastic container body and the coating layer contain the ultraviolet absorber (a), the total amount thereof is included in the above range.

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

(Layer made of synthetic resin film)
The layer made of the synthetic resin film (hereinafter, simply the synthetic resin film layer) is formed on the main body of the resin container, and may be 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.

Examples of the resin constituting the synthetic resin film include polyvinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, nylon 610, nylon 11, and nylon. 12. Polyamide resin such as MXD nylon (polymethoxylylen adipamide) and copolymers thereof; polyaramid resin; polycarbonate resin; polystyrene resin; polyacetal resin; fluororesin; polyether type, adipate ester type, caprolactone ester type , Polycarbonate ester-based thermoplastic polyurethane; Polyvinylidene chloride, polyvinyl chloride and other halogenated vinyl resins; Polyacrylonitrile; α-olefins and copolymers of vinyl acetate, acrylic acid esters, methacrylic acid esters, etc., for example. , Ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylate copolymer; α- of polyethylene, polypropylene, etc. Acid-modified olefin resin obtained by modifying an olefin (co) polymer with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid; Ionomer resins on which Na ions, Zn ions, etc. are allowed to act; mixtures thereof; and the like; and at least one thereof can be used.

In the plastic container of the present embodiment, when the ultraviolet absorber (a) is contained 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 to 10 parts by mass, preferably 0.2 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the resin. When the synthetic resin film layer has a laminated structure, it may be within the above range as a whole.
When the plastic container body and the synthetic resin film layer contain the ultraviolet absorber (a), the total amount thereof is included in the above range.

In the present embodiment, an adhesive layer can be formed between the resin container main body and the synthetic resin film layer, and between the layers of the synthetic resin film layer which is a plurality of layers.
The adhesive layer may be, for example, a polyvinyl acetate adhesive, a polyacrylic acid ester adhesive, a cyanoacrylate adhesive, an ethylene copolymer adhesive, a cellulose adhesive, a polyester adhesive, a polyamide adhesive, or a polyimide. It can be formed from a system adhesive, an amino resin system adhesive, a phenol resin system adhesive, an epoxy system adhesive, a polyurethane system adhesive, a rubber system adhesive, a silicone system adhesive and the like. The coating method can be a conventionally known method.

[Laminate]
In the present embodiment, it is also possible to form a laminated body having two or more layers in which a coating layer and a layer made of a synthetic resin film are combined on the main body of the resin container. The stacking order of the coating layer and the layer made of the synthetic resin film is not particularly limited. The thickness of the laminate is about 10 to 100 μm.

When the ultraviolet absorber (a) is contained only in the laminated body in the plastic container of the present embodiment, the blending amount of the ultraviolet absorber (a) is 100 parts by mass of the resin constituting the laminated body from the viewpoint of the effect of the present invention. On the other hand, it 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 laminated body, or may be contained in a plurality of layers.
When the plastic container body and the laminate contain the ultraviolet absorber (a), the total amount thereof is included in the above range.

[Use]
The plastic container of the present embodiment is a chemical container such as a medicine, a vitamin preparation, a drink preparation, an eye medicine; a cosmetic container such as a lotion, a milky lotion, and a sunscreen; a food container; a liquor, wine, a beer, a fruit juice, a soft drink, and a tea. , Tea, coffee and other beverage containers; can be used for daily necessities containers such as shampoo, rinse, mouthwash, toothpaste and disinfectant. In particular, it can be preferably used for a transparent container in which the state of the contents can be confirmed.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted as long as the effects of the present invention are not impaired.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[Manufacturing Example 1]
(Production of Exemplified Compound 1-14)
40.0 g of N, N-dimethylformamide and 130 g of 1,2-dichloroethane were inserted into a 1 L three-necked flask and cooled to 5 ° C. by an ice bath. Then, 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. This solution was cooled to 5 ° C. in an ice bath, and 103.6 g of N-methyl-2-phenylindole was added in 10 portions over 60 minutes. Then, it was heated to 60 ° C., heated and stirred for 40 minutes, and then cooled again by an ice bath to bring the temperature of the reaction solution to 5 ° C. After adding 260 g of 1,2-dichloroethane and 67.0 g of ethyl acetoacetate, 152.5 g of triethylamine was added dropwise over 40 minutes. Then, the mixture was heated to 80 ° C. and stirred for 20 minutes, and then heated and 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 separated by filtration and recrystallized twice from ethanol to obtain 61.2 g of the target product (exemplified 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. ¹ As is clear from the 1 H-NMR chart, this compound was a mixture of E-form and Z-form.

[Manufacturing Example 2]
(Production of Exemplified Compound 1-18)
4.00 g of N, N-dimethylformamide and 13 g of 1,2-dichloroethane were inserted into a 100 ml three-necked flask and cooled to 5 ° C. by an ice bath. Then, 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. This solution was cooled to 5 ° C. in an ice bath, and 10.36 g of N-methyl-2-phenylindole was added in 5 portions over 10 minutes. Then, it was heated to 60 ° C., heated and stirred for 40 minutes, and then cooled again by an ice bath to bring the temperature of the reaction solution to 5 ° C. 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. Then, the mixture was heated to 80 ° C. and stirred for 20 minutes, and then heated and stirred at 100 ° C. for 2 hours. After cooling the reaction mixture, the mixture 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 separated by filtration and recrystallized twice from ethanol to obtain 13.8 g of the target product (exemplified 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. ¹ As is clear from the 1 H-NMR chart, this compound was a mixture of E-form and Z-form.

[Manufacturing Example 3]
(Production of Exemplified 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, and the mixture was heated and stirred at 170 ° C. for 1 hour. After cooling the reaction mixture, 70 g of methanol was added and the crystals formed 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. ¹ As is clear from the 1 H-NMR chart, this compound was a trans form.

[Manufacturing Example 4]
(Production of Exemplified Compound 2-17)
In Production Example 3, 2.7 g of Exemplified Compound 2-17 was obtained as pale yellow crystals according to the operation described in Production Example 3 except that 3.0 g of 4-methoxyacetophenone was used instead of 2.5 g of acetophenone. rice field.
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. ¹ As is clear from the 1 H-NMR chart, this compound was a trans form.

[Manufacturing Example 5]
(Production of Exemplified Compound 2-21)
5.33 g of Exemplified Compound 2-21 was obtained as pale yellow crystals according to the procedure described in Production Example 3 except that 2.8 g of 2-hydroxyacetophenone was used instead of 2.5 g of acetophenone in Production Example 3. ..
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. ¹ As is clear from the 1 H-NMR chart, this compound was a trans form.

The materials and evaluation methods used in this example are as follows.
[1] Polyester resin-1: Polyethylene terephthalate manufactured by Mitsui Chemicals, Inc. Mitsui PET J-125
[2] Polyester resin-2: Tritan TX-2001 manufactured by Eastman Chemical Company
[3] Ultraviolet absorber-A (hereinafter, may be abbreviated as UVA-A): Exemplified compound 1-14
[4] Ultraviolet absorber-B (hereinafter, may be abbreviated as UVA-B): Exemplified compound 1-18
[5] Ultraviolet absorber-C (hereinafter, may be abbreviated as UVA-C): Exemplified compound 2-11
[6] Ultraviolet absorber-D (hereinafter, may be abbreviated as UVA-D): Exemplified compound 2-17
[7] Ultraviolet absorber-E (hereinafter, may be abbreviated as UVA-E): Exemplified compound 2-21
[8] Ultraviolet absorber-F (hereinafter, may be abbreviated as UVA-F): 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole [9] Processing Heat 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 spectra were measured with a spectrophotometer Multispec manufactured by Shimadzu Corporation.
[Measurement of YI value]
It was measured with a colorimeter Cute-i manufactured by Suga Test Instruments Co., Ltd.
[Total light transmittance]
It was measured according to JIS K 7136 with NDH2000 manufactured by Nippon Denshoku Co., Ltd.

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

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

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

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

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

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

[Comparative Example 1]
In Example 1, the 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 by an injection molding machine [SE-180DU manufactured by Sumitomo Heavy Industries, Ltd.] at a resin temperature of 280 ° C. and a mold temperature of 60 ° C. to form a preform (outer diameter: 25 mm, weight 25 g). Next, the obtained preform was blow-molded by biaxial stretching at a mold temperature of 130 ° C. to prepare a plastic bottle having a volume of 500 ml and a thickness of 0.8 mm. The visible light transmittance at wavelengths of 500 nm and 420 nm, the transmittance of ultraviolet rays at a wavelength of 400 nm, the total light transmittance and the YI value of the obtained plastic bottles were measured and summarized in Table 1.

[Comparative Example 2]
In Example 1, the volume is 500 ml and the thickness is according to the operation described in Example 1, except that UVA-F 6 parts by mass (60,000 ppm) is used instead of UVA-A 0.080 parts by mass (800 ppm). A 0.8 mm plastic bottle was made.
This plastic bottle had a powdery powder that seems to be UVA-F on the surface. The visible light transmittance at wavelengths of 500 nm and 420 nm, the transmittance of ultraviolet rays at a wavelength of 400 nm, the total light transmittance and the YI value of the obtained plastic bottles were measured and summarized in Table 1.

[Example 8]
A commercially available mouthwash (registered trademark: Listerine, tartar-suppressing disinfectant mouthwash) was placed in the plastic bottle obtained in Example 1 and the plastic bottle obtained in Comparative Example 1 and used with a cold white fluorescent lamp (40 watts) for 2 days. Irradiation was performed. Two days later, the mouthwash inside was taken out, L *, a *, and b * were measured with a spectrocolorimeter (COH7700) manufactured by Nippon Denshoku Kogyo, and ΔE was calculated by the following formula.
ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2
The smaller ΔE is, the less the discoloration is.

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 absorber of the present invention has less discoloration of the contents than the plastic bottle containing no ultraviolet absorber.

Claims (11)

A plastic container containing at least one ultraviolet absorber selected from the indole-based 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, an aralkyl group, a substituted or unsubstituted aromatic group, and -COR ₃ groups, and R ₂ is a substituted or unsubstituted aromatic group. Represents a group. R ₃ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group. X ₁ to X ₄ may be the same or different, respectively, and 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, an ester group. Y ₁ and Z ₁ may be the same or different, respectively. Represents a ₄ -CO-group, an R5 _- OC (= O) _-group , an R6 _- group, or an _{R7 -} SO2-group. _R4 , R5 and _R7 are linear, branched or cyclic. Represents an alkyl group, an aralkyl group, a linear, branched or cyclic fluoroalkyl group, or a substituted or unsubstituted aromatic group, where _R6 is a linear, branched or cyclic alkyl group, linear, branched or cyclic fluoro. Represents an alkyl group, a nitro group or a substituted or unsubstituted aromatic group. Y ₁ and Z ₁ cannot be -R ₆ groups at the same time. Wavy lines in the formula are E-form and Z-form for a double bond. , Or a mixture of these.)

(In the general formula [2], R ₁ , R ₂ and X ₁ to X ₄ have the same meaning as the general formula [1], and one of Y ₂ and Z ₂ has an R ₇ -CO- group and the other. Represents a hydrogen atom and R ₇ represents a substituted or unsubstituted aromatic group. The broken line in the formula indicates that the double bond is an E-form, a Z-form, or a mixture thereof.) 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 is made of a resin container main body. The plastic container is
With the 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 or 2. The plastic container according to claim 4, wherein the ultraviolet absorber is contained in at least one of the resin container body and the layer. The plastic container according to claim 4 or 5, wherein the layer is a single layer or a laminated body having two or more layers selected from a layer composed of a coating layer and a synthetic resin film. The plastic container according to any one of claims 1 to 6, which is in the shape of a bottle. The plastic container according to any one of claims 1 to 7, which is for chemicals. The plastic container according to any one of claims 1 to 7, which is for cosmetics. The plastic container according to any one of claims 1 to 7, which is for beverages or foods. A composition for forming a plastic container, which comprises at least one ultraviolet absorber selected from the indole-based 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, an aralkyl group, a substituted or unsubstituted aromatic group, and -COR ₃ groups, and R ₂ is a substituted or unsubstituted aromatic group. Represents a group. R ₃ represents a linear, branched or cyclic alkyl group, aralkyl group, substituted or unsubstituted aromatic group. X ₁ to X ₄ may be the same or different, respectively, and 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, an ester group. Y ₁ and Z ₁ may be the same or different, respectively. Represents a ₄ -CO-group, an R5 _- OC (= O) _-group , an R6 _- group, or an _{R7 -} SO2-group. _R4 , R5 and _R7 are linear, branched or cyclic. Represents an alkyl group, an aralkyl group, a linear, branched or cyclic fluoroalkyl group, or a substituted or unsubstituted aromatic group, where _R6 is a linear, branched or cyclic alkyl group, linear, branched or cyclic fluoro. Represents an alkyl group, a nitro group or a substituted or unsubstituted aromatic group. Y ₁ and Z ₁ cannot be -R ₆ groups at the same time. Wavy lines in the formula are E-form and Z-form for a double bond. , Or a mixture of these.)

(In the general formula [2], R ₁ , R ₂ and X ₁ to X ₄ have the same meaning as the general formula [1], and one of Y ₂ and Z ₂ has an R ₇ -CO- group and the other. Represents a hydrogen atom and R ₇ represents a substituted or unsubstituted aromatic group. The broken line in the formula indicates that the double bond is an E-form, a Z-form, or a mixture thereof.)

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