JP2023139796A - Ultraviolet sensing member and ultraviolet sensing kit - Google Patents

Abstract

To provide an ultraviolet sensing member which exhibits a large difference in developed color density before and after ultraviolet irradiation and is less likely to develop color even after being stored for a certain period of time without ultraviolet irradiation.SOLUTION: An ultraviolet sensing member is provided, comprising a first layer containing a photoacid generator that generates acid when irradiated with ultraviolet light and a coloring agent, and a second layer containing a basic compound.SELECTED DRAWING: None

Description

The present invention relates to an ultraviolet sensing member and an ultraviolet sensing kit.

Measurement of ultraviolet irradiation amount is carried out in various fields. Specific examples include measurement of the amount of ultraviolet irradiation on an object to be irradiated in the curing reaction of an ultraviolet curing resin, and measurement of the amount of ultraviolet irradiation on an object to be irradiated in ultraviolet sterilization of foods and the like.
For example, Patent Document 1 discloses a photosensitive color-forming composition containing specific components.

Japanese Unexamined Patent Publication No. 161860/1986

Ultraviolet sensing members are required to be difficult to color even after being stored for a certain period of time without being irradiated with ultraviolet light (for example, light with a wavelength of 10 to 400 nm). For example, it is required that an ultraviolet sensing member using a coloring agent that develops a magenta color does not develop a magenta color or remains weakly colored even after being stored for a certain period of time without UV irradiation. There is.

It is also required that there be a large difference in color density before and after irradiation with ultraviolet rays.
For example, when using a coloring agent that develops a magenta color, the ultraviolet sensing member may not develop a magenta color before irradiation with ultraviolet rays, or it may be colored weakly (a state in which the coloring density is low), and it may become sufficiently magenta after irradiation with ultraviolet rays. By developing color (high color density), the difference in color density before and after UV irradiation becomes large. As described above, it is required that there be a large difference in color density between before and after irradiation with ultraviolet rays.
Note that the difference in color density includes not only a change in color density due to a change from a substantially colorless state to a colored state due to ultraviolet rays, but also a change in color density due to a change from a colored state to a colored state different from the above-mentioned colored state. It also includes variations in color density from a colored state to a substantially colorless state.

The present inventors investigated an ultraviolet sensing member using the member described in Patent Document 1, and found that the difference in color density before and after irradiation with ultraviolet rays, and the difference in color density for a certain period of time without irradiating ultraviolet rays There was room for improvement regarding the difficulty of coloring of the ultraviolet sensing member after storage.

In view of the above circumstances, the present invention aims to provide an ultraviolet sensing member that has a large difference in color density before and after irradiation with ultraviolet rays, and that is difficult to color even after being stored for a certain period of time without irradiating ultraviolet rays. Take it as a challenge.
Another object of the present invention is to provide an ultraviolet sensing kit.

As a result of intensive study to solve the above problem, the present inventors found that the problem could be solved by the configuration shown below, and completed the present invention.

[1]
An ultraviolet sensing member having a first layer and a second layer,
The first layer includes a photoacid generator that generates acid when exposed to ultraviolet light, and a coloring agent,
An ultraviolet sensing member, wherein the second layer contains a basic compound.
[2]
The ultraviolet sensing member according to [1], wherein the basic compound has a nitrogen atom.
[3]
The ultraviolet sensing member according to [1] or [2], wherein the basic compound contains a resin having a nitrogen atom.
[4]
The ultraviolet sensing member according to any one of [1] to [3], wherein the first layer does not contain a colorant that does not develop color due to the action of an acid, oxidation, or light irradiation.
[5]
The ultraviolet sensing member according to any one of [1] to [4], further comprising an intermediate layer between the first layer and the second layer.
[6]
The ultraviolet sensing member according to [5], wherein the intermediate layer contains a water-soluble resin.
[7]
The ultraviolet sensing member according to any one of [1] to [6], wherein the photoacid generator is a compound represented by formula (B1) described below.
[8]
The ultraviolet sensing member according to any one of [1] to [7], which is in the form of a sheet.
[9]
An ultraviolet sensing kit comprising the ultraviolet sensing member according to any one of [1] to [8].

According to the present invention, it is possible to provide an ultraviolet sensing member that has a large difference in color density before and after irradiation with ultraviolet rays, and is difficult to color even after being stored for a certain period of time without irradiating with ultraviolet rays.
Further, according to the present invention, an ultraviolet sensing kit can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the ultraviolet sensing member of the present invention.

The present invention will be explained in detail below.
Although the constituent elements of the present invention described below may be explained based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
As used herein, "solid content" refers to components forming composition layers (e.g., first layer, second layer, intermediate layer, etc.) formed using the composition; , first layer, second layer, intermediate layer, etc.) contains a solvent (for example, an organic solvent, water, etc.), it means all components excluding the solvent. In addition, liquid components are also considered solid components as long as they are components that form composition layers (for example, the first layer, second layer, intermediate layer, etc.).
As used herein, "ultraviolet light" means light with a wavelength in the range of 10 to 400 nm.
In this specification, "(meth)acrylic" means at least one of acrylic and methacryl.

[Ultraviolet sensing member]
The ultraviolet sensing member of the present invention is an ultraviolet sensing member having a first layer and a second layer, wherein the first layer is a photoacid generator (hereinafter simply referred to as "photoacid generator") that generates an acid by ultraviolet light. ) and a coloring agent, and the second layer contains a basic compound.

The ultraviolet sensing member of the present invention has a large difference in color density before and after irradiation with ultraviolet rays, and the ultraviolet sensing member is difficult to develop color even after being stored for a certain period of time without irradiation with ultraviolet rays (hereinafter referred to as "storage stability"). Although the detailed mechanism is not clear, the present inventors speculate as follows.
A feature of the present invention is that the ultraviolet sensing member has a second layer containing a basic compound.
For example, even if an ultraviolet sensing member is stored for a certain period of time without being irradiated with ultraviolet rays, acid is generated from the photoacid generator contained in the first layer, and the acid causes unintended color development. May be less stable. On the other hand, in the ultraviolet sensing member of the present invention, since the acid can be neutralized by the basic compound contained in the second layer, it is presumed that the storage stability of the ultraviolet sensing member is excellent.
Moreover, even if the ultraviolet sensing member has a second layer, the second layer does not easily inhibit color development of the ultraviolet sensing member, so it is presumed that the difference in color density before and after ultraviolet irradiation is large.
Hereinafter, the fact that at least one of the effects of a larger difference in color density before and after UV irradiation and better storage stability is obtained will also be referred to as "more excellent effects of the present invention."

Hereinafter, the main color estimation mechanism of the present invention will be explained in detail.
The photoacid generator absorbs ultraviolet light and is activated to generate acid, and the color former reacts with the generated acid, causing the structure of the color former to change as described below, and the color to change. Conceivable.
For example, the color former X having the following lactone structure can be a closed ring form that is substantially colorless and an open ring form that is colored, as shown in the scheme below. More specifically, in the color former X, the lactone structure is ring-opened by the action of acid (H ⁺ ) to become a ring-opened product, and the ring is closed by deacidification to become a ring-closed product. When an acid is supplied to the ring-closed form of color former X, the reaction from the closed-ring form to the open-ring form proceeds, and the reaction from the open-ring form to the closed-ring form also proceeds. That is, the reaction from the closed ring form to the open ring form and the reaction from the open ring form to the closed ring form proceed reversibly. In other words, when acid (H ⁺ ) is generated from the photoacid generator by irradiation with ultraviolet rays, the equilibrium between the reaction from the closed ring form to the open ring form and the reaction from the open ring form to the closed ring form changes from the closed ring form to the closed ring form. The color forming agent develops color by biasing the reaction toward the open ring form.

Examples of the shape of the ultraviolet sensing member include various shapes such as a sheet shape and a block shape such as a rectangular parallelepiped and a cylindrical shape, with a sheet shape being preferred. In other words, a sheet-like ultraviolet sensing member (ultraviolet sensing sheet) can be suitably used.
The shape of the sheet-like ultraviolet sensing member includes, for example, various shapes such as square, rectangle, circle, ellipse, and polygons other than quadrangles such as hexagons, as well as irregular shapes. Further, the sheet-like ultraviolet sensing member may be elongated.
The ultraviolet sensing member may have other members in addition to the first layer, second layer, intermediate layer, and support described below. When the ultraviolet sensing member has other members, the ultraviolet sensing member may be bonded to the other member via an adhesive layer (e.g., adhesive, adhesive, etc.), or it may be manufactured as a part of the other member. It's okay. Other members include, for example, business cards, name tags, masks, cloth products (for example, shirts, etc.), cases (for example, smartphone cases, etc.), and paper products (for example, notebooks, calendars, etc.).

When the first layer included in the ultraviolet sensing member is irradiated with ultraviolet rays when measuring the amount of ultraviolet irradiation, the amount of ultraviolet irradiation (for example, integrated illuminance, etc.) changes in the area that has been irradiated with ultraviolet rays (the area that is irradiated with ultraviolet rays). The color density changes accordingly.

FIG. 1 is a schematic cross-sectional view of an example of an ultraviolet sensing member.
The ultraviolet sensing member 10 has a support 12, a second layer 14, and a first layer 16 in this order. The order of the support 12, the second layer 14, and the first layer 16 is not limited to the order shown in FIG. You may do so. The first layer 16 includes a photoacid generator and a coloring agent. The second layer 14 contains a basic compound. In the first layer 16 that has been irradiated with ultraviolet rays, a colored portion (not shown) is formed with a color density that corresponds to the amount of ultraviolet irradiation.
As described above, although FIG. 1 shows an embodiment in which the ultraviolet sensing member is in the form of a sheet, the present invention is not limited to this embodiment.

Note that, as described later, the ultraviolet sensing member 10 only needs to have the first layer 16 and the second layer 14, and does not need to have the support 12.
Further, the ultraviolet sensing member 10 shown in FIG. 1 has a three-layer structure including a support 12, a first layer 16, and a second layer 14, but the structure is not limited to this, and as described later, the support 12, It may have layers other than the first layer 16 and the second layer 14 (for example, an intermediate layer, a reflective layer, a glossy layer, a filter layer, etc.).
The ultraviolet sensing member preferably has a support, a second layer, and a first layer in this order, and more preferably has a support, a second layer, an intermediate layer, and a first layer in this order.

The thickness of the ultraviolet sensing member is preferably 5 μm to 1 cm, more preferably 25 μm to 2 mm.

Each member that the ultraviolet sensing member may have will be described in detail below.

[First layer]
The ultraviolet light sensing member has a first layer.
The first layer includes a photoacid generator and a color former.
Hereinafter, various components that can be included in the first layer will be explained in detail.

<Photoacid generator that generates acid by ultraviolet rays>
A photoacid generator is a compound that generates acid when exposed to ultraviolet light.
It is also preferable that the acid generated from the photoacid generator activated by ultraviolet rays acts on the color former, which will be described later, to cause the color former to develop color.

Examples of the photoacid generator include nonionic photoacid generators and ionic photoacid generators, with nonionic photoacid generators being preferred. Examples of the nonionic photoacid generator include organic halogen compounds and oxime compounds, with organic halogen compounds being preferred and compounds represented by formula (B1) being more preferred.
The number of halogen atoms contained in the organic halogen compound is preferably three or more. The upper limit is preferably 9 or less, more preferably 5 or less.
Examples of the halogen atom contained in the organic halogen compound include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred.

Examples of acids generated by the photoacid generator include hydrogen halides, inorganic acids such as sulfuric acid and nitric acid, and organic acids such as carboxylic acids and sulfonic acids. Inorganic acids are preferred, and hydrogen halides are more preferred. Preferably, HF, HCl, HBr or HI are more preferable, with HBr being particularly preferable.

The photoacid generator is preferably a compound represented by formula (B1) or a compound represented by formula (B2), and more preferably a compound represented by formula (B1).

In formula (B1), R ^b1 represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. L ^b represents -CO-, -CO ₂ -, -SO- or -SO ₂ -. X ^b1 to X ^b3 each independently represent a hydrogen atom or a halogen atom. However, the case where all of X ^b1 to X ^b3 are hydrogen atoms is excluded.

In formula (B1), R ^b1 represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 14, even more preferably 6 to 10.
The number of carbon atoms in the above heteroaryl is preferably 4 to 20, more preferably 4 to 13, even more preferably 4 to 9.
Examples of the substituents that the aryl group and the heteroaryl group may have include a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an acetyl group, a haloacetyl group, and a carbon Examples include 1 to 3 alkoxy groups.
As R ^b1 , an aryl group which may have a substituent is preferable, and a benzene ring group is more preferable.

In formula (B1), L ^b represents -CO-, -CO ₂ -, -SO- or -SO ₂ -.
L ^b is preferably -CO-, -SO- or -SO ₂ -, more preferably -SO ₂ -.
The bonding direction of the divalent groups described herein is not limited unless otherwise specified. For example, when Y in the compound represented by the formula "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO- Good too. Further, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".

In formula (B1), X ^b1 to X ^b3 each independently represent a hydrogen atom or a halogen atom. However, the case where all of X ^b1 to X ^b3 are hydrogen atoms is excluded.
Examples of X ^b1 to X ^b3 include fluorine atom, chlorine atom, bromine atom, and iodine atom, preferably chlorine atom, bromine atom, or iodine atom, and more preferably bromine atom.

Examples of the compound represented by formula (B1) include tribromomethylphenylsulfone (BMPS), trichloromethylphenylsulfone (CMPS), trichloro-p-chlorophenylsulfone, tribromomethyl-p-nitrophenylsulfone, 2- Trichloromethylbenzothiazolesulfone, 4,6-dimethylpyrimidine-2-tribromomethylsulfone, 2,4-dichlorophenyl-trichloromethylsulfone, 2-methyl-4-chlorophenyltrichloromethylsulfone, 2,5-dimethyl-4- Chlorophenyltrichloromethylsulfone, 2,4-dichlorophenyltrimethylsulfone, tri-p-tolylsulfonium trifluoromethanesulfonate, o-nitro-α,α,α-tribromoacetophenone, m-nitro-α,α,α-tribromo Examples include acetophenone, p-nitro-α,α,α-tribromoacetophenone, α,α,α-tribromoacetophenone and α,α,α-tribromo-3,4-cycloacetophenone, including tribromomethylphenylsulfone. (BMPS) is preferred.

In formula (B2), R ^b2 represents a heteroaryl group which may have a substituent. X ^b4 to X ^b6 each independently represent a hydrogen atom or a halogen atom. However, the case where all of X ^b4 to X ^b6 are hydrogen atoms is excluded.

The number of carbon atoms in the heteroaryl group is preferably 4 to 20, more preferably 4 to 13, even more preferably 4 to 9.
As the above-mentioned heteroaryl group, a triazine group which may have a substituent is preferable.
Examples of substituents that the heteroaryl group may have include a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an acetyl group, a haloacetyl group, and a haloacetyl group having 1 to 3 carbon atoms. Examples include alkoxy groups.
Examples ^of the halogen atom represented by any of X ^b4 to is more preferable.

Examples of the compound represented by formula (B2) include 2,4,6-tris(trichloromethyl)-1,3,5-triazine and 2-methyl-4,6-bis(trichloromethyl)-1, 3,5-triazine is mentioned.

Examples of the ionic photoacid generator include diazonium salt compounds, iodonium salt compounds, and sulfonium salt compounds, with sulfonium salt compounds and iodonium salt compounds being preferred.
Examples of ionic photoacid generators include compounds described in JP-A-62-161860, JP-A-61-067034, and JP-A-62-050382, the content of which is incorporated herein by reference. Incorporated into the specification.

The molecular weight of the photoacid generator is preferably 100 to 2,000, more preferably 150 to 1,500, even more preferably 200 to 1,000.

The photoacid generators may be used alone or in combination of two or more.
The content of the photoacid generator is preferably 0.005 to 5.000 g/m ² , more preferably 0.010 to 2.000 g/m 2 , and more preferably 0.040 to 0.04 g/m ² per unit area of the first layer. More preferably 500g/ ^m2 .
The content of the photoacid generator can be measured, for example, by the following method.
It can be calculated by cutting out the first layer from the ultraviolet sensing member, immersing the first layer in methanol for two days, and then analyzing the obtained methanol using liquid chromatography. Note that methanol should not be volatilized while the first layer is being immersed. Note that a calibration curve for the content of the photoacid generator to be detected is created under the same measurement conditions as in the liquid chromatography measurement. The measurement conditions for liquid chromatography are as follows.
Device: Nexera (manufactured by Shimadzu Corporation)
Column: Capcell pak C18 UG-120
Eluent: Water/methanol Oven: 40℃
Injection: 5μL
Detection: Maximum absorption wavelength of the object to be measured Flow rate: 0.2mL/min

<Coloring agent>
The first layer contains a color former.
"Coloring" in "coloring agent" is a concept that includes both coloring and discoloration. "Coloring" means changing from a substantially colorless state (colorless or weakly colored state) to coloration due to the action of an acid, oxidation, light irradiation, etc. In addition, "discoloration" refers to a change in color from a specific color to another color or substantially colorless (colorless or weakly colored state) due to the action of acids, oxidation, light irradiation, etc. (for example, change from yellow to red).
It is preferable that the coloring agent develops color by the action of an acid.
The acid that acts on the coloring agent to develop color may be an acid generated from a photoacid generator, or may be an acid other than the acid generated from a photoacid generator.

Whether or not a coloring agent develops color due to the action of an acid can be determined, for example, by the following method.
The first layer before irradiation with ultraviolet rays is cut out from the ultraviolet sensing member, and the first layer is immersed in methanol for two days to obtain a methanol solution A in which the color former is extracted. Thereafter, methanol solution A is analyzed using liquid chromatography (Analysis 1). Note that while the first layer is immersed in methanol, a lid or the like is provided to prevent methanol from volatilizing.
On the other hand, 0.01 mol/L (1N) hydrochloric acid is added to methanol solution A to adjust the pH to 1, and the solution is analyzed using liquid chromatography in the same manner as Analysis 1 (Analysis 2).
Compare the data obtained in analysis 1 (maximum absorption wavelength) with the data obtained in analysis 2 (maximum absorption wavelength), check whether the maximum absorption wavelength has changed, and if so, the acid means that it is colored. It is preferable that the maximum absorption wavelength changes by 10 nm or more. Moreover, the color often changes visually between before and after adjusting the pH to 1 by adding 0.01 mol/L (1N) hydrochloric acid.
The measurement conditions for liquid chromatography are as follows.
Device: Nexera (manufactured by Shimadzu Corporation)
Column: Capcell pak C18 UG-120
Eluent: Water/methanol Oven: 40℃
Injection: 5μL
Flow rate: 0.2mL/min

The color former preferably has at least one selected from the group consisting of a lactone structure, a lactam structure, a sultone structure, a sultine structure and their ring-opened structures, and an azobenzene structure; It is more preferable to have at least one selected from the group consisting of phthalide structure and its ring-opened structure.
The photoacid generator is often oil-soluble, and it is preferable that the color former is also oil-soluble because the color former and the photo acid generator are likely to mix and react.

If isomers (eg, structural isomers, stereoisomers, etc.) exist in the compounds disclosed herein, the above compounds include those isomers, unless otherwise specified.

As the color former, leuco dyes are preferred.
Examples of leuco dyes include triarylmethane phthalide compounds having a triarylmethane structure and a phthalide structure, fluoran compounds having a xanthene structure and a phthalide structure, indolyl phthalide compounds having an indolyl structure and a phthalide structure, and azaindolyl. Examples include azaindolyl phthalide compounds having a structure and a phthalide structure, and rhodamine lactam compounds having a xanthene structure and a lactam structure.
As the coloring agent, a fluoran compound or an indolylphthalide compound is preferable, and a fluoran compound is more preferable.

As the coloring agent, a compound represented by formula (C1) or a compound represented by formula (C2) is preferable, and a compound represented by formula (C3) is more preferable.

In formula (C1), X ^c1 represents an oxygen atom, a sulfur atom, or -NR ^c1 -. R ^c1 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R represents a hydrogen atom or a substituent. A plurality of R's may be the same or different.
In formula (C2), R ^c2 to R ^c5 each independently represent a hydrogen atom or an alkyl group which may have a substituent.

In formula (C1), X ^c1 represents an oxygen atom, a sulfur atom, or -NR ^c1 -. R ^c1 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
Examples of the alkyl group which may have a substituent represented by R ^c1 or the aryl group which may have a substituent represented by R c1 include those having a substituent represented by either R ^a2 or R ^a3 . Examples include an optionally substituted alkyl group or an optionally substituted aryl group.
As X ^c1 , an oxygen atom is preferable.

In formula (C1), R represents a hydrogen atom or a substituent. When a plurality of R's exist, the R's may be the same or different.
Examples of the above-mentioned substituents include an optionally substituted amino group, nitro group, halogen atom, alkyl group having 1 to 3 carbon atoms, haloalkyl group having 1 to 3 carbon atoms, acetyl group, haloacetyl group, and Examples include an alkoxy group having 1 to 3 carbon atoms, preferably an amino group which may have a substituent, and a secondary amino group which may have a substituent or a substituent. A tertiary amino group is more preferred.
Examples of substituents that the amino group may have include an alkyl group and an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 10. The number of carbon atoms in the aryl group is preferably 6 to 10.
It is preferable that at least one of R represents an amino group that may have a substituent, and it is more preferable that at least two of R represent an amino group that may have a substituent. , R represents an optionally substituted amino group, and the remaining R represents a hydrogen atom.

In formula (C2), R ^c2 to R ^c5 each independently represent a hydrogen atom or an alkyl group which may have a substituent.
The alkyl group may be linear, branched, or cyclic, and preferably linear or branched.
The alkyl group which may have a substituent represented by R ^c2 and R ^c3 is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent. An alkyl group having 1 to 3 carbon atoms is more preferred.
The alkyl group which may have a substituent represented by R ^c4 and R ^c5 is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. An alkyl group having 5 to 10 carbon atoms is more preferred.
Examples of substituents that the alkyl group may have include a halogen atom and an aryl group.
It is also preferable that the alkyl group has no substituent.
It is preferable that R ^c2 and R ^c3 represent the same group. Moreover, it is preferable that R ^c4 and R ^c5 represent the same group.

In formula (C3), R ^c6 and R ^c7 each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. R ^c8 and R ^c9 each independently represent an alkyl group that may have a substituent or an aryl group that may have a substituent.

Examples of the alkyl group which may have a substituent represented by any of R ^c6 to R ^c9 or the aryl group which may have a substituent are, for example, those represented by any of R ^a2 and R ^a3 . Examples include an alkyl group which may have a substituent or an aryl group which may have a substituent.

Examples of coloring agents include 3,3-bis(2-methyl-1-octyl-3-indolyl)phthalide, 6'-(dibutylamino)-2'-bromo-3'-methylspiro[phthalide-3,9 '-xanthene], 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylamino-2-ethoxyphenyl) )-3-(1-n-octyl-2-methylindol-3-yl)phthalide, 3-[2,2-bis(1-ethyl-2-methylindol-3-yl)vinyl]-3-( 4-diethylaminophenyl)-phthalide, 2-anilino-6-dibutylamino-3-methylfluoran, 6-diethylamino-3-methyl-2-(2,6-xylidino)-fluoran, 2-(2-chloroanilino) -6-dibutylaminofluorane, 2-anilino-6-diethylamino-3-methylfluorane, 9-[ethyl(3-methylbutyl)amino]spiro[12H-benzo[a]xanthene-12,1'(3') H) isobenzofuran]-3'-one, 2'-methyl-6'-(N-p-tolyl-N-ethylamino)spiro[isobenzofuran-1(3H),9'-[9H]xanthene]- 3-one, 3',6'-bis(diethylamino)-2-(4-nitrophenyl)spiro[isoindole-1,9'-xanthene]-3-one, 9-(N-ethyl-N-iso pentylamino) spiro[benzo[a]xanthene-12,3'-phthalide], 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9' -[9H]xanthene] and 6'-(diethylamino)-1',3'-dimethylfluorane.

The maximum absorption wavelength of the coloring agent may be in the wavelength range of 10 to 400 nm, preferably in the wavelength range of 200 to 350 nm, and more preferably in the wavelength range of 200 to 300 nm.

The molecular weight of the coloring agent is preferably 300 or more, more preferably 500 or more. The upper limit is preferably 2000 or less, more preferably 1000 or less.

From the viewpoint of visibility, the color developed by the coloring agent is preferably red (for example, red, magenta, orange, etc.). Specifically, a ^* in L ^* a ^* b ^* standardized by the CIE color system is preferably greater than 0. L ^* a ^* b ^* can be measured using a spectrophotometer X-Lite (manufactured by X-Lite) in accordance with JIS Z 8781-4:2013.

The color formers may be used alone or in combination of two or more.
The content of the color former is preferably 0.0010 to 1.0000 g/m ² , more preferably 0.0020 to 0.5000 g/m ² , and 0.0040 to 0.1000 g/m 2 per unit area of the first layer. m ² is more preferred.
The content of the coloring agent can be measured by the same method as the method for measuring the content of the photoacid generator.

The molar ratio of the content of photoacid generator B to the content of color former may be 100.0 or less, preferably 70.0 or less, more preferably 1.0 to 70.0, and 5.0. ~70.0 is more preferred.
Note that the above molar ratio can be measured by the same method as the method for measuring the content of photoacid generator B.

<Binder>
The first layer may include a binder.
The binder may be either a water-soluble resin or an oil-soluble resin, and an oil-soluble resin is preferred. "Water-soluble" in water-soluble resin means that the amount of the target substance dissolved in 100 g of water at 25° C. is 5 g or more, and oil-soluble resin means resins other than water-soluble resins.
Examples of the binder include cellulose resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, and hydroxypropylcellulose, polyvinyl alcohol, polyvinyl butyral, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer. , (meth)acrylic resin, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride and ethylene-vinyl acetate Examples include copolymers.
Examples of the binder include the binder described in paragraph 0078 of Japanese Patent Application Publication No. 2017-167155, the contents of which are incorporated herein.
As the binder, a resin having substantially no aromatic ring group is preferable, and an acrylic resin having no aromatic ring group is more preferable, since it can develop color with a low exposure amount to light having a wavelength of 222 nm. "Substantially free of aromatic ring groups" means that the content of aromatic ring groups is 0 to 1% by mass based on the total mass of the binder. The content of the aromatic ring group is preferably 0 to 0.1% by mass based on the total mass of the binder.
As the binder, a resin having a hydroxyl group is also preferable.

The lower the acid value of the binder, the better the storage stability. Specifically, 0 to 50 mgKOH/g is preferable, and 0 to 20 mgKOH/g is more preferable.
Further, the binder may have a crosslinked structure using a crosslinking agent.

The binder may be used alone or in combination of two or more.
The binder content is preferably 0.10 to 20.00 g/m ² , more preferably 0.50 to 10.00 g/m 2 , and 1.00 to 5.00 g/m ² per unit area of the first layer. ² is more preferred.

<Light stabilizer>
The first layer may include a light stabilizer.
The light stabilizer may be any material as long as it is stabilized by light, and preferably acts as a so-called free radical trapping substance that traps the free radicals of the photoacid generator activated by ultraviolet light.
Examples of light stabilizers include polyhydric phenols such as 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, hydroquinone, catechol, resorcinol, and hydroxyhydroquinone, and o-aminophenol and Examples include aminophenols such as p-aminephenol.
The light stabilizers may be used alone or in combination of two or more.

<Ultraviolet absorber>
The first layer may include a UV absorber.
Examples of the ultraviolet absorber include benzotriazole compounds having a benzotriazole structure, benzophenone compounds, triazine compounds, and benzodithiol compounds.
It is preferable that the ultraviolet absorber has low absorption of light with a wavelength of 222 nm, since the sensitivity to light with a wavelength of 222 nm is better. As the ultraviolet absorber, a triazine compound, a benzophenone compound or a benzodithiol compound is preferred.

Further, it is preferable that the first layer does not contain a benzotriazole compound that has a large absorption of light at a wavelength of 222 nm. When the first layer contains a benzotriazole compound, the content of the benzotriazole compound is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total mass of the photoacid generator. The lower limit may be 0.0001% by mass or more based on the total mass of the photoacid generator. Further, the content of the benzotriazole compound is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total mass of the color former. The lower limit may be 0.0001% by mass or more based on the total mass of the color former.

Examples of triazine compounds include ADEKA STAB LA-F70 (manufactured by ADEKA), Tinuvin 1577 ED, Tinuvin 1600 (manufactured by BASF), 2,4-Bis(2,4-dimethylphenyl)-6-(2-hydroxy-4 -n-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-Dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine and Ethylhexyl Triazine (manufactured by Tokyo Kasei Co., Ltd.). .
Examples of the benzophenone compound include Chimassorb 81 and Chimassorb 81 FL (manufactured by BASF).
Examples of the benzodithiol compound include compounds described in International Publication No. 2019/159570.
The ultraviolet absorbers may be used alone or in combination of two or more.

<Surfactant>
The first layer may include a surfactant.
The surfactant is a component different from the binder that may be included in the first layer described above.
Examples of the surfactant include fluorine surfactants, anionic surfactants, and nonionic surfactants.
Examples of the fluorine-based surfactant include (meth)acrylic resins having an alkyl group having a fluorine atom.
Examples of anionic surfactants and nonionic surfactants include alkylbenzenesulfonates (e.g., sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate, etc.), alkylsulfonates (e.g., sodium lauryl sulfate, sulfosuccinic acid, etc.) dioctyl sodium, etc.) and polyalkylene glycols (eg, polyoxyethylene nonylphenyl ether, etc.).

The surfactants may be used alone or in combination of two or more.
The content of the surfactant may be 0.0001 g/m ² or more, more preferably 0.0005 to 0.005 g/m ² per unit area of the first layer.

<Other ingredients>
The first layer may contain other components in addition to the various components that may be included in the first layer described above.
Other ingredients include, for example, wax and odor suppressants.

It is also preferable that the first layer does not contain any coloring agent other than the coloring agent mentioned above. In other words, it is preferable not to contain a coloring agent that does not develop color due to the action of acid, oxidation, or light irradiation.
Examples of the coloring agent include pigments. Examples of the pigment include inorganic particles such as the yellow pigment and white pigment described in paragraphs 0018 to 0022 of International Publication No. 2016/017701.

The thickness of the first layer is preferably 0.5 to 10.0 μm, more preferably 1.0 to 5.0 μm.
The above-mentioned thickness is an arithmetic average value obtained by observing ten arbitrary points in the cross section of the ultraviolet sensing member using an electron microscope and measuring the thickness.

<Method for forming the first layer>
As a method for forming the first layer, a known method may be used.
For example, a method may be used in which the composition for forming the first layer is applied onto a support to form a coating film, and if necessary, the coating film is subjected to a drying treatment.
The composition for forming the first layer preferably contains various components that the first layer may contain and a solvent.
Examples of the solvent include ethyl acetate, isopropyl acetate, methyl ethyl ketone, and methylene chloride.

Examples of the method for applying the first layer forming composition include a method of applying using a coating machine. Examples of the coating machine include an air knife coater, a rod coater, a bar coater, a curtain coater, a gravure coater, an extrusion coater, a die coater, a slide bead coater, and a blade coater.

After coating the first layer forming composition on the support, the coating film may be subjected to a drying treatment, if necessary. Examples of the drying treatment include blowing treatment and heating treatment.

Alternatively, the first layer may be manufactured by forming the first layer on a temporary support and peeling off the temporary support.
Examples of the temporary support include a removable support.

[Second layer]
The ultraviolet sensing member has a second layer.
The second layer contains a basic compound.

<Basic compound>
The basic compound may be either a resin (high molecular compound) or a low molecular compound.
When the basic compound is a resin, the weight average molecular weight of the resin is preferably more than 2,000 and 2,000,000 or less, more preferably 5,000 to 1,000,000, and even more preferably 10,000 to 500,000.
The above weight average molecular weight is a value calculated using polystyrene as a standard substance measured by a gel permeation chromatography (GPC) analyzer.
When the basic compound is a low molecular compound, the molecular weight of the low molecular compound is preferably 150 to 2,000, more preferably 200 to 1,500, and even more preferably 300 to 1,000.
It is preferable that the basic compound has a nitrogen atom. Moreover, it is also preferable that the basic compound contains a resin having a nitrogen atom, and it is more preferable that the basic compound is a resin having a nitrogen atom.

Examples of the basic compound include basic inorganic compounds and basic organic compounds, with basic organic compounds being preferred.
Examples of basic organic compounds include guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and their like. Examples include derivatives and basic resins such as polyvinylpyridine and polyethyleneimine.
The basic compound preferably contains a basic tree species, more preferably contains a resin having a nitrogen atom, and still more preferably contains at least one selected from the group consisting of polyvinylpyridine and polyethyleneimine.

The basic compounds may be used alone or in combination of two or more.
The content of the basic compound is preferably 0.01 to 20.00 g/m ² , more preferably 0.05 to 10.00 g/m ² , and 0.10 to 5.00 g per unit area of the second layer. /m ² is more preferred.
When the basic compound is a low molecular weight compound, the content of the basic compound can be measured by the same method as the method for measuring the content of the photoacid generator.
When the basic compound is a resin (polymer compound), the content of the basic compound is determined by HPLC (high performance liquid chromatography), pyrolysis GC/MS (pyrolysis gas chromatography/mass spectrometry), and NMR (nuclear The measurement can be performed by combining known measurement methods such as magnetic resonance).

<Surfactant>
The second layer may include a surfactant.
Examples of the surfactant include surfactants that the first layer may have.

<Other ingredients>
The second layer may contain other components in addition to the various components that may be included in the second layer described above.
Examples of other components include various components that the first layer may have.

The thickness of the second layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5.0 μm.
The above thickness can be measured in the same manner as for the first layer.

<Method for forming second layer>
As a method for forming the second layer, a known method may be used.
Examples of the method for forming the second layer include a method in which a composition for forming the second layer is applied onto a support to form a coating film, and if necessary, the coating film is subjected to a drying treatment. .
Examples of the coating method and drying method include the coating method and drying method of the first layer forming method.
The composition for forming the second layer preferably contains various components that the second layer may contain and a solvent.
Examples of the solvent include ethanol, methanol, and isopropyl alcohol.

[Middle layer]
The UV sensing member may have an intermediate layer.
Preferably, the ultraviolet sensing member further includes an intermediate layer between the first layer and the second layer. That is, it is preferable that the ultraviolet sensing member has a first layer, an intermediate layer, and a second layer in this order.
When the ultraviolet sensing member has an intermediate layer, it may be possible to prevent the basic compound (especially the basic compound of a low molecular weight compound) in the second layer from diffusing into the first layer and inhibiting color development of the color former.

<Water-soluble resin>
The intermediate layer may contain a water-soluble resin.
It is preferable that the water-soluble resin has a hydroxyl group.
Examples of water-soluble resins include cellulose resins such as methylcellulose, ethylcellulose, carboxymethylcellulose, and hydroxypropylcellulose, polyvinyl alcohol, polyvinyl butyral, gum arabic, gelatin, polyvinylpyrrolidone, and casein, with polyvinyl alcohol being preferred. The resin may be a resin in which a part of the chemical structure of the resin is modified.

The water-soluble resins may be used alone or in combination of two or more.
The content of the water-soluble resin is preferably 0.01 to 10.00 g/m ² , more preferably 0.05 to 5.00 g/m 2 , and 0.10 to 2.00 g/m ² per unit area of the intermediate layer. m ² is more preferred.

<Other ingredients>
The intermediate layer may contain other components in addition to the various components that can be included in the intermediate layer described above.
Examples of other components include various components that the first layer may have and other components.

The thickness of the intermediate layer is preferably 0.1 to 5.0 μm, more preferably 0.2 to 2.0 μm, and even more preferably 0.2 to 1.0 μm.
The above thickness can be measured in the same manner as for the first layer.

<Method for forming intermediate layer>
Known methods can be used to form the intermediate layer.
Examples of the method for forming the intermediate layer include a method in which a composition for forming an intermediate layer is applied onto a support to form a coating film, and if necessary, the coating film is subjected to a drying treatment.
Examples of the coating method and drying method include the coating method and drying method of the first layer forming method.
The composition for forming an intermediate layer preferably contains various components that the intermediate layer may contain and a solvent.
Examples of the solvent include water, isopropyl alcohol, methanol, and ethanol.

[Support]
The ultraviolet sensing member may have a support.
The support is a member for supporting the first layer and the second layer.
If the first and second layers themselves can be handled, the ultraviolet sensing member may not have a support.

Examples of the support include resin sheets, paper (including synthetic paper), cloth (including woven fabrics and non-woven fabrics), glass, wood, and metal. The support is preferably a resin sheet or paper, more preferably a resin sheet or synthetic paper, and even more preferably a resin sheet.
Materials for the resin sheet include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride resin, fluororesin, and poly(meth)acrylic. Resin, polycarbonate resin, polyester resin (for example, polyethylene terephthalate and polyethylene naphthalate), polyamide resin such as nylon, polyimide resin, polyamideimide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone Examples include resins, polyurethane resins, acetal resins, and cellulose resins.
Examples of synthetic paper include, for example, synthetic paper made from biaxially stretched polypropylene or polyethylene terephthalate to form a large number of microvoids (for example, Yupo, etc.); synthetic paper made using synthetic fibers such as polyethylene, polypropylene, polyethylene terephthalate, and polyamide; Paper: Examples include synthetic paper in which these are laminated on a portion of paper, on one side, or on both sides.

Further, another suitable embodiment of the resin sheet includes, for example, a white resin sheet in which a white pigment is dispersed in a resin. Examples of the resin material in the white resin sheet include the same materials as the resin sheet described above.
The white resin sheet has ultraviolet reflective properties. Therefore, when the support is a white resin sheet, the ultraviolet rays irradiated onto the ultraviolet sensing member are reflected by the support, so that scattering of the ultraviolet rays inside the ultraviolet sensing member can be suppressed. As a result, the detection accuracy of the amount of ultraviolet rays irradiated by the ultraviolet sensing member can be further improved.

Examples of the white pigment include the white pigment described in paragraph 0080 of International Publication No. 2016/017701, the contents of which are incorporated herein.
As the white resin sheet, a white polyester sheet is preferred, and a white polyethylene terephthalate sheet is more preferred.
Examples of commercially available white resin sheets include Yupo (manufactured by Yupo Corporation), Lumirror (manufactured by Toray Industries, Inc.), and Crisper (for example, Crisper K1212, manufactured by Toyobo).

The thickness of the support is preferably 5 μm or more, more preferably 25 μm or more, and even more preferably 50 μm or more. The upper limit is preferably 1 cm or less, more preferably 2 mm or less, and even more preferably 500 μm or less.
The above thickness can be measured in the same manner as for the first layer.

[Other layers]
The ultraviolet sensing member may have other layers in addition to the above-mentioned layers and the support.
Examples of other layers include a reflective layer, a glossy layer, a filter layer, and a sensitivity adjustment layer.

<Reflection layer>
The ultraviolet sensing member may have a reflective layer.
When the ultraviolet sensing member has a reflective layer, the ultraviolet rays irradiated on the ultraviolet sensing member can be reflected by the ultraviolet reflective layer, which suppresses the scattering of the ultraviolet rays inside the ultraviolet sensing member and improves the detection accuracy of the amount of ultraviolet irradiation. can be further improved.
The reflectance of the reflective layer for light with a wavelength of 180 to 300 nm is preferably 10 to 100%, more preferably 50 to 100%. The reflectance can be measured, for example, by diffuse reflection measurement using an ultraviolet-visible spectrophotometer (UV-2700, manufactured by Shimadzu Corporation).
Note that when the support is disposed adjacent to the reflective layer, an adhesion layer may be provided between the support and the reflective layer.
Examples of the reflective layer and adhesion layer and their manufacturing method include the reflective layer and adhesive layer and their manufacturing method described in paragraphs 0082 to 0091 of International Publication No. 2016/017701, and these The contents are incorporated herein.

<Glossy layer>
The UV sensing member may have a glossy layer.
When the ultraviolet sensing member has a glossy layer, visibility of the front and back sides can be improved.
Examples of the glossy layer and its manufacturing method include the glossy layer and its manufacturing method described in paragraphs 0092 to 0094 of International Publication No. 2016/017701, the contents of which are incorporated herein.

<Filter layer>
The ultraviolet sensing member may have a filter layer.
The filter layer is a layer that selectively transmits light of a certain arbitrary wavelength (hereinafter also referred to as "predetermined wavelength"). Selectively transmitting light of a predetermined wavelength means transmitting light of a predetermined wavelength and blocking light of other wavelengths. The predetermined wavelength can be adjusted as appropriate depending on the intended use of the ultraviolet sensing member. The transmittance of light having a wavelength to be transmitted is preferably 70 to 100%, more preferably 80 to 100%, and even more preferably 90 to 100%. The transmittance of light having a wavelength to be blocked is preferably 0 to 30%, more preferably 0 to 20%, and even more preferably 0 to 10%.
Ultraviolet bandpass filters and/or filters containing dielectrics are preferred.
The spectral characteristics of the filter layer and the sensitivity adjustment layer described below can be measured using, for example, an ultraviolet-visible spectrophotometer (UV-2700, manufactured by Shimadzu Corporation).
Preferably, the filter layer contains an ultraviolet absorber. Examples of the ultraviolet absorber include known ultraviolet absorbers.

Examples of the filter layer and its manufacturing method include the filter layer and its manufacturing method described in paragraphs 0016 to 0026 of International Publication No. 2016/017701, the contents of which are incorporated herein.

<Sensitivity adjustment layer>
When the ultraviolet sensing member has a filter layer, the ultraviolet sensing member may have a sensitivity adjustment layer on the surface of the filter layer.
Examples of the sensitivity adjustment layer and its manufacturing method include the sensitivity adjustment layer and its manufacturing method described in paragraphs 0095 to 0109 of International Publication No. 2016/017701, the contents of which are incorporated herein.

[Ultraviolet ray detection kit]
The present invention also relates to a UV sensing kit comprising the UV sensing member described above.
The ultraviolet sensing kit includes at least the ultraviolet sensing member described above.
The ultraviolet sensing kit includes, for example, an ultraviolet sensing member and a member having a filter layer that selectively transmits light with a predetermined wavelength (preferably a filter sheet that blocks light with a wavelength of 400 nm or more, more preferably a filter sheet with a wavelength of 300 nm or more). From the group consisting of a filter sheet that blocks light), a light-blocking bag (UV-blocking bag), a judgment sample, a limit sample (calibration sheet), a light-concentrating jig such as a lens and a concave mirror, and a holding member that holds a UV-sensing member. and other selected elements.
Note that the holding member may have an opening through which the held ultraviolet sensing member is irradiated with ultraviolet rays, or the holding member and the judgment sample may be integrated.

EXAMPLES The features of the present invention will be explained in more detail with reference to Examples and Comparative Examples below. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Hereinafter, "%" and "part" are based on mass unless otherwise specified.
In addition, all processes from the preparation process of the first layer forming composition, the second layer forming composition, and the intermediate layer forming composition to various evaluations are carried out under a yellow light environment to avoid irradiation with ultraviolet rays. It was carried out in

[Various ingredients]
The various components used to produce the ultraviolet sensing member are shown.

[Binder]
・Binder 1: Polymethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, Dianal BR80)

[Photoacid generator]
・Photoacid generator 1: Tribromomethylphenylsulfone, manufactured by Sumitomo Seika Co., Ltd.

[Coloring agent]
Color former 1: Rhodamine B base, manufactured by Sigma-Aldrich Color former 1 corresponds to a color former that develops color under the action of acid, and exhibits a magenta color under the action of acid.

[Surfactant]
- Surfactant 1: The following compound In the following compound, the unit of the proportion of each repeating unit is a molar ratio, and t-Bu means a tert-butyl group.

[Basic compound]
・Basic resin 1: Polyvinylpyridine (product name "Poly(4-vinylpyridine)", manufactured by Sigma-Aldrich)
・Basic resin 2: Polyethyleneimine (product name "Polyethyleneimine", branched, M.W. 70,000, 30% w/vaq.soln., manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[Water-soluble resin]
・Water-soluble resin 1: modified polyvinyl alcohol (water-soluble resin, manufactured by Kuraray Co., Ltd., Kuraray Excelval AQ-4105, saponification degree 98-99 mol%)

[Support]
・Support 1: White polyethylene terephthalate sheet (trade name "CRISPR K1212", thickness 188 μm, manufactured by Toyobo Co., Ltd.)

[Example 1]
The ultraviolet sensing member of Example 1 was produced according to the following procedure.

[Preparation of various compositions]
(1) Preparation of composition for forming first layer The composition shown below was mixed to prepare composition 1 for forming first layer.
――――――――――――――――――――――――――――
Composition of first layer forming composition 1――――――――――――――――――――――――――
・Binder 1 88.8 parts by mass ・Photoacid generator 1 10.8 parts by mass ・Coloring agent 1 0.30 parts by mass ・Surfactant 1 0.1 parts by mass ・Ethyl acetate (solvent) 1251 parts by mass --- ――――――――――――――――――――――――
Next, the obtained first layer forming composition 1 was filtered using a filter paper (#63, manufactured by Toyo Roshi Co., Ltd.) with an absolute filtration accuracy of 10 μm, and further filtered with a metal sintered filter (product name) with an absolute filtration accuracy of 2.5 μm. It was filtered using Pall Filter (PMF, media code: FH025, manufactured by Pall Corporation) and used for producing an ultraviolet sensing member.

(2) Preparation of second layer forming composition The composition shown below was mixed to prepare second layer forming composition 1.
――――――――――――――――――――――――――――
Composition of second layer forming composition 1――――――――――――――――――――――――――――
・Basic resin 1 99.9 parts by mass ・Surfactant 1 0.1 parts by mass ・Ethanol (solvent) 635.3 parts by mass―――――――――――――――――― ――――――――――
Next, the obtained second layer forming composition 1 was filtered using a filter paper (#63, manufactured by Toyo Roshi Co., Ltd.) with an absolute filtration accuracy of 10 μm, and then a metal sintered filter (product name) with an absolute filtration accuracy of 2.5 μm. The product was filtered using Pall Filter (PMF, media code: FH025, manufactured by Pall Corporation) and used to produce an ultraviolet sensing member.

(3) Preparation of Composition for Forming Intermediate Layer Composition 1 for forming intermediate layer was prepared by mixing the composition shown below and stirring in a constant temperature bath at 90° C. for 1 hour to dissolve water-soluble resin 1.
――――――――――――――――――――――――――――
Composition of intermediate layer forming composition 1――――――――――――――――――――――――――――
・Water-soluble resin 1 4.0 parts by mass ・Pure water (solvent) 88.5 parts by mass ・Isopropyl alcohol (solvent) 7.5 parts by mass―――――――――――――――― ――――――――――――
Next, the obtained intermediate layer forming composition 1 was filtered using a filter with an absolute filtration accuracy of 5 μm (trade name: Hydrophobic Fluorepore Membrane, manufactured by Millex), and used for producing an ultraviolet sensing member.

[Preparation of ultraviolet sensing member]
(1) Formation of the second layer The composition 1 for forming the second layer is applied onto the support 1 using a bar coater so that the thickness of the second layer after drying is 1.8 μm, It was dried at 120°C to obtain a support with a second layer.
Note that the support with the second layer is a laminate having the support 1 and the second layer in this order.

(2) Formation of intermediate layer The composition 1 for forming an intermediate layer is applied to the surface of the support with the second layer opposite to the second layer support 1 so that the thickness of the intermediate layer after drying is 0. It was coated using a bar coater to give a thickness of .6 μm and dried at 120° C. for 60 seconds to obtain a support with a second layer and an intermediate layer.
Note that the support with the second layer and the intermediate layer is a laminate having the support 1, the second layer, and the intermediate layer in this order.

(3) Formation of the first layer The composition 1 for forming the first layer is applied to the surface of the support with the second layer and the intermediate layer opposite to the support 1 of the intermediate layer, after drying. It was applied using a bar coater to a thickness of 2.5 μm, and dried at 80° C. to obtain the ultraviolet sensing member (ultraviolet sensing sheet) of Example 1.
The ultraviolet sensing member of Example 1 is a laminate having the support 1, the second layer, the intermediate layer, and the first layer in this order.

The ultraviolet sensing members of Examples other than Example 1 and Comparative Examples were prepared in the same manner as the ultraviolet sensing member of Example 1, except that the various configurations, types and contents of various components were changed as shown in the table below. , was created.

[Storage stability]
The ultraviolet sensing members of each Example and each Comparative Example were placed in a light-shielding bag and stored at 25° C. for 2 hours or 2 weeks.
After being stored for a predetermined period of time, each ultraviolet sensing member was taken out from the light-shielding bag. Then, the optical density value of magenta was measured using a spectrophotometer X-Lite (manufactured by X-Rite), and the storage stability was evaluated according to the following criteria. Note that the above evaluation was conducted under a yellow light environment so as not to be irradiated with ultraviolet rays.
A: Magenta optical density is 0.05 or less B: Magenta optical density is 0.06 to 0.08
C: Magenta optical density exceeds 0.08

[Difference in optical density before and after UV irradiation (optical density difference)]
After producing the ultraviolet sensing member of each Example and each Comparative Example, using Care222 (registered trademark), each ^Example and each Comparative Example was The ultraviolet light sensing member was irradiated with ultraviolet light. After UV irradiation, the optical density of magenta after UV irradiation was measured using a spectrophotometer X-Lite (manufactured by X-Rite). It was large enough and of a practical level.

In the table below, each description indicates the following.
The content (g/m ² ) of various components means the content (mass) per unit area of each layer (first layer, second layer, or intermediate layer).
Specifically, the "content" of "binder" in the "first layer" column indicates the content per unit area of the first layer. Further, the "content" of "basic compound" in the "first layer" column indicates the content per unit area of the second layer.

As shown in the table above, it was confirmed that the ultraviolet sensing member of the present invention exhibited the desired effects.

10 Ultraviolet sensing member 12 Support 14 Second layer 16 First layer

Claims (9)

An ultraviolet sensing member having a first layer and a second layer,
The first layer includes a photoacid generator that generates acid when exposed to ultraviolet light, and a coloring agent,
An ultraviolet sensing member, wherein the second layer contains a basic compound. The ultraviolet sensing member according to claim 1, wherein the basic compound has a nitrogen atom. The ultraviolet sensing member according to claim 1 or 2, wherein the basic compound contains a resin having a nitrogen atom. The ultraviolet sensing member according to any one of claims 1 to 3, wherein the first layer does not contain a colorant that does not develop color due to the action of an acid, oxidation, or light irradiation. The ultraviolet sensing member according to claim 1, further comprising an intermediate layer between the first layer and the second layer. The ultraviolet sensing member according to claim 5, wherein the intermediate layer contains a water-soluble resin. The ultraviolet sensing member according to any one of claims 1 to 6, wherein the photoacid generator is a compound represented by formula (B1).
In formula (B1), R ^b1 represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. L ^b represents -CO-, -CO ₂ -, -SO- or -SO ₂ -. X ^b1 to X ^b3 each independently represent a hydrogen atom or a halogen atom. However, the case where all of X ^b1 to X ^b3 are hydrogen atoms is excluded. The ultraviolet sensing member according to any one of claims 1 to 7, which is in the form of a sheet. An ultraviolet sensing kit comprising the ultraviolet sensing member according to any one of claims 1 to 8.