JP2017195825A - Wavelength conversion film and cultivation methods of agricultural crops - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wavelength conversion film excellent in weather resistance.SOLUTION: The wavelength conversion film of the present invention is a film used for wavelength conversion of the light irradiating agricultural products, characterized by containing particles which are emulsion polymers having a first structural unit derived from a monomer having fluorescence function. By emulsion polymerization of a monomer having fluorescence function, a site which is not involved in the fluorescence function of the monomer forms a capsule-like coat and thereby a side chain or the like having fluorescence function is difficult to contact to oxygen, which suppresses oxidized deterioration, a principal factor of lowered fluorescence function.SELECTED DRAWING: None

Description

  The present invention relates to a wavelength conversion film and a crop cultivation method.

  In recent years, as a production system that stably supplies crops at low cost, plant factories that cultivate crops while controlling the internal environment by temperature management or artificial light irradiation in closed spaces or semi-closed spaces have attracted attention. . In this plant factory, the growth of crops is promoted by irradiating artificial light using, for example, a fluorescent lamp, a light emitting diode (LED) or the like as a light source.

  Here, red light with a wavelength of 600 nm or more and 800 nm or less and blue light with a wavelength of 450 nm or more and less than 500 nm are particularly important for the growth of plants, and light of other wavelengths (for example, green light with a wavelength of 500 nm or more and less than 570 nm). Light or yellow light having a wavelength of 570 nm or more and less than 600 nm) is not always necessary. Therefore, in the plant factory, from the viewpoint of reducing power consumption, it is required to irradiate only light of a specific wavelength. As a specific method, the light emitted from the white LED with a wavelength conversion film containing a fluorescent substance is used. A method of irradiating by converting to a specific wavelength has been studied. According to this method, it is considered that only light of a specific wavelength can be irradiated at a low cost by using a white LED that is low in power consumption and widely used and is cheaper than other LEDs.

  However, the wavelength conversion film has an inconvenience that the weather resistance is insufficient and the fluorescent material tends to lose its fluorescent function due to oxidative degradation in a relatively short period of time. Therefore, as a method for improving the weather resistance of the wavelength conversion film, for example, a base film formed of a polyolefin resin composition containing a specific amount of a fluorescent substance having a specific structure, and an inorganic layer laminated on the base film Agricultural polyolefin films comprising a layer formed of an anti-fogging agent composition containing fine particles and / or a synthetic resin binder as main components have been proposed (see JP 2011-115073 A). However, even with the conventional method, it is difficult to improve the weather resistance of the wavelength conversion film to a sufficiently satisfactory level.

JP 2011-115073 A

  This invention is made | formed based on the above situations, The objective is to provide the wavelength conversion film excellent in drought tolerance, and the cultivation method of the agricultural crops using this wavelength conversion film.

  As a result of intensive studies, the present inventors have found that by subjecting a monomer having a fluorescence function to emulsion polymerization, particles that are less likely to cause oxidative degradation and the like can be obtained, and the above problems can be solved.

  That is, the invention made in order to solve the above-mentioned problems is a wavelength conversion film used for wavelength conversion of light irradiated on agricultural products, and is a first structural unit derived from a monomer having a fluorescence function (hereinafter referred to as “structural unit”). It is characterized by containing particles (hereinafter also referred to as “[A] particles”) which are emulsion polymers having I) and also “”.

  Another invention made to solve the above problems is a method for cultivating a crop using an LED as a light source, wherein the emitted light of the LED is wavelength-converted by the above-described wavelength conversion film and irradiated to the crop. And

  Here, the “fluorescence function” refers to a function of emitting light having a longer wavelength than the irradiated light when irradiated with light having a specific wavelength. The “monomer having a fluorescence function” refers to a monomer that imparts a fluorescence function to an incorporated polymer, for example, a compound in which a chromophore having a fluorescence function and a polymerizable unsaturated group are chemically bonded. The “wavelength conversion film” refers to a film that absorbs at least part of light having a specific wavelength incident from one surface and emits light having a longer wavelength than incident light from the other surface. “Organic group” refers to a group containing at least one carbon atom.

  The wavelength conversion film of the present invention is excellent in weather resistance. The crop cultivation method of the present invention can grow crops at low cost.

<Wavelength conversion film>
The said wavelength conversion film contains the [A] particle | grains which are used for wavelength conversion of the light irradiated to agricultural crops, and are an emulsion polymer which has the structural unit (I) derived from the monomer which has a fluorescence function. The wavelength conversion film usually further contains a [B] binder resin as a matrix, and [A] particles are dispersed in the [B] binder resin.

  The wavelength conversion film is excellent in weather resistance by containing [A] particles having the structural unit (I). The reason why the wavelength conversion film has the above-described configuration provides the above-mentioned effects is not necessarily clear, but can be inferred as follows, for example. That is, when a monomer having a fluorescence function is emulsion-polymerized, a portion not participating in the fluorescence function, such as the main chain of the monomer, forms a capsule-like outer shell due to a difference in affinity with an aqueous dispersion medium. A part such as a side chain having a fluorescent function is confined in the inside. As a result, in the obtained [A] particles, the outer shell makes it difficult for oxygen to come into contact with the side chain or the like having the fluorescence function, and oxidative deterioration that is a main factor for the decrease in fluorescence function is suppressed. As a result, the wavelength conversion film is considered to have excellent weather resistance.

  As a minimum of the average thickness of the said wavelength conversion film, 10 micrometers is preferable and 50 micrometers is more preferable. On the other hand, the upper limit of the average thickness of the wavelength conversion film is preferably 1,000 μm, and more preferably 500 μm. When the average thickness of the wavelength conversion film is smaller than the lower limit, the strength of the wavelength conversion film may be insufficient, or the irradiated light may not be sufficiently wavelength converted. Conversely, when the average thickness of the wavelength conversion film exceeds the upper limit, the production cost may increase.

  The wavelength conversion film is preferably a film that converts light (green light and yellow light) having a wavelength of 500 nm or more and less than 600 nm into light (red light) having a wavelength of 600 nm or more and 800 nm or less, and has a wavelength of 500 nm or more and less than 600 nm. What converts the wavelength of light into light having a wavelength of 600 nm or more and 700 nm or less is more preferable. Thus, since the said wavelength conversion film is what converts the green light and yellow light which are not so important for the cultivation of a plant into red light, it can be used suitably by promotion of cultivation of agricultural products. Here, “converting light of a specific wavelength into light of another wavelength” means converting at least a part of the light of the specific wavelength into light of another wavelength.

[[A] particles]
[A] The shape of the particles is not particularly limited, but is preferably spherical. Thus, by making the shape of the [A] particles spherical, the surface area per volume can be reduced, and oxidation deterioration can be further suppressed. However, it is not necessary that all of the [A] particles are spherical particles, and some non-spherical particles such as a double spherical shape in which two spherical particles are joined or a shape in which a part of the spherical particles is missing are included. It may be. [A] The lower limit of the ratio of the number of spherical particles to the total number of particles is preferably 30%, more preferably 50%, and even more preferably 70%. Here, the term “spherical” is a concept including a true spherical shape and a substantially spherical shape, and specifically means that the ratio of the major axis / minor axis of the particles is 1.0 or more and 2.0 or less. [A] A transmission electron microscope is used to observe the shape of the particles. Furthermore, “the ratio of the number of spherical particles to the total number of particles” refers to the ratio of the number of spherical particles in 100 particles existing in the observation field of the transmission electron microscope.

  [A] When the particles include spherical particles, the average value of the major axis / minor axis ratio of the spherical particles is preferably 1.0 or more and 1.5 or less, and more preferably 1.0 or more and 1.2 or less. Here, the “average value of the ratio of major axis / minor axis of spherical particles” means the average value of the ratio of major axis / minor axis of each spherical particle when 100 spherical particles are observed with a transmission electron microscope.

  [A] The lower limit of the average particle diameter of the particles is preferably 25 nm, more preferably 40 nm, still more preferably 60 nm, and particularly preferably 90 nm. On the other hand, the upper limit of the average particle size of the [A] particles is preferably 1,000 nm, more preferably 600 nm, still more preferably 500 nm, and particularly preferably 400 nm. [A] By setting the average particle size of the particles within the above range, light having a wavelength that is less important in plant growth can be efficiently wavelength-converted into light having a higher importance. When the average particle size of [A] particles exceeds the above upper limit, light scattering and absorption by [A] particles are promoted, and the transparency of the wavelength conversion film may be reduced. Here, the “average particle diameter” is a value obtained by measuring the long diameters of 100 primary particles existing in the observation field of the transmission electron microscope and calculating the average value thereof.

(Structural unit (I))
The structural unit (I) is derived from a monomer having a fluorescence function. Examples of the monomer having a fluorescence function include i) a salt of a cationic chromophore and an anionic moiety having an anionic group and a polymerizable unsaturated group (hereinafter also referred to as “compound (a1)”),
ii) a salt of an anionic chromophore and a cation moiety having a cationic group and a polymerizable unsaturated group (hereinafter also referred to as “compound (a2)”),
iii) a compound having an electrically neutral chromophore and a polymerizable unsaturated group (hereinafter also referred to as “compound (a3)”),
iv) a salt of a cationic chromophore having a polymerizable unsaturated group and an anion moiety;
v) A salt of an anionic chromophore having a polymerizable unsaturated group and a cation moiety can be exemplified. Among these, from the viewpoint of solvent resistance, the compound (a1), the compound (a2), the compound (a3) and a combination thereof are preferable, and the compound represented by the following formula (A) and the following formula (B) The compound represented, the compound represented by the following formula (C), and a combination thereof are more preferable.

  As used herein, the “chromophore” refers to an atomic group that emits light by absorbing light from the visible light region to the infrared region. The “cationic chromophore” refers to an atomic group having a positive charge. In addition, when the atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a positive charge, it is included in the cationic chromophore. . Further, “anionic chromophore” refers to an atomic group having a negative charge. In addition, when an atomic group has a functional group having a positive charge and a functional group having a negative charge, and the total of these charges becomes a negative charge, it is included in the anionic chromophore. . Further, in the present specification, an atomic group that does not correspond to either a cationic chromophore or an anionic chromophore, and has no functional group having a positive charge and a functional group having a negative charge, or Even if it has a functional group having a positive charge and a functional group having a negative charge, the number of functional groups in both is the same, and an atomic group that is electrically neutral as a whole is referred to as “electrically neutral coloring. A group.

  The lower limit of the wavelength at which the chromophore exhibits an absorption maximum is preferably 400 nm, and more preferably 500 nm. On the other hand, the upper limit of the wavelength at which the chromophore exhibits an absorption maximum is preferably 700 nm, and more preferably 600 nm.

(Compound (a1))
Compound (a1) is a salt of a cationic chromophore and an anionic moiety having an anionic group and a polymerizable unsaturated group. The cationic chromophore constitutes the cation part of the compound (a1).

  Examples of the cationic chromophore include polymethine chromophore, quinone imine chromophore, xanthene chromophore, squarylium chromophore, and quinophthalone chromophore. The cationic chromophore is preferably a polymethine chromophore or a xanthene chromophore from the viewpoint of easy availability of raw materials.

  As said polymethine chromophore, what is represented by following formula (3) is preferable.

In the above formula (3),
R ²¹ and R ²² are each independently a substituted or unsubstituted monovalent hydrocarbon group.
R ^{23 to} R ²⁵ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted monovalent hydrocarbon group.
Ring Z ¹ and ring Z ² are each independently a substituted or unsubstituted aromatic hydrocarbon ring.
G ¹ and G ² are each independently —O—, —S—, or —CR ²⁶ R ²⁷ —. R ²⁶ and R ²⁷ are each independently a substituted or unsubstituted monovalent hydrocarbon group.
s is an integer of 1 to 3.
When s is 2 or more, the plurality of R ²³ and R ²⁴ may be the same or different.

Examples of the monovalent hydrocarbon group represented by R ^{21 to} R ²⁷ include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. be able to.

  The monovalent aliphatic hydrocarbon group may be either linear or branched, and may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. As carbon number of the said monovalent | monohydric aliphatic hydrocarbon group, 1-30 are preferable, 1-15 are more preferable, and 1-8 are more preferable. Specific examples of the alkyl group include, for example, methyl group, ethyl group, isopropyl group, propyl group, butyl group, 2-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl, undecyl, 1-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl, tetradecyl, tert-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl Examples include groups. Specific examples of the alkenyl group include, for example, ethenyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4- Ethenyl) -5-hexenyl group, 2-decenyl group and the like. Specific examples of the alkynyl group include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group, and 2-octynyl. Group, (4-ethynyl) -5-hexynyl group, 2-decynyl group and the like.

The monovalent alicyclic hydrocarbon group may be saturated or unsaturated. As carbon number of the said monovalent | monohydric alicyclic hydrocarbon group, 3-30 are preferable and 3-12 are more preferable. Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a monovalent condensed polycyclic hydrocarbon group, a monovalent bridged ring hydrocarbon group, a monovalent spiro hydrocarbon group, A monovalent cyclic terpene hydrocarbon group etc. can be mentioned. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the cycloalkenyl group include a 1-cyclohexenyl group. Specific examples of the condensed polycyclic hydrocarbon group include a tricyclodecanyl group, a decahydro-2-naphthyl group, an adamantyl group, and the like. Specific examples of the monovalent bridged ring hydrocarbon group include, for example, a tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, a pentacyclopentadecanyl group, an isobornyl group, and a dicyclopentenyl group. Group, tricyclopentenyl group and the like. Specific examples of the monovalent spiro hydrocarbon group include a monovalent group obtained by removing one hydrogen atom from spiro [3,4] heptane or spiro [3,4] octane. Specific examples of the monovalent cyclic terpene hydrocarbon group include, for example, a monovalent group obtained by removing one hydrogen atom from p-menthane, tujang, curan and the like.

  The monovalent aromatic hydrocarbon group may have a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring. As carbon number of the said monovalent | monohydric aromatic hydrocarbon group, 6-20 are preferable and 6-10 are more preferable. As said monovalent | monohydric aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group etc. can be mentioned, for example, Among these, a phenyl group and a naphthyl group are preferable.

  Examples of the substituent for the monovalent hydrocarbon group include a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms. In addition, when the said monovalent hydrocarbon group is an alicyclic hydrocarbon group or an aromatic hydrocarbon group, it can also have a C1-C6 alkyl group as a substituent. Specific examples of the alkoxy group having 1 to 6 carbon atoms include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, sec-butoxy group, and n-pentyloxy. Group, iso-pentyloxy group, n-hexyloxy group, methoxymethoxy group, ethoxyethoxy group, 3- (iso-propyloxy) propyloxy group and the like.

Specific examples of the halogen atom represented by R ^{23 to} R ²⁵ and the halogen atom contained in the hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The aromatic hydrocarbon ring represented by the ring Z ¹ and the ring Z ² may be a monocyclic aromatic hydrocarbon ring or a polycyclic aromatic hydrocarbon ring. As carbon number of the said aromatic hydrocarbon ring, 6-20 are preferable and 6-10 are more preferable. Specific examples of the aromatic hydrocarbon ring include a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, naphthacene ring, and triphenylene ring.

The monovalent hydrocarbon group represented by R ²¹ and R ²² is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable.

As the ^R 23 ^{to R 25,} a hydrogen atom is preferable.

The ring Z ¹ and ring Z ² are preferably benzene rings.

As the ^{G 1} and ^{G 2,} -O-, and ^-CR 26 ^{R 27} - it is preferred. As the ^{R 26} and ^{R 27,} preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably methyl and ethyl.

  As said s, 1 and 2 are preferable and 1 is more preferable.

Specific examples of the polymethine chromophore represented by the above formula (3) include those represented by the following formula.

  As said polymethine chromophore, what is represented with a following formula other than what is represented with said Formula (3) can also be used.

  As the quinoneimine chromophore, for example, one represented by the following formula can be used.

  As said xanthene chromophore, what is represented by following formula (4) is preferable.

In the above formula (4),
R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, —R ³⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. However, the hydrogen atom contained in the monovalent aromatic hydrocarbon group is a halogen atom, —R ³⁸ , —OH, —OR ³⁸ , —SO ₃ H, —SO ₃ M ¹ , —CO ₂ H, —CO ₂ M ¹ , —CO ₂ R ³⁸ , —SO ₃ R ³⁸ , —SO ₂ NHR ³⁹ or —SO ₂ NR ³⁹ R ⁴⁰ may be substituted.
R ³⁵ and R ³⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ³⁷ is —SO ₃ H, —SO ₃ M ¹ , —CO ₂ H, —CO ₂ R ³⁸ , —SO ₃ R ³⁸ , —SO ₂ NHR ³⁹ or —SO ₂ NR ³⁹ R ⁴⁰ .
u is an integer of 0-5.
When u is an integer of 2 or more, the plurality of R ³⁷ may be the same or different.
R ³⁸ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom. The monovalent saturated hydrocarbon group may have —O—, —CO—, or —NR ³⁸ — between the C—C bonds.
R ³⁹ and R ⁴⁰ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^a , or R ³⁹ and R ⁴⁰ are combined with each other. It is a C1-C10 substituted or unsubstituted monovalent | monohydric heterocyclic group comprised with the atom or atomic chain to couple | bond. However, the hydrogen atoms contained in the alkyl group and cycloalkyl group, a hydroxyl group, a halogen ^atom, -X a, it may be substituted with -CH = CH ₂ or -CH = ^{CHR 38.} The alkyl group and cycloalkyl group may have —O—, —CO—, or —NR ³⁸ — between the C—C bonds. Furthermore, the hydrogen atom contained in the monovalent heterocyclic group may be substituted with —R ³⁸ , —OH or —X ^a .
M ¹ is a sodium atom or a potassium atom.
X ^a is a monovalent aromatic hydrocarbon group, or a monovalent aromatic heterocyclic group having 5 to 10 carbon atoms having 6 to 10 carbon atoms. However, the hydrogen atom contained in this monovalent aromatic hydrocarbon group and monovalent aromatic heterocyclic group is —OH, —R ³⁸ , —OR ³⁸ , —NO ₂ , —CH═CH ₂ , —CH. = CHR ³⁸ or a halogen atom may be substituted.

The monovalent saturated hydrocarbon group represented by R ³⁸ may be linear, branched or cyclic, and may have a bridge structure as long as it has 1 to 10 carbon atoms. Specific examples of the monovalent saturated hydrocarbon group include a monovalent saturated aliphatic hydrocarbon group and a monovalent saturated alicyclic hydrocarbon group. Examples of the monovalent saturated aliphatic hydrocarbon group include an alkyl group. Examples of the monovalent saturated alicyclic hydrocarbon group include a cycloalkyl group. Examples of the alkyl group and cycloalkyl group include the same groups as described above.

Examples of the monovalent heterocyclic group having 1 to 10 carbon atoms configured together with the atom or atomic chain to which R ³⁹ and R ⁴⁰ are combined with each other include, for example, a pyrrolidinyl group, a pyrazolinyl group, a morpholinyl group, a theomorpholinyl group, Piperidyl group, piperidino group, piperazinyl group, homopiperazinyl group, tetrahydropyrimidine group, 1,3-dioxolan-2-yl group, pyridyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group Imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, indolyl group, indazolyl group, benzimidazolyl group, phthalimide group and the like. Examples of the substituent for the monovalent heterocyclic group include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an amino group, and an alkyl group having 1 to 6 carbon atoms.

The monovalent aromatic heterocyclic group having 5 to 10 carbon atoms represented by X ^a, such as furyl group, a thienyl group, a pyridyl group, pyrrolyl group, oxazolyl group, isoxazol group, thiazolyl group, isothiazolyl group, imidazolyl Group, pyrazolyl group, pyrimidyl group and the like.

As the monovalent aromatic hydrocarbon group represented by R ³¹ , R ³² , R ³³ , R ³⁴ and X ^a , an aryl group having 6 to 10 carbon atoms is preferable. And a naphthyl group.

Examples of —SO ₃ R ³⁸ represented by R ³¹ , R ³² , R ³³ , R ^34, and R ³⁷ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group.

Examples of the —CO ₂ R ³⁸ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropyloxycarbonyl group.

The _-SO 2 ^NHR _39, as the ^{R 39} and ^{R 40} in -SO ^{2 NR} 39 ^{R 40,} branched alkyl groups having 6 to 8 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 7 carbon atoms, An aralkyl group having 8 to 10 carbon atoms, an alkyl group having 2 to 8 carbon atoms substituted with a hydroxyl group or an alkoxy group, and an aryl group are preferable.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³⁵ and R ^36, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group.

  Typical examples of the chromophore represented by the above formula (4) include those represented by the following formula.

  The anion portion of the compound (a1) has an anionic group and a polymerizable unsaturated group. Examples of the anionic group include a sulfonate anion, an imide anion, and a carboxylate anion. As said anionic group, an imide anion is preferable and a sulfonylimide anion is more preferable.

  Examples of the polymerizable unsaturated group include a (meth) acryloyloxy group, a vinylaryl group, a vinyloxy group, and an allyl group. As the polymerizable unsaturated group, a (meth) acryloyloxy group and a vinylaryl group are preferable, and a vinylaryl group is more preferable.

  As the compound (a1), a compound represented by the following formula (A) is preferable.

In the above formula (A),
W ¹ is a monovalent polymerizable unsaturated group.
X ¹ is a monovalent group having a halogen atom, a monovalent halogenated hydrocarbon group, or a linking group containing a hetero atom other than a halogen atom between carbon-carbon atoms of the monovalent halogenated hydrocarbon group.
Y ¹ is a single bond or a divalent organic group.
Q ⁺ is a cationic chromophore.

As the monovalent polymerizable unsaturated group represented by W ¹ , a (meth) acryloyloxy group and a vinylaryl group are preferable, and a vinylaryl group is more preferable.

Examples of the halogen atom represented by X ¹ include the same halogen atoms as those described above.

Examples of the hydrocarbon group forming the skeleton of the monovalent halogenated hydrocarbon group represented by X ¹ include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and an alicyclic ring as a substituent. A monovalent aliphatic hydrocarbon group having a hydrocarbon group (hereinafter referred to as “alicyclic hydrocarbon-substituted aliphatic hydrocarbon group”), a monovalent aromatic hydrocarbon group, and an aliphatic hydrocarbon as a substituent Monovalent aromatic hydrocarbon group having a group (hereinafter referred to as “aliphatic hydrocarbon-substituted aromatic hydrocarbon group”), and monovalent aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as “aliphatic hydrocarbon-substituted aromatic hydrocarbon group”). , "Referred to as" aromatic hydrocarbon-substituted aliphatic hydrocarbon group ").

  The hydrocarbon group constituting the skeleton of the monovalent halogenated hydrocarbon group is a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent alicyclic hydrocarbon-substituted aliphatic hydrocarbon. Group, monovalent aromatic hydrocarbon group, monovalent aliphatic hydrocarbon-substituted aromatic hydrocarbon group, or monovalent aromatic hydrocarbon-substituted aliphatic hydrocarbon group, these groups include the following: Are preferable from the viewpoint of solubility in organic solvents.

  That is, the monovalent aliphatic hydrocarbon group is preferably an alkyl group. This alkyl group may be linear or branched. As carbon number of the said alkyl group, 1-20 are preferable, 1-8 are more preferable, and 1-6 are more preferable. Specific examples of the alkyl group include the same groups as described above.

  In the monovalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be a 2- to 4-ring bridged alicyclic hydrocarbon group. 3-20 are preferable, as for carbon number of an alicyclic hydrocarbon group, 3-12 are more preferable, and 3-6 are more preferable. Specific examples of the monovalent alicyclic hydrocarbon group include the same groups as described above.

  The monovalent alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group. As carbon number of the said monovalent | monohydric alicyclic hydrocarbon substituted aliphatic hydrocarbon group, 4-20 are preferable and 6-14 are more preferable. Specific examples of the monovalent alicyclic hydrocarbon-substituted aliphatic hydrocarbon group include, for example, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclohexylmethyl group, a cyclohexylpropyl group, an adamantylmethyl group, and 1- (1-adamantyl). ) An ethyl group, a cyclopentylethyl group, etc. can be mentioned.

  As carbon number of the said monovalent | monohydric aromatic hydrocarbon group, 6-14 are preferable and 6-10 are more preferable. Specific examples of the monovalent aromatic hydrocarbon group include the same groups as those described above, and among these, a phenyl group is preferable.

  The monovalent aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group. As carbon number of the said monovalent | monohydric aliphatic hydrocarbon substituted aromatic hydrocarbon group, 7-30 are preferable and 7-20 are more preferable. Specific examples of the monovalent aliphatic hydrocarbon-substituted aromatic hydrocarbon group include a tolyl group, a xylyl group, and mesityl.

  The monovalent aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group. As carbon number of the said monovalent | monohydric aromatic-hydrocarbon substituted aliphatic hydrocarbon group, 7-30 are preferable and 7-20 are more preferable. Specific examples of the monovalent aromatic hydrocarbon-substituted aliphatic hydrocarbon group include a benzyl group and a phenethyl group. Among these, a benzyl group is preferable.

Examples of the hydrocarbon group constituting the skeleton of the monovalent halogenated hydrocarbon group represented by X ¹ include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, 1 A monovalent aromatic hydrocarbon group, a monovalent aliphatic hydrocarbon-substituted aromatic hydrocarbon group, and a monovalent aromatic hydrocarbon-substituted aliphatic hydrocarbon group are preferred, an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl Group, phenyl group, alkyl-substituted phenyl group and aralkyl group are more preferred, and alkyl group and aralkyl group are particularly preferred.

As the halogen atom in the monovalent halogenated hydrocarbon group represented by X ^1, from the viewpoint of the heat resistance of [A] particles, fluorine atom is preferable. It is considered that when the halogen atom of the monovalent halogenated hydrocarbon group is a fluorine atom, a salt having a stronger ionic bond strength is formed and the heat resistance of the [A] particle is improved. The fluorine atom may substitute part or all of the hydrogen atoms of the hydrocarbon group forming the skeleton of the monovalent halogenated hydrocarbon group.

Examples of the monovalent group having a linking group containing a hetero atom other than a halogen atom between C—C bonds of the monovalent halogenated hydrocarbon group represented by X ¹ include, for example, —O—, -S -, - CO -, - COO -, - CONH -, - SO 2 - and the like. Examples of the monovalent halogenated hydrocarbon group constituting the monovalent group having the linking group include the same groups as those described above. In the monovalent halogenated hydrocarbon group constituting the monovalent group having the linking group, the “carbon number” means the total number of carbons in the portion excluding the carbon atoms constituting the linking group. .

X ¹ includes a monovalent halogenated hydrocarbon group and a heteroatom other than a halogen atom between C—C bonds of the monovalent halogenated hydrocarbon group from the viewpoint of heat resistance of the [A] particle. A monovalent group having a linking group is preferred, a group represented by the following formula (6) or (7) is more preferred, and from the viewpoint of forming a conjugate base of an organic acid having a stronger acidity, the following formula (6) Is more preferable.

In the above formula (6),
R ⁵⁰ is a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, a monovalent alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ⁵¹ COOR ⁵² —, or R ⁵³ COOR ⁵⁴ CFH—. is there.
R ⁵¹ and R ⁵³ are each independently an alkyl group, a monovalent alicyclic hydrocarbon group, a heteroaryl group, or a substituted or unsubstituted aryl group.
R ⁵² and R ⁵⁴ are each independently an alkanediyl group.
q is an integer of 1 or more.
* Is a bond. )

In the above formula (7),
R ^{55 to} R ⁵⁹ are each independently a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group or an alkoxy group.
* Is a bond.
Provided ^that at least one of R 55 ^{to R 59} is a fluorine atom or a fluorinated alkyl group.

In the above formula (6), the alkyl group represented by R ⁵⁰ may be linear or branched. As carbon number of the said alkyl group, 1-20 are preferable, 1-8 are more preferable, and 1-4 are more preferable. Specific examples of the alkyl group include the same groups as described above.

The fluorinated alkyl group represented by R ⁵⁰ may be linear or branched. As carbon number of the said fluorinated alkyl group, 1-20 are preferable, 1-8 are more preferable, and 1-4 are more preferable. Examples of the fluorinated alkyl group include those in which part or all of the hydrogen atoms of the above-described alkyl group are substituted with fluorine atoms, and a perfluoroalkyl group is particularly preferable.

The monovalent alicyclic hydrocarbon group represented by R ⁵⁰ may be a 2- to 4-ring monovalent bridged alicyclic hydrocarbon group. As carbon number of the said monovalent | monohydric alicyclic hydrocarbon group, 3-20 are preferable and 3-12 are more preferable. Examples of the monovalent alicyclic hydrocarbon group include the same groups as those described above.

The alkoxy group represented by R ⁵⁰ may be linear or branched. As carbon number of the said alkoxy group, 1-10 are preferable, 1-8 are more preferable, and 1-4 are more preferable. Specific examples of the alkoxy group include the same groups as described above.

The fluorinated alkoxy group represented by R ⁵⁰ may be linear or branched. As carbon number of the said fluorinated alkoxy group, 1-10 are preferable, 1-6 are more preferable, and 1-4 are more preferable. Specific examples of the fluorinated alkoxy group include those in which part or all of the hydrogen atoms of the above alkoxy group are substituted with fluorine atoms, and a perfluoroalkoxy group is preferred.

In R ⁵¹ COOR ⁵² — and R ⁵³ COOR ⁵⁴ CFH— represented by R ⁵⁰ , R ⁵¹ and R ⁵³ are each independently an alkyl group, a monovalent alicyclic hydrocarbon group, or heteroaryl. Or a substituted or unsubstituted aryl group. The alkyl group may be linear or branched. As carbon number of the said alkyl group, 1-12 are preferable and 1-8 are more preferable. Specific examples of the alkyl group include the same groups as described above. The monovalent alicyclic hydrocarbon group may be a 2- to 4-ring monovalent bridged alicyclic hydrocarbon group. As carbon number of the said monovalent | monohydric alicyclic hydrocarbon group, 3-20 are preferable and 3-12 are more preferable. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples of the heteroaryl group include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. As said aryl group, a C6-C14 aryl group is preferable, a C6-C10 aryl group is more preferable, and a phenyl group is further more preferable. In addition, as a substituent of the said aryl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, a trifluoromethyl group etc. are mentioned, for example. The position and number of substituents in the aryl group are arbitrary, and when two or more substituents are present, the two or more substituents may be the same or different.

The alkanediyl group represented by R ⁵² and R ⁵⁴ may be linear or branched. As carbon number of the said alkanediyl group, 1-10 are preferable. Specific examples of the alkanediyl group include methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3- Diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane- Examples include 1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decane-1,10-diyl group and the like. Of these, the alkanediyl group is preferably an alkanediyl group having 2 to 6 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and from the viewpoint of ease of production, an ethylene group is further included. preferable.

  The upper limit of q is preferably 10, and more preferably 8.

As R ⁵⁰ , a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ⁵¹ COOR ⁵² —, and R ⁵³ COOR ⁵⁴ CFH— are preferable, and a fluorine atom, an alicyclic hydrocarbon is preferable. Group, perfluoroalkoxy group, R ⁵¹ COOCH ₂ CH ₂ —, and R ⁵³ COOCH ₂ CH ₂ CFH— are more preferred.

In the above formula ^(7), the alkyl group represented by R 55 ^{to R 59,} as the fluorinated alkyl group and an alkoxy group, an alkyl group, fluorinated alkyl and alkoxy represented by ^{R 50} in the formula (6) A configuration similar to that of the base can be employed. Provided that at least one of the R ^{55 ~} above and R ⁵⁹ is a fluorine atom or a fluorinated alkyl group, is preferably at least three of fluorine atom or a fluorinated alkyl group of the R ⁵⁵ to R ^59.

Examples of the divalent organic group represented by Y ¹ include a divalent hydrocarbon group, a group formed by combining a divalent hydrocarbon group and a linking group containing a hetero atom, and one of the hydrogen atoms of these groups. And a group in which a part is substituted with a halogen atom. Examples of such divalent organic groups include alkanediyl groups having 1 to 10 carbon atoms, arylene groups having 6 to 20 carbon atoms, arylene alkanediyl groups having 7 to 20 carbon atoms, and alkanes having 1 to 10 carbon atoms. At least one selected from a diyl group and an arylene group having 6 to 20 carbon atoms, -O-, -S-, -COO-, -CONR ^b- (R ^b is a hydrogen atom or an alkyl having 1 to 8 carbon atoms). And a group formed by combining at least one selected from —SO ₂ —.

  Specific examples of the alkanediyl group include the same groups as described above. Among these, the alkanediyl group is preferably an alkanediyl group having 2 to 8 carbon atoms, and more preferably an alkanediyl group having 2 to 6 carbon atoms.

  Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, and an anthryl group. As said arylene group, a C6-C10 arylene group is preferable and a phenylene group is more preferable.

The arylene alkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group. The arylenealkanediyl group is preferably an arylenealkanediyl group having 7 to 15 carbon atoms, and more preferably an arylenealkanediyl group having 7 to 13 carbon atoms from the viewpoint of availability of raw materials and production. Specific examples of the arylenealkanediyl group include phenylene C _1-6 alkanediyl groups such as a phenylenemethylene group, a phenylenedimethylene group, a phenylenetrimethylene group, a phenylenetetramethylene group, a phenylenepentamethylene group, and a phenylenehexamethylene group. Can be mentioned. In addition, examples of the arylenealkanediyl group include ortho, meta, and para isomers, and para isomers are preferable from the viewpoint of low steric hindrance.

Further, at least one selected from the arylene group having 6 to 20 alkanediyl group and the number of carbon atoms of 1 to 10 carbon atoms, -O -, - S -, - COO -, - CONR b - (R b represents a hydrogen atom Or an alkyl group having 1 to 8 carbon atoms) and at least one selected from —SO ₂ — are the alkanediyl group having 1 to 10 carbon atoms and the arylene group having 6 to 20 carbon atoms. And a group formed by combining at least one selected from —O—, —COO—, and —SO ₂ — is preferable, and an alkanediyl group having 1 to 10 carbon atoms and 6 to 20 carbon atoms. A group formed by combining at least one selected from arylene groups of the above and at least one selected from —O— and —SO ₂ — is more preferable. In addition, as a specific example of a C1-C8 alkyl group represented by ^Rb , the group similar to what was mentioned above etc. can be mentioned.

As the cationic chromophore represented by Q ⁺ , those described above can be used.

  Specific examples of the anion portion having an anionic group and a polymerizable unsaturated group of the compound represented by the above formula (A) include a structure represented by the following formula.

  Among the compounds (a1), examples of the anion portion having a sulfonate anion as an anionic group include p-styrene sulfonate, an anion having a sulfonate anion and a polymerizable unsaturated group described in International Publication No. 2006/121096. The part can be exemplified.

(Compound (a2))
Compound (a2) is a salt of an anionic chromophore and a cation moiety having a cationic group and a polymerizable unsaturated group. The anionic chromophore constitutes the anion portion of the compound (a2).

Examples of the anionic chromophore include polymethine chromophore, quinone imine chromophore, xanthene chromophore, squarylium chromophore, and quinophthalone chromophore. The anionic chromophore is preferably a xanthene chromophore, more preferably one having one or more substituents selected from —SO ₃ — and —CO ₂ —.

  Specific examples of the anionic chromophore include a xanthene chromophore represented by the following formula (8).

In the above formula (8),
R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are each independently a hydrogen atom, —R ⁶⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. However, the hydrogen atoms contained in the aromatic hydrocarbon group, a halogen _{^{atom, -R 68, -OH, -OR 68}} , -SO 3 H, -SO 3 M 2, -SO 3 -, - CO 2 H, _{^{-CO 2 M 2, -COO -,}} - CO 2 R 68, -SO 3 R 68, which may be substituted with -SO 2 ^{NHR 69} or _-SO 2 ^NR 69 ^{R 70.}
R ⁶⁵ and R ⁶⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^{67 _{is, -SO 3 H, -SO 3 M}} 2, -SO 3 -, - CO 2 H, -CO 2 M 2, -COO -, - CO 2 R 68, -SO 3 R 68, -SO 2 NHR ⁶⁹ or —SO ₂ NR ⁶⁹ R ⁷⁰ .
v is an integer of 0-5.
When v is an integer of 2 or more, the plurality of R ⁶⁷ may be the same or different.
^R68 is a C1-C10 saturated hydrocarbon group. However, the hydrogen atoms contained in this saturated hydrocarbon group may be substituted with a halogen atom, and this saturated hydrocarbon group, -O between C-C bond -, - CO- or -NR ⁶⁸ - You may have.

R ⁶⁹ and R ⁷⁰ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^b , or R ⁶⁹ and R ⁷⁰ are bonded to each other. Or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, —X ^b , —CH═CH ₂ or —CH═CHR ^68. The alkyl group may have —O—, —CO—, or —NR ⁶⁸ — between the C—C bonds, and the hydrogen atom contained in this heterocyclic group is —R ⁶⁸ , —OH, or — It may be substituted with ^Xb .
M ² is a sodium atom or a potassium atom.
^Xb is a C6-C10 aromatic hydrocarbon group or a C5-C10 aromatic heterocyclic group. The hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is substituted with —OH, —R ⁶⁸ , —OR ⁶⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁶⁸ or a halogen atom. May be.
However, any two or more of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁷ have —SO ₃ — or —COO—.

Aromatic hydrocarbon groups represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ , alkyl groups represented by R ⁶⁵ and R ⁶⁶ , saturated hydrocarbon groups represented by R ⁶⁸ , R ⁶⁹ And the alkyl group, cycloalkyl group and heterocyclic group represented by R ⁷⁰ , and the aromatic hydrocarbon group and aromatic heterocyclic group represented by ^Xb are the aromatic hydrocarbon groups of the above formula (4). , An alkyl group, a saturated hydrocarbon group, a heterocyclic group, and an aromatic heterocyclic group can be employed, and a preferred embodiment is also as described in the above formula (4).

The xanthene chromophore represented by the formula (8) has at least two of R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁷ having —SO ₃ — or —COO—. Specific examples thereof include an aromatic hydrocarbon group in which two or more of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are substituted with —SO ₃ — or —COO—, or the above R ⁶⁷ is An aromatic in which two or more selected from —SO ₃ — and —COO— or one or more of the above R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are substituted with —SO ₃ — or —COO— Examples thereof include a hydrocarbon group and one or more of the above-mentioned R ⁶⁷ is —SO ₃ — or —COO—.

  Examples of the xanthene chromophore represented by the above formula (8) include a chromophore represented by the following formula.

  The cation part of the compound (a2) has a cationic group and a polymerizable unsaturated group. Examples of the cationic group include an ammonium cation, a phosphonium cation, a sulfonium cation, an iodonium cation, and a diazonium cation. As the cationic group, an ammonium cation is preferable.

  Examples of the polymerizable unsaturated group include a (meth) acryloyloxy group, a vinylaryl group, a vinyloxy group, and an allyl group. As said polymerizable unsaturated group, a (meth) acryloyloxy group and an allyl group are preferable, and a (meth) acryloyloxy group is more preferable.

  As the compound (a2), a compound represented by the following formula (B) is preferable.

In the above formula (B),
R ^{71 to} R ⁷³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
W ² is a polymerizable unsaturated group.
Y ² is a single bond or a divalent organic group.
Q ⁻ is an anionic chromophore.

The monovalent hydrocarbon group represented by R ^{71 to} R ⁷³ may be linear, branched or cyclic, and may be a monovalent saturated hydrocarbon group as long as it has 1 to 10 carbon atoms. Even a valent unsaturated hydrocarbon group may have a bridged structure. Specific examples of the monovalent hydrocarbon group include, for example, a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, and a monovalent group. An aromatic hydrocarbon group, a monovalent aliphatic hydrocarbon-substituted aromatic hydrocarbon group, a monovalent aromatic hydrocarbon-substituted aliphatic hydrocarbon group, and the like. Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a monovalent hydrocarbon group having 7 to 10 carbon atoms. Aromatic hydrocarbon-substituted aliphatic hydrocarbon groups are preferred. As said C1-C6 monovalent | monohydric aliphatic hydrocarbon group, a C1-C4 alkyl group is preferable and a methyl group and an ethyl group are more preferable. The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group. As said C7-10 aromatic-hydrocarbon substituted aliphatic hydrocarbon group, a benzyl group is preferable.

The polymerizable unsaturated group represented by W ² is preferably a (meth) acryloyloxy group and an allyl group, and more preferably a (meth) acryloyloxy group.

Examples of the divalent organic group represented by Y ² include the same groups as those exemplified as the divalent organic group represented by Y ¹ . As the divalent organic group, an alkanediyl group having 1 to 6 carbon atoms and a group formed by combining an alkanediyl group having 1 to 6 carbon atoms and —O— are preferable. The alkanediyl group having 1 to 6 carbon atoms is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an ethane-1,2-diyl group and a propane-1,3-diyl group. The group formed by combining the alkanediyl group having 1 to 6 carbon atoms and —O— is preferably a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and —O—, and ethane-1,2 -Diyloxy group, ethane-1,2-diyloxy group, propane-1,3-diyloxy group, and propane-1,3-diyloxy group are more preferable.

Specific examples of the compound (a2) in which the cation part has an ammonium cation and a polymerizable unsaturated group include, for example, (meth) acryloyloxyethyltrimethylammonium, (meth) acryloyloxyethyltriethylammonium, (meth) acryloyloxyethyldimethylbenzyl Quaternary ammonium having a (meth) acryloyloxy group such as ammonium or (meth) acryloyloxyethylmethylmorpholino ammonium;
Quaternary ammonium having a (meth) acryloylamino group such as (meth) acryloylaminopropyltrimethylammonium, (meth) acryloylaminoethyltriethylammonium, (meth) acryloylaminoethyldimethylbenzylammonium;
Examples thereof include dimethyldiallylammonium and trimethylvinylphenylammonium.

As the anionic chromophore represented by Q ⁻ , those described above can be used.

(Compound (a3))
The compound (a3) is a compound having an electrically neutral chromophore and a polymerizable unsaturated group. Examples of the electrically neutral chromophore include a polymethine chromophore, a quinoneimine chromophore, a xanthene chromophore, a squarylium chromophore, and a quinophthalone chromophore. These chromophores either have no positively charged functional group and no negatively charged functional group, or have the same number of positively charged functional groups and negatively charged functional groups. As the electrically neutral chromophore, polymethine chromophore, xanthene chromophore, squarylium chromophore and quinophthalone chromophore are preferred.

Specific examples of the electrically neutral chromophore having the same number of positively charged functional groups and negatively charged functional groups include xanthene chromophore represented by the following formula (10). Can do.

In the above formula (10),
R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are each independently a hydrogen atom, —R ⁸⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. However, the hydrogen atom contained in this aromatic hydrocarbon group is a halogen atom, —R ⁸⁸ , —OH, —OR ⁸⁸ , —SO ₃ H, —SO ₃ M ³ , —SO ₃ —, —CO ₂ H, _{^{-CO 2 M 3, -COO -,}} - CO 2 R 88, -SO 3 R 88, which may be substituted with -SO 2 ^{NHR 89} or _-SO 2 ^NR 89 ^{R 90.}
R ⁸⁵ and R ⁸⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^{87 _{is, -SO 3 H, -SO 3 M}} 3, -SO 3 -, - CO 2 H, -CO 2 M 3, -COO -, - CO 2 R 88, -SO 3 R 88, -SO 2 NHR ⁸⁹ or —SO ₂ NR ⁸⁹ R ⁹⁰ .
w is an integer of 0-5.
When w is an integer of 2 or more, the plurality of R ⁸⁷ may be the same or different.
R ⁸⁸ is a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in this saturated hydrocarbon group may be substituted with a halogen atom, and this saturated hydrocarbon group is -O-, -CO- or -NR ^88- between C-C bonds. You may have.
R ⁸⁹ and R ⁹⁰ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or —X ^c , or R ⁸⁹ and R ⁹⁰ are bonded to each other. Or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms. However, the hydrogen atoms contained in the alkyl group and cycloalkyl group, a hydroxyl group, a halogen ^atom, -X c, may be substituted with -CH = CH ₂ or -CH = ^{CHR 88,} also the alkyl group and cycloalkyl The alkyl group may have —O—, —CO— or —NR ⁸⁸ — between the C—C bonds, and the hydrogen atom contained in this heterocyclic group is —R ⁸⁸ , —OH or —X. ^It may be substituted with ^c .
M ³ is a sodium atom or a potassium atom.
^Xc is a C6-C10 aromatic hydrocarbon group or a C5-C10 aromatic heterocyclic group. The hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is substituted with —OH, —R ⁸⁸ , —OR ⁸⁸ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁸⁸ or a halogen atom. May be.
However, any one of R ⁸¹ , R ⁸² , R ⁸³ , R ^84, and R ⁸⁷ has —SO ₃ — or —COO—.

Aromatic hydrocarbon groups represented by the above R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ , alkyl groups represented by R ⁸⁵ and R ⁸⁶ , saturated hydrocarbon groups represented by R ⁸⁸ , R ⁸⁹ and R ⁹⁰ An alkyl group, a cycloalkyl group and a heterocyclic group, and an aromatic hydrocarbon group and an aromatic heterocyclic group represented by ^Xc are an aromatic hydrocarbon group, an alkyl group of the above formula (4), A configuration similar to that of the saturated hydrocarbon group, the heterocyclic group, and the aromatic heterocyclic group can be employed, and a preferable aspect is also as described in the above formula (4).

In the xanthene chromophore represented by the formula (10), any one of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁷ has —SO ₃ — or —COO—. As an embodiment, any one of R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ is an aromatic hydrocarbon group substituted with —SO ₃ — or —COO—, or R ⁸⁷ is —SO 4. _The aspect which is 1 type chosen from _3- and -COO- is mentioned.

  Examples of the squarylium chromophore include compounds described in paragraphs [0132] to [0135] of JP2012-013945A.

  Examples of the quinophthalone chromophore include compounds described in paragraphs [0084] to [0115] of JP2013-209614A.

  Examples of the polymerizable unsaturated group include a (meth) acryloyloxy group, a vinylaryl group, a vinyloxy group, and an allyl group. As the polymerizable unsaturated group, a (meth) acryloyloxy group is preferable.

As the compound (a3), those represented by the following formula (C) are preferable.

In the above formula (C),
R ⁹¹ is a hydrogen atom or a methyl group.
X ³ is a single bond, a substituted or unsubstituted divalent hydrocarbon group, or a divalent group formed by combining a divalent hydrocarbon group and one or more linking groups containing a hetero atom.
Q is an electrically neutral p-valent chromophore.
p is an integer of 1 or more.

  Examples of the electrically neutral p-valent chromophore represented by Q include those obtained by removing p hydrogen atoms from an electrically neutral chromophore. Examples of the electrically neutral chromophore include the polymethine chromophore, quinoneimine chromophore, xanthene chromophore, squarylium chromophore, and quinophthalone chromophore. The electrically neutral chromophore is preferably a polymethine chromophore, a xanthene chromophore, a squarylium chromophore, or a quinophthalone chromophore. The electrically neutral chromophore does not have a functional group having a positive charge and a functional group having a negative charge, or has the same number of functional groups having a positive charge and functional groups having a negative charge. Specific examples of the electrically neutral chromophore having one positively charged functional group and one negatively charged functional group include xanthene chromophore represented by the above formula (10), for example. Can do.

  As said p, the integer of 1-8 is preferable and the integer of 1-4 is more preferable.

Examples of the divalent hydrocarbon group represented by X ³ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. . The divalent aliphatic hydrocarbon group may be either linear or branched. The divalent aliphatic hydrocarbon group and divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group.

  Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group. As a minimum of carbon number of the said bivalent aliphatic hydrocarbon group, 1 is preferable and 2 is more preferable. On the other hand, the upper limit of the carbon number is preferably 20, more preferably 12, and still more preferably 6. Specific examples of the divalent aliphatic hydrocarbon group include the same groups as those described above.

  Examples of the divalent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group. As carbon number of the said bivalent alicyclic hydrocarbon group, 3-20 are preferable and 3-12 are more preferable. Specific examples of the divalent alicyclic hydrocarbon group include monocyclic hydrocarbons such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group. Examples include a cyclic group, a norbornylene group such as a 1,4-norbornylene group and a 2,5-norbornylene group, and a bridged cyclic hydrocarbon ring group such as a 1,5-adamantylene group and a 2,6-adamantylene group. it can.

  The divalent aromatic hydrocarbon group may be a monocyclic aromatic hydrocarbon group or a polycyclic aromatic hydrocarbon group. As carbon number of the said bivalent aromatic hydrocarbon group, 6-14 are preferable. Specific examples of the divalent aromatic hydrocarbon group include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

In the divalent group formed by combining the divalent hydrocarbon group and one or more linking groups containing a hetero atom, examples of the linking group include -O-, -S-, -SO _2- , and -CO. —, —COO—, —OCO—, —CONR ^d — (R ^d is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —NR ^d — (R ^d is as defined above). ) And the like, and one or more of these may be included. The connecting position of the linking group is arbitrary, and for example, it can have a terminal of a divalent hydrocarbon group or a C-C bond, but among these, it can have one terminal or a C-C bond. preferable. In addition, a divalent hydrocarbon group and the linking group may be bonded to form a ring structure. In the divalent group, “carbon number” means the total number of carbon atoms in the portion excluding the carbon atoms constituting the linking group.

Specific examples of the divalent hydrocarbon group having the linking group between the C—C bonds include, for example, —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₂ —, —CH ₂ —CH ( _{-CH 3) -CH 2 -COO-CH} 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -COO _{-CH 2 -CH (CH 2 -CH 3} ) -CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) - _{CH 2 -CH 2 -CH 2 -CH 2} -, - (CH 2) 5 -COO- (CH 2) 11 -CH 2 -, - CH 2 -CH 2 -CH 2 -C- (COO-CH 2 - _{CH 3) 2 -, - CH} 2 -CH 2 -O-CH 2 -CH 2 -, _{CH 2 -CH 2 -CH 2 -O-} CH 2 -CH 2 -, - (CH 2 -CH 2 -O) n-CH 2 - (n is an integer from 1 to 8), - (CH _{2 -CH 2 -CH 2 -O) m-} CH 2 - (m is an integer of 1 to _{5), - CH 2 -CH (CH} 3) -O-CH 2 -CH 2 -, - CH 2 - _{CH- (OCH 3) -, -} CH 2 -CH 2 -COO-CH 2 -CH 2 -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 2 -, _{-CH 2 -CH 2 -CH 2 -O-} CO-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -COO-CH 2 _{-CH 2 -O-CH 2 -CH 2} -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH _{2 -CH 2 -, - CH 2} -CH 2 -NH-COO-CH 2 -CH 2 -, - those but can be given, to be limited to - CH 2 -CH 2 -OCO-CH 2 is not.

  Specific examples of the group having a ring structure formed by combining the divalent hydrocarbon group and the linking group include the following, but are not limited thereto.

  Examples of the substituent that the divalent hydrocarbon group has include a halogen atom, a nitro group, a hydroxy group, a substituted or unsubstituted alkoxyl group, and a substituted or unsubstituted aryloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxyl group may be linear or branched, and the number of carbon atoms is preferably 1-6. Specific examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. As said aryloxy group, a C6-C14 aryloxy group is preferable and a phenoxy group and a benzyloxy group are more preferable. Examples of the substituent for the alkoxyl group and aryloxy group include a halogen atom, a nitro group, a hydroxy group, an amino group, a carboxy group, and a sulfanyl group. Furthermore, when the divalent hydrocarbon group is a divalent aromatic hydrocarbon group, it may be substituted with a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. As carbon number of the said alkyl group and alkenyl group, 1-6 are preferable. Specific examples of the alkyl group and alkenyl group, and specific examples of the substituents thereof include the same groups as described above.

(Structural unit (II))
[A] The emulsion polymer constituting the particles further includes a second structural unit derived from a monomer having no fluorescent function (hereinafter also referred to as “structural unit (II)”) together with the structural unit (I). May be. The monomer having no fluorescence function is not particularly limited as long as it is a compound copolymerizable with compound (a1) to compound (a3), but a compound having two or more crosslinkable groups is preferable. Thus, by using a compound having two or more crosslinkable groups as the monomer having no fluorescence function, the conversion rate during the polymerization reaction can be improved, and the oxidative deterioration of the obtained [A] particles is further suppressed. can do.

Examples of the compound having two or more crosslinkable groups include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 2,3-dimethyl-1,3- Aliphatic conjugated diene compounds such as butadiene;
Non-conjugated divinyl compounds such as divinylbenzene, diisopropenylbenzene and trivinylbenzene;
Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, 1,6-hexane glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, alkylene glycol di (meth) acrylate compounds such as polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypropyroxyphenyl) propane, 2, Examples include di (meth) acrylate compounds such as 2-bis (4- (meth) acryloxydiethoxyphenyl) propane.

  The compound having two or more crosslinkable groups is preferably a non-conjugated divinyl compound and a di (meth) acrylate compound, more preferably a non-conjugated divinyl compound and an alkylene glycol di (meth) acrylate compound, divinylbenzene and ethylene glycol di- More preferred is (meth) acrylate.

Examples of the monomer having no fluorescence function other than the compound having two or more crosslinkable groups include (meth) acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2- (meth) acryloyloxyethyl]. , Ω-carboxypolycaprolactone mono (meth) acrylate,
ethylenically unsaturated monomers having a carboxy group such as p-vinylbenzoic acid;
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;
Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3- (Meth) acrylic acid esters such as [(meth) acryloyloxymethyl] oxetane and 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;
Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane and the like.

  As a monomer having no fluorescence function other than the compound having two or more crosslinkable groups, a (meth) acrylic acid ester is used from the viewpoints of conversion rate, mechanical strength and solvent resistance of the obtained [A] particles. Is preferred.

  [A] When the emulsion polymer constituting the particles has the structural unit (II), the lower limit of the content ratio of the structural unit (I) in all the structural units is preferably 5% by mass, more preferably 10% by mass. 15% by mass is more preferable. On the other hand, as an upper limit of the said content rate, 50 mass% is preferable, 40 mass% is more preferable, and 35 mass% is further more preferable. By making the said content rate into the said range, the conversion rate at the time of a polymerization reaction can be improved, and the oxidation deterioration of the [A] particle | grains obtained can be suppressed more.

  [A] When the emulsion polymer constituting the particles contains a structural unit derived from a compound having two or more crosslinkable groups as the structural unit (II), the compound having two or more crosslinkable groups in all the structural units As a minimum of the content rate of the derived structural unit, 10 mass% is preferable and 15 mass% is more preferable. On the other hand, as an upper limit of the said content rate, 50 mass% is preferable and 40 mass% is more preferable. By making the said content rate into the said range, the conversion rate at the time of a polymerization reaction can be improved, and the oxidation deterioration of the [A] particle | grains obtained can be suppressed more.

[[A] Particle Production Method]
[A] The particles are produced by emulsion polymerization. As the above emulsion polymerization method, a monomer having a fluorescent function and a monomer having no fluorescent function which are used as necessary in an aqueous dispersion medium such as water (hereinafter, these monomers are collectively referred to as “precursor”). And a method of carrying out emulsion polymerization by adding a chain transfer agent, a polymerization initiator, an emulsifier, and the like.

[A] The particles are preferably produced by a production method comprising at least the following step (1) and step (2).
Step (1): A step of preparing a mixed solution containing at least water, (i) an emulsifier, and a precursor monomer, and (ii) a solution containing a polymerization initiator.
Step (2): A step of emulsion polymerization by mixing a mixed solution containing the precursor monomer obtained in Step (1) and a solution containing a polymerization initiator.
Hereinafter, each step will be described.

(Process (1))
Step (1) includes at least water, (i) a mixture containing an emulsifier and a precursor monomer (hereinafter, also referred to as “precursor monomer mixture”), and (ii) a solution containing a polymerization initiator (hereinafter, “ A polymerization initiator solution ”). This polymerization initiator solution may further contain water and (i) an emulsifier. The mass ratio of the polymerization initiator solution to the precursor monomer mixture is, for example, from 0.5 to 2.0. First, each component will be described.

((I) Emulsifier)
(I) As the emulsifier, a general emulsifier generally known in emulsion polymerization can be used. Examples of such emulsifiers include alkali metal salts (particularly sodium and potassium salts) of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid;
Sodium lauryl sulfate, sodium lauryl sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl diphenyl ether sulfonate, sodium oxalic acid dialkyl ester sulfonate, alkali metal rosin acid (especially sodium salt, potassium salt), sodium formaldehyde condensed sodium naphthalene sulfonate, etc. Anionic surfactants of
Nonionic surfactants such as polyoxyethylene alkyl esters and polyoxyethylene alkyl aryl ethers;
Alkyl betaine type salts such as lauryl betaine and stearyl betaine salts;
Examples include double-sided surfactants such as amino acid types such as lauryl-β-alanine, lauryl di (aminoethyl) glycine, and octyldi (aminoethyl) glycine.

  (I) As a minimum of the usage-amount of an emulsifier, it is 0.1 mass part normally with respect to 100 mass parts of precursor monomers, 1 mass part is preferable and 10 mass parts is more preferable. On the other hand, (i) As an upper limit of the usage-amount of an emulsifier, it is 60 mass parts normally with respect to 100 mass parts of precursor monomers, and 40 mass parts is preferable. Here, the “use amount” of each material used for the emulsion polymer refers to the total of the content contained in the precursor monomer mixed solution and the content contained in the polymerization initiator solution.

((Ii) polymerization initiator)
(Ii) As the polymerization initiator, a general polymerization initiator generally known in emulsion polymerization can be used. (Ii) Examples of the polymerization initiator include inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate;
Organic peroxides such as cumene hydroperoxide, benzoyl peroxide, isopropylbenzene peroxide;
An azo initiator such as azoisobutyronitrile is used. These polymerization initiators may be used alone or in combination of two or more.

These polymerization initiators can also be used as so-called redox initiators in combination with a reducing agent. Examples of the reducing agent include reducing sulfoxylates such as sulfite, hydrogen sulfite, pyrosulfite, nitrite, nithionate, thiosulfate, formaldehyde sulfonate, and benzaldehyde sulfonate;
Examples thereof include ferrous sulfate, ferrous ammonium sulfate, and cuprous naphthenate.

  (Ii) As the polymerization initiator, inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate are preferable from the viewpoint of polymerization stability.

  (Ii) As a minimum of the usage-amount of a polymerization initiator, it is 0.1 mass part normally with respect to 100 mass parts of precursor monomers, and 0.2 mass part is preferable. On the other hand, the upper limit of the amount used is usually 5 parts by mass and preferably 2 parts by mass with respect to 100 parts by mass of the precursor monomer.

((Iii) chain transfer agent)
(Iii) A chain transfer agent may be added to the precursor monomer mixed solution and the polymerization initiator solution. (Iii) As a chain transfer agent, the usual chain transfer agent generally known in emulsion polymerization can be used. Examples of such chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan;
Xanthogen disulfides such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide;
Thiuram disulfides such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide;
Halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide;
Hydrocarbons such as pentaphenylethane, 1,1-diphenylethylene, α-methylstyrene dimer;
Acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, terpinolene, α-terpinene, γ-terpinene, dipentene and the like can be mentioned. These chain transfer agents can be used alone or in combination of two or more.

  (Iii) As a minimum of the usage-amount of a chain transfer agent, it is 0.05 mass part normally with respect to 100 mass parts of precursor monomers, 0.1 mass part is preferable and 0.2 mass part is more preferable. On the other hand, the upper limit of the amount used is usually 20 parts by mass, preferably 15 parts by mass, and more preferably 10 parts by mass.

((Iv) Other ingredients)
To the precursor monomer mixed solution and the polymerization initiator solution, a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as polycarboxylate, and an inorganic salt such as phosphate may be added. In addition, for the above emulsion polymerization, if necessary, for example, a pH adjuster such as ammonia, sodium hydroxide or potassium hydroxide; an anti-aging agent such as styrenated phenol, hindered phenol, imidazoles or paraphenylenediamine; acetophenone Flavoring agents such as cinnamaldehyde, panillin, lavender oil; antibacterial agents such as siabendazole, preventol, and binadin; antifoaming agents such as silicones and higher alcohols; dimethyldithiocarbamate, NNdimethylhydroxyamine, thio Reaction stoppers such as urea; additives such as antifreezing agents such as ethylene glycol, diethylene glycol and urea may be added as appropriate.

  It does not specifically limit as a preparation method of a precursor monomer liquid mixture and a polymerization initiator solution, Each component may be added separately or all the components may be added simultaneously. When adding each component separately, the addition order of each component is not specifically limited. In addition, although the density | concentration of the precursor monomer in a precursor monomer liquid mixture can be selected suitably, it is 10 to 50 mass% normally. The concentration of the polymerization initiator in the polymerization initiator solution can be appropriately selected, but is usually 0.01% by mass or more and 0.5% by mass or less. The precursor monomer mixed solution and the polymerization initiator solution may be emulsified after preparation, but can be used as they are without emulsification. The emulsification method is not particularly limited, and a conventionally known method can be appropriately selected.

(Process (2))
Step (2) is a step of emulsion polymerization by mixing a mixed solution containing the precursor monomer obtained in step (1) and a polymerization initiator solution. In the step (2), as a method of charging the precursor monomer mixed solution into the reaction vessel, a method of charging all of the precursor monomer mixed solution at once, the precursor monomer mixed solution continuously or intermittently as the polymerization proceeds. Any of the method of charging automatically, starting a polymerization by charging a part of the precursor monomer mixture, and then polymerizing the remaining precursor monomer mixture in a batch or continuously or intermittently A method may be adopted. In addition, as a method of charging the polymerization initiator solution into the reaction solution in the step (2), a method of charging all of the polymerization initiator solution all together, a polymerization initiator solution being continuously or intermittently accompanied with the progress of polymerization. Any method such as a method of charging to a polymer, starting a polymerization by charging a part of the polymerization initiator solution, and then charging the remaining polymerization initiator solution all at once or continuously or intermittently is employed. May be. In these cases, the composition of the precursor monomer mixed solution and / or the polymerization initiator solution added continuously or intermittently may be the same or may be changed.

  As a minimum of polymerization temperature of emulsion polymerization, it is 5 ° C usually and 20 ° C is preferred. On the other hand, the upper limit of the polymerization temperature is usually 85 ° C and preferably 80 ° C. The polymerization time for emulsion polymerization is usually from 1 hour to 12 hours. The emulsion polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas. The lower limit of the final polymerization conversion rate in emulsion polymerization is preferably 90%.

  You may refine | purify the obtained [A] particle | grains as needed. Examples of the method for purifying [A] particles contained in the reaction liquid (suspension) after emulsion polymerization include filter filtration, centrifugation, decantation and the like.

  In addition, it is preferable that the refractive index of [A] particle | grains is substantially identical or close to the refractive index of the binder resin mentioned later.

  The lower limit of the content of [A] particles in the wavelength conversion film is preferably 0.001% by mass, and 0.01% by mass from the viewpoints of heat resistance, solvent resistance, dye transfer control, and wavelength conversion efficiency. Is more preferable. On the other hand, the upper limit of the content is preferably 10% by mass, and more preferably 1% by mass.

[[B] Binder resin]
[B] The binder resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin, and may be a crosslinked resin or a non-crosslinked resin. [B] Examples of the binder resin include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and resins having an acidic functional group such as a carboxy group and a phenolic hydroxyl group. [B] The binder resin is preferably polyester. Examples of the polymer having a carboxy group (hereinafter also referred to as “carboxy group-containing polymer”) include, for example, an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as “unsaturated monomer (b1)”. ) ”) And other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as“ unsaturated monomer (b2) ”). [B] Binder resins can be used alone or in admixture of two or more.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. And p-vinylbenzoic acid. These unsaturated monomers (b1) can be used alone or in admixture of two or more.

  Examples of the unsaturated monomer (b2) include N-position substituted maleimide, aromatic vinyl compound, (meth) acrylic acid ester, vinyl ether, and a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain. Specific examples include the same compounds as those described above for the monomer having no fluorescence function. An unsaturated monomer (b2) can be used individually or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the lower limit of the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is 5% by mass. Preferably, 10 mass% is more preferable. On the other hand, the upper limit of the copolymerization ratio is preferably 50% by mass, and more preferably 40% by mass. By setting the copolymerization ratio in the above range, a wavelength conversion film having excellent storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Name the coalition party.

  Examples of the [B] binder resin include JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, and JP-A-11-140144. As disclosed in JP-A-2008-181095 and the like, a carboxy group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used.

  [B] The lower limit of the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter also referred to as “GPC”) of the binder resin (elution solvent: tetrahydrofuran) is usually 1,000. 3,000 is preferred. On the other hand, the upper limit of the Mw of the [B] binder resin is usually 100,000, and preferably 50,000. [B] By setting the Mw of the binder resin in the above range, the heat resistance can be improved, and the generation of dry foreign matters during film formation can be suppressed at a high level.

  [B] The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin fat is preferably 1.0 or more and 5.0 or less, and 1.0 or more and 3.0. The following is more preferable. Here, “Mn” refers to a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

  [B] The binder resin can be produced by a known method. For example, the method disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. Thus, the structure, Mw, Mw / Mn and the like can be controlled.

  As a minimum of content of [B] binder resin in the said wavelength conversion film, it is 50 mass parts normally with respect to 100 mass parts of [A] particle | grains, and 300 mass parts is preferable. On the other hand, the upper limit of the content of the [B] binder resin is usually 1,000 parts by mass and preferably 700 parts by mass with respect to 100 parts by mass of the [A] particles. [B] By making content of binder resin into the said range, the storage stability of the raw material composition of the said wavelength conversion film, a chromaticity characteristic, etc. can be improved.

[Other colorants]
The wavelength conversion film may contain a colorant other than [A] particles. The other colorant is not particularly limited, and the color and material can be appropriately selected according to the application. Examples of the other colorant include pigments and dyes, and these can be used alone or in combination of two or more. As the other colorant, from the viewpoint of colorability, an organic pigment is preferable as the pigment, and an organic dye is preferable as the dye. These other colorants can be used alone or in admixture of two or more.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyersand Colorists), that is, the following color index (CI) numbers. You can list what you have.

C. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 264;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment green 59;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 215;
C. I. Pigment orange 38;
C. I. Pigment Violet 23.

  Other examples of the organic pigment include JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237369, JP-A-2011-006602, Examples include lake pigments described in Japanese Unexamined Patent Publication No. 2011-145346.

  The pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, the pigment surface may be modified with a resin if desired. Examples of the resin that modifies the pigment particle surface include vehicle resins described in JP-A No. 2001-108817, commercially available resins for dispersing pigments, and the like. As a method for modifying the pigment surface with a resin, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used by refining primary particles by so-called salt milling. As the salt milling method, for example, a method disclosed in Japanese Patent Laid-Open No. 8-179111 can be adopted.

  The other colorants can be used in combination with known dispersants and dispersion aids. Known dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Agents, polyester dispersants, acrylic dispersants and the like. In addition, examples of known dispersion aids include pigment derivatives.

  Examples of commercially available dispersants include acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)) and the like, and urethane dispersants such as Disperbyk. -161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol), etc. As a polyester-based dispersant such as Solsperse 24000 (manufactured by Lubrizol), Addispar PB821, Addispar PB822, Addisper PB880, Addispa PB881 (above, manufactured by Ajinomoto Fine-Techno Co., Inc.), and the like, respectively. In addition, BYK-LPN21324 (manufactured by BYK Corporation (BYK)) can also be used.

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

  When the wavelength conversion film contains the other colorant, the lower limit of the content of the other colorant is not particularly limited, but for example, 0.01 parts by mass with respect to 100 parts by mass of the [A] particles. is there. On the other hand, as an upper limit of content of said other coloring agent, 250 mass parts is preferable with respect to 100 mass parts of [A] particle | grains, and 100 mass parts is more preferable.

<Method for producing wavelength conversion film>
Although it does not specifically limit as a manufacturing method of the said wavelength conversion film, For example, the method etc. which shape | mold the film formation composition containing a [A] particle | grain into a film form can be used. The film-forming composition usually further contains a [B] binder resin. Moreover, it is preferable that the said film formation composition further contains a solvent, and may contain another additive. Hereinafter, each component used for the film-forming composition will be described.

[solvent]
The solvent used in the film-forming composition is not particularly limited as long as it can disperse or dissolve [A] particles and other optional components and does not react with these components and has appropriate volatility. However, an organic solvent is preferable.

Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl. Ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, Dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Cyclic ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Fatty acid alkyl esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  Examples of the organic solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol from the viewpoints of solubility of [B] binder resin, dispersibility of [A] particles, coatability, and the like. Monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol Diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyrate Butyl and ethyl pyruvate are preferred. The said solvent can be used individually or in mixture of 2 or more types.

  Although it does not specifically limit as a minimum of solid content concentration in the said film formation composition, 5 mass% is preferable and 10 mass% is more preferable. On the other hand, the upper limit of the solid content concentration is preferably 50% by mass, and more preferably 40% by mass. By making the said solid content concentration into the said range, the dispersibility of the said composition for film formation, stability, and applicability | paintability can be improved. Here, the “solid content” refers to all components other than the solvent of the film-forming composition.

  Examples of additives that the film-forming composition may contain include, for example, fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); fluorine-based surfactants, and silicones Surfactants such as surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as tildimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) ), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones Anticoagulant such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol 3-amino-1,2-propanediol, 2-amino-1,3-propane Residue improvers such as all, 4-amino-1,2-butanediol; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- Examples include developability improvers such as carboxypolycaprolactone mono (meth) acrylate.

  The film-forming composition can be prepared, for example, by mixing [A] particles with a solvent or an optional component.

  As a method for forming the film-forming composition into a film, for example, a so-called casting method including a step of applying the film-forming composition on a support and a step of drying the obtained coating film is preferable. .

  The method for coating the film-forming composition on the support in the casting method is not particularly limited, and a conventionally known method can be employed.

  It does not specifically limit as a method of drying the said coating film, You may stand still at room temperature and you may heat at 30 to 100 degreeC.

  The film-forming composition may be formed into a film by a melt extrusion method, a calendar method, or the like. A so-called T-die method comprising a step of melting the film-forming composition and a step of extruding the obtained melt using a T-die is preferred as a method of forming into a film by melt extrusion. The temperature at the time of melting can be, for example, 120 ° C. or higher and 220 ° C. or lower.

<Cultivation method for crops>
The method for cultivating the crop is characterized in that the LED is used as a light source, and the output light of the LED is wavelength-converted by the wavelength conversion film described above to irradiate the crop. The cultivation method of the crop uses an LED with low power consumption as a light source, and irradiates the crop with the light emitted from the LED by converting the wavelength of the emitted light with the wavelength conversion film. be able to. Moreover, since the said wavelength conversion film is excellent in weather resistance, it can suppress replacement frequency. As a result, the crop cultivation method can cultivate the crop at a low cost.

  As said LED, white LED which is cheap compared with another LED is preferable. As the white LED, one that emits blue light (for example, a wavelength of 450 nm or more and less than 500 nm) and yellow light (for example, a wavelength of 570 nm or more and less than 600 nm), blue light, red light (for example, a wavelength of 600 nm or more and less than 800 nm), and green light (for example, Those that irradiate with a wavelength of 500 nm or more and less than 570 nm are generally used, but any of them can be used.

  In the method for cultivating the crop, the crop may be irradiated only with light obtained by converting the wavelength of the emitted light of the LED with the wavelength conversion film (hereinafter also referred to as “wavelength converted light”). Irradiation may be performed in combination with the light. As said other light, the light radiate | emitted from other artificial light sources, such as a fluorescent lamp, sunlight, etc. are mentioned, for example. Further, in the method for cultivating the crop, the wavelength-converted light may be irradiated to the crop during at least a part of the cultivation period. For example, the wavelength-converted light is used only in a time zone in which sunlight is not available, such as at night, rainy weather, and cloudy weather. May be applied to crops.

  The crops cultivated by the crop cultivation method are not particularly limited. For example, grains such as wheat and corn, vegetables such as lettuce, cabbage and tomatoes, fruits such as apples and strawberries, and ornamental items such as tulips, roses and orchids. Examples include plants.

  In the cultivation method of the said crop, it is not specifically limited except the point which irradiates the said wavelength-converted light to a crop, For example, hydroponics, house cultivation, etc. can be performed.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Synthesis Example 1] (Production of (A-1) Particles)
According to Synthesis Example 1 of JP-A-2015-214682, particles (A-1), which is an emulsion polymer having a structural unit derived from a monomer having a fluorescence function, were synthesized. Specifically, 20.0 g of methyl methacrylate, 5.00 g of ethylene glycol dimethacrylate, and 6.50 g of monomer (1) represented by the following formula were mixed uniformly. This mixed solution was added to a container containing 6.3 g of sodium dodecyl sulfonate and 56.9 g of ion-exchanged water to prepare a precursor monomer mixed solution.

  Separately, 0.6 g of sodium dodecyl sulfonate, 1.5 g of a 5% by weight aqueous solution of sodium persulfate, and 110.5 g of ion-exchanged water were mixed to prepare a polymerization initiator solution. The precursor monomer mixture was heated to 80 ° C. under a nitrogen flow. The polymerization initiator solution was added dropwise to the heated precursor monomer mixture over 3 hours. After completion of the dropping, the reaction solution was aged by maintaining the internal temperature at 80 ° C. for 1 hour. Subsequently, an aqueous solution in which 1.3 g of a 2% by weight aqueous solution of sodium persulfate and 0.5 g of ion-exchanged water were mixed was added to the reaction solution. The reaction solution was further aged at 80 ° C. for 2 hours, and then allowed to cool to room temperature. Thereafter, the reaction solution was filtered and the solvent was removed under reduced pressure. The resulting emulsion polymer particles were designated as (A-1) particles. As for (A-1) particle | grains, 90% or more of spherical particles were on the number basis, and the average particle diameter calculated | required by observation of a transmission electron microscope was 250 nm.

<Example 1> (Production of wavelength conversion film 1)
[B] Polyester ("DYNARON (registered trademark) 8903P" manufactured by JSR), which is a thermoplastic resin, was prepared as a binder resin. 0.2% by mass of the particles (A-1) obtained in Synthesis Example 1 was blended with this polyester and kneaded with a Henschel mixer to prepare a film-forming composition. Subsequently, the said film formation composition was shape | molded by the T-die method (melting temperature 180 degreeC) using an extruder, and the wavelength conversion film 1 with an average thickness of 150 micrometers was manufactured.

<Comparative Example 1> (Production of wavelength conversion film 2)
(A-1) A wavelength conversion film 2 was produced in the same manner as in Example 1 except that 0.04% by mass of the monomer (1) was added to the polyester instead of the particles.

<Comparative Example 2> (Production of wavelength conversion film 3)
In Synthesis Example 1, the same amount of the phosphor (1) represented by the following formula was used in place of the monomer (1), and the same operation was performed without changing the other points. -2) Particles were synthesized. As for (A-2) particle | grains, 90% or more of spherical particles were based on the number basis, and the average particle diameter calculated | required by observation of a transmission electron microscope was 240 nm. (A-1) A wavelength conversion film 3 was produced in the same manner as in Example 1 except that 0.04% by mass of (A-2) particles was blended with polyester instead of particles.

<Comparative Example 3> (Production of wavelength conversion film 4)
In Synthesis Example 1, 0.02 g of azobisisobutyronitrile was used in place of sodium dodecyl sulfonate and sodium persulfate, and the rest of the procedure was performed in the same manner without changing, and the suspension polymer (A -3) Particles were synthesized. As for (A-3) particles, 90% or more of the particles were spherical particles on the basis of the number, and the average particle size determined by observation with a transmission electron microscope was 10 μm. (A-1) A wavelength conversion film 4 was produced in the same manner as in Example 1 except that 0.04% by mass of (A-3) particles was blended with polyester instead of particles.

[Measurement of wavelength conversion efficiency and weather resistance test]
About the obtained wavelength conversion film, using a sunshine weather meter (“300 Sunshine Weather Meter” by Suga Test Instruments Co., Ltd.) equipped with an open frame carbon arc lamp in accordance with JIS-K7350-4: 2008, 1,000 hours A weather resistance test was conducted. About the wavelength conversion film before and after the weather resistance test, the intensity L1 of light having a wavelength of 600 nm to 700 nm contained in sunlight, and 600 nm to 700 nm contained in wavelength converted light obtained by transmitting the sunlight through the wavelength conversion film. The light intensity L2 of the wavelength was obtained, and the ratio of L2 to L1 (L2 / L1) was defined as the wavelength conversion efficiency. The ratio (R2 / R1) of the wavelength conversion efficiency R2 after the weather resistance test to the wavelength conversion efficiency R1 before the weather resistance test was used as an index of the weather resistance of each wavelength conversion film. Table 1 shows the wavelength conversion efficiency R1 before the weather resistance test and the ratio (R2 / R1) of the wavelength conversion efficiency R2 after the weather resistance test to the wavelength conversion efficiency R1 before the weather resistance test.

  Although not shown in Table 1, the sunlight transmitted through the wavelength conversion films 1 to 4 is 400 nm or more and less than 600 nm in the photosynthetic effective radiation (PAR: light having a wavelength of 400 nm to 700 nm) than the sunlight before transmission. The intensity of light of the wavelength of was reduced. However, as shown in Table 1, the wavelength conversion efficiency R1 of the wavelength conversion films 1 and 2 exceeded 1. That is, the intensity of light having a wavelength of 600 nm or more and less than 700 nm was increased in sunlight transmitted through the wavelength conversion films 1 and 2 compared to sunlight before transmission. From this, it is determined that the wavelength conversion films 1 and 2 of Example 1 and Comparative Example 1 can convert the wavelength of yellow light, green light, and the like, which are less important for plant growth, to red light with higher importance. The

  On the other hand, the wavelength conversion films 3 to 4 of Comparative Examples 2 to 3 had a wavelength conversion efficiency R1 of less than 1. In other words, the sunlight transmitted through the wavelength conversion films 3 to 4 of Comparative Examples 2 to 3 had a lower intensity of red light than the sunlight before transmission. This is because the (A-2) particles used in Comparative Example 2 are not chemically bonded to the phosphor (1) and the polymer contained in the (A-2) particles. ) Is likely to be lost by elution into the polymerization solvent. As a result, the wavelength conversion film 3 cannot exhibit the wavelength conversion effect due to the insufficient content of the phosphor (1), and the (A-2) particles and the [B] binder resin are solar. It is considered that the wavelength conversion efficiency R1 is less than 1 because red light contained in the light is scattered and absorbed. Moreover, since the wavelength conversion film 4 has a relatively large average particle diameter of (A-3) particles, the effect of promoting the scattering and absorption of sunlight and reducing the transparency of the film rather than the wavelength conversion effect. As a result, the wavelength conversion efficiency R1 is considered to be less than 1.

  Moreover, as shown in Table 1, the wavelength conversion film 1 of Example 1 had good weather resistance, and the wavelength conversion efficiency hardly decreased before and after the weather resistance test. On the other hand, the wavelength conversion film 2 of Comparative Example 1 was not good in weather resistance, and the wavelength conversion efficiency significantly decreased before and after the weather resistance test. The reason why the wavelength conversion film 1 has good weather resistance is that the particles (A-1) used are emulsion polymers using a monomer having a fluorescence function, and therefore the main chain of the emulsion polymer is not a capsule-like outer layer. It is thought that this is because the formation of a shell and confinement of a side chain having a fluorescence function in this outer shell inhibited the contact between the side chain and oxygen, and as a result, the decrease in fluorescence function due to oxidative degradation was suppressed. . On the other hand, the reason that the weather resistance of the wavelength conversion film 2 is not good is that the unpolymerized monomer (1) is used, so that the protective effect from the above-mentioned oxidation degradation cannot be received, and as a result, the weather resistance test is in progress. This is considered to be because the fluorescence function of the monomer (1) was deactivated due to oxidative degradation.

  Furthermore, the wavelength conversion film 4 of Comparative Example 3 had a wavelength conversion efficiency that was insufficient as less than 1 even before the weather resistance test, and further significantly decreased after the weather resistance test. This is considered to be because the wavelength conversion function of the particles (A-3) was deactivated due to oxidative degradation. From this, even if it has a structural unit derived from a monomer having a fluorescence function, it is judged that the suspension polymer hardly receives the above-mentioned protective effect from oxidative degradation.

  As described above, the wavelength conversion film 1 of Example 1 contains the (A-1) particles that are emulsion polymers having a structural unit derived from a monomer having a fluorescence function, and thus has a wavelength conversion film excellent in weather resistance. It can be used as

[Cultivation test]
Next, a crop cultivation test was performed using each wavelength conversion film. Under artificial light irradiated with white LED using five cultivation devices with light sources (plant cultivation container, Ewing “Green Farm (registered trademark) UH-A01E1”) (hereinafter referred to as devices A to E, respectively) Gentina Green (manufactured by Ewing) was cultivated. In the devices A to D, the light source was covered with the wavelength conversion films 1 to 4 so that the light emitted from the light source was applied to the gentina green after passing through the wavelength conversion film. In the apparatus E, the wavelength conversion film was not used, and the light emitted from the light source was directly applied to the gentina green. Each device was covered with a light-shielding curtain to prevent the influence of external light.

  In the main cultivation test, each device was installed in a room adjusted to a temperature of 20 ° C. and a relative humidity of 50%, and the carbon dioxide concentration was not adjusted and was set to the same concentration as the atmosphere. The artificial light irradiation condition was a one-day cycle of lighting for 16 hours and turning off for 8 hours. The cultivation period was from October 28, 2015 to November 28, 2015. After cultivation, Gentina green was harvested from the devices A to E, and its mass was measured. The average mass of the first to sixth heaviest gentina greens harvested from each device was calculated and used as an index of the yield (g) of each device.

  As is clear from Table 2, in Example 1, by using the wavelength conversion film 1, Comparative Example 1 using the wavelength conversion film 2 having the same degree of wavelength conversion efficiency but not good weather resistance, wavelength conversion The yield was higher than any of Comparative Examples 2 to 3 using wavelength conversion films 3 to 4 having low efficiency and Comparative Example 4 using no wavelength conversion film. From this, by using the wavelength conversion film 1, among the light irradiated from the white LED which is the light source of the cultivation apparatus, green light and yellow light which are less important in the growth of plants are converted into red light which is highly important. Wavelength conversion can be performed, and as a result, it is determined that the yield can be increased.

  In addition, although the wavelength conversion efficiency of the wavelength conversion films 1-2 is comparable, the wavelength conversion film 1 is hard to fall in wavelength conversion efficiency during a cultivation period, whereas the wavelength conversion film 2 is a single amount during a cultivation period. Since the wavelength conversion efficiency tends to decrease due to the oxidative degradation of the body (1), it is determined that Example 1 had a larger yield than Comparative Example 1.

  From the above, it is determined that the yield can be increased by applying the wavelength conversion film to a method for cultivating crops using LEDs as a light source. Moreover, since the said wavelength conversion film is excellent in drought tolerance, it is judged that exchange frequency can be suppressed when it applies to the cultivation method of agricultural products. Accordingly, it is determined that the crop cultivation method using the wavelength conversion film can cultivate the crop at low cost.

  The wavelength conversion film of the present invention is excellent in weather resistance. The crop cultivation method of the present invention can grow crops at low cost.

Claims (7)

A wavelength conversion film used for wavelength conversion of light irradiated on agricultural products,
A wavelength conversion film comprising particles which are emulsion polymers having a first structural unit derived from a monomer having a fluorescence function. The wavelength according to claim 1, wherein the monomer having a fluorescence function is at least one compound selected from the group consisting of compounds represented by the following formulas (A), (B), and (C). Conversion film.

(In the formula (A),
W ¹ is a monovalent polymerizable unsaturated group.
X ¹ is a monovalent group having a halogen atom, a monovalent halogenated hydrocarbon group, or a linking group containing a hetero atom other than a halogen atom between carbon-carbon atoms of the monovalent halogenated hydrocarbon group.
Y ¹ is a single bond or a divalent organic group.
Q ⁺ is a cationic chromophore. )

(In the formula (B),
R ^{71 to} R ⁷³ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
W ² is a monovalent polymerizable unsaturated group.
Y ² is a single bond or a divalent organic group.
Q ⁻ is an anionic chromophore. )

(In the formula (C),
R ⁹¹ is a hydrogen atom or a methyl group.
X ³ is a single bond, a substituted or unsubstituted divalent hydrocarbon group, or a divalent group formed by combining this divalent hydrocarbon group and one or more linking groups containing a hetero atom.
Q is an electrically neutral p-valent chromophore.
p is an integer of 1 or more. )   The wavelength conversion film according to claim 1 or 2, wherein the emulsion polymer further has a second structural unit derived from a monomer having no fluorescence function.   The wavelength conversion film according to claim 3, wherein the monomer having no fluorescence function has two or more crosslinkable groups.   The wavelength conversion film according to any one of claims 1 to 4, wherein wavelength conversion of light having a wavelength of 500 nm or more and less than 600 nm is performed to light having a wavelength of 600 nm or more and 800 nm or less.   The wavelength conversion film according to any one of claims 1 to 5, wherein an average particle diameter of the particles is 30 nm or more and 1,000 nm or less. A method for cultivating crops using LEDs as a light source,
A method for cultivating a crop, wherein the light emitted from the LED is wavelength-converted by the wavelength conversion film according to any one of claims 1 to 6 and irradiated to the crop.