CN118043408A - Near infrared transmitting black particles - Google Patents
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- CN118043408A CN118043408A CN202280056080.5A CN202280056080A CN118043408A CN 118043408 A CN118043408 A CN 118043408A CN 202280056080 A CN202280056080 A CN 202280056080A CN 118043408 A CN118043408 A CN 118043408A
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Abstract
The present invention provides near infrared ray transmitting black particles having high transmittance in the near infrared ray region and low transmittance in the visible light region. The present invention relates to near infrared ray transmitting black particles, wherein the transmittance T 600 (%) at a wavelength of 600nm and the transmittance T 900 (%) at a wavelength of 900nm measured by using a spectrophotometer satisfy the relationship of the following formula (1). T 900－T600 is more than or equal to 60 (1).
Description
Technical Field
The present invention relates to near infrared ray transmitting black particles.
Background
Conventionally, carbon black is generally used as a black material, and iron oxide black (ferroferric oxide) or the like is used in addition to this. They display black and absorb light of a wavelength ranging from the visible light region to the far infrared region, and therefore articles such as coating films colored with these black materials are liable to become high in temperature due to the absorption of sunlight. Further, carbon black has conductivity, and thus an article colored with carbon black has a property of lacking electrical insulation.
On the other hand, in recent years, in the fields of electronic devices and optical devices, there has been an increasing field of black materials having properties not found in black materials such as carbon black which have been conventionally used generally, due to the use of infrared laser radiation and the progress of sensors corresponding thereto.
For example, in infrared communication, infrared camouflage, optical filters, and the like, oil-soluble dyes are used as coloring materials for infrared transmission filters, but these oil-soluble dyes have problems in durability such as heat resistance, solvent resistance, light resistance, and the like, and therefore dark color materials having excellent durability and excellent infrared transmission are being sought. In addition, from the viewpoint of energy saving, it is desired to obtain heat-insulating coating that reflects sunlight, and a heat-ray reflective material used for this purpose is desired to be used as a heat-raising material such as a roof, wall coating, road pavement, exterior and interior of an automobile, and also as an electronic component coating, and a heat-ray reflective material such as a heat-insulating material is also desired in agricultural applications.
In particular, a black material having sufficient transmittance for light having a wavelength from near infrared to infrared is being put into practical use. For example, patent document 1 describes a dark-colored azo pigment obtained by using 2-hydroxy-11H-benzo [ a ] carbazole-3-carboxy-N-benzimidazolone-5-amide as a coupling component, using a known diazo compound as a diazo component, and performing a coupling reaction between the two.
Patent document 2 describes a black film in which the volume fraction of the black material is 2% to 30% by volume, the average dispersion particle diameter in the film is 1nm to 200nm, the optical density per 1 μm thickness is 1 to 1, and the volume resistivity is 10 11 Ω·cm or more.
Prior art literature
Patent literature
Patent document 1: international publication No. 2010/044393
Patent document 2: international publication No. 2012/026577
Disclosure of Invention
Problems to be solved by the invention
However, even with the materials of patent document 1 and patent document 2, the transmittance of near infrared rays is still insufficient. In addition, there is a problem that the transmittance of visible light becomes high.
Therefore, in patent document 1 and patent document 2, there are cases where it is necessary to thicken the formed coating film or to increase the amount of black material added to block visible light or the like, thereby restricting the design of the coating film.
In view of the above-described situation, an object of the present invention is to provide: the near infrared transmitting black particles have high transmittance in the near infrared region and low transmittance in the visible region.
Means for solving the problems
The present disclosure (1) is a near infrared ray transmitting black particle whose transmittance T 600 (%) at a wavelength of 600nm and transmittance T 900 (%) at a wavelength of 900nm measured using a spectrophotometer satisfy the relationship of the following formula (1).
T900－T600≥60 (1)
The present disclosure (2) relates to the near infrared ray transmitting black particles described in the present disclosure (1), wherein T 600 is less than 10% and T 900 is more than 80%.
The present disclosure (3) relates to the near infrared ray-transmissive black particles described in the present disclosure (1) or (2), wherein the diffuse transmittance Td 900 (%) at a wavelength of 900nm measured using a spectrophotometer is 10% or less.
The present disclosure (4) relates to the near infrared ray-transmissive black particles described in any one of (1) to (3) of the present disclosure, wherein the diffuse transmittance Td 1100 (%) at a wavelength of 1100nm measured using a spectrophotometer is 10% or less.
The present disclosure (5) relates to the near infrared-transmitting black particles according to any one of the present disclosure (1) to (4), comprising: a copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group, and a structural unit derived from an amino group-containing compound.
The present disclosure (6) relates to the near infrared-transmitting black particles according to any one of the present disclosure (1) to (5), which contain a crosslinking agent.
The present disclosure (7) relates to the near infrared-transmitting black particles according to any one of the present disclosure (1) to (6), wherein the copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group and a structural unit derived from an amino group-containing compound contains a color assisting group.
The present invention is described in detail below.
As a result of intensive studies, the present inventors have found that near infrared ray-transmitting black particles having a high transmittance in the near infrared ray region and a low transmittance in the visible light region can be obtained by satisfying a predetermined relationship between the transmittance T 600 at a wavelength of 600nm and the transmittance T 900 at a wavelength of 900nm, and have completed the present invention.
Regarding the near infrared ray-transmissive black particles of the present invention, the transmittance T 600 (%) at the wavelength 600nm and the transmittance T 900 (%) at the wavelength 900nm measured using a spectrophotometer satisfy the following relation of formula (1) (hereinafter, the transmittance at the wavelength λnm is referred to as T λ (%)).
T900－T600≥60 (1)
By satisfying the above relation, near infrared ray transmitting black particles having high transmittance in the near infrared ray region and low transmittance in the visible light region can be produced.
The "T 900－T600" is preferably 65% or more, more preferably 70% or more.
The upper limit of "T 900－T600" is not particularly limited, but the higher the upper limit, the more preferable the upper limit is 100%.
The above-mentioned T 600 and T 900 can be measured by, for example, using a spectrophotometer with an integrating sphere, and attaching a reflecting plate on the opposite side to the light incident side (hereinafter, T 850、T800、T600 also uses the same measuring method). In the present specification, the term "transmittance" refers to "total light transmittance" and is distinguished from "diffuse transmittance" described later.
As samples for measuring T 600 and T 900, glass plates obtained by: the near infrared-transmitting black particles of the present invention were mixed with a polyvinyl acetal resin at a ratio of 1:9, dissolved in a solvent, and then the solution was applied to a glass plate, and the solvent was dried to form a coating film having a thickness of 30. Mu.m.
Further, from the viewpoint of making the transmittance in the infrared region higher and the transmittance in the visible region lower, the following expression (2) is preferably satisfied, and the following expression (3) is more preferably satisfied.
T850－T600≥60 (2)
T800－T600≥50 (3)
The "T 850－T600" is preferably 65% or more, more preferably 70% or more. The upper limit of "T 850－T600" is not particularly limited, but the higher the upper limit, the more preferable the upper limit is 100%.
The "T 800－T600" is preferably 55% or more, more preferably 60% or more. The upper limit of "T 800－T600" is not particularly limited, but the higher the upper limit, the more preferable the upper limit is 100%.
For the near infrared ray transmitting black particles of the present invention, the above-mentioned T 600 is preferably less than 10%, more preferably less than 5%. By setting the range to the above range, the visible light blocking property improves, and defects such as discoloration of the filter and malfunction of the sensor are reduced. The lower limit of T 600 is not particularly limited, but is preferably 0%.
Further, T 900 is preferably more than 80%, more preferably more than 85%. By setting the range to the above range, the operation efficiency of the sensor can be improved. The upper limit of T 900 is not particularly limited, but is preferably 100%.
The near infrared ray transmitting black particles of the present invention preferably have a diffuse transmittance Td 900 (%) of 10% or less at a wavelength of 900nm as measured using a spectrophotometer. By setting the range to the above range, the diffusion of near infrared light (Japanese: near-red outside light) is suppressed, and the use efficiency of transmitted near infrared light is improved, so that near infrared light can be effectively utilized. Further, the Td 900 is more preferably 3% or less. The lower limit of Td 900 is not particularly limited, but is preferably 0%.
The near infrared ray transmitting black particles of the present invention preferably have a diffuse transmittance Td 1100 (%) at a wavelength of 1100nm as measured using a spectrophotometer of 10% or less. By setting the range to the above range, the diffusion of near infrared light is suppressed, and the use efficiency of transmitted near infrared light is improved, so that near infrared light can be effectively utilized. Further, the Td 1100 is more preferably 3% or less. The lower limit of Td 1100 is not particularly limited, but is preferably 0%.
The Td 900、Td1100 can be measured by, for example, using a spectrophotometer with an integrating sphere, removing a reflecting plate on the opposite side to the light incident side so that only the diffused light stays in the integrating sphere.
The numerical range of ,"T900－T600""T850－T600""T800－T600""T600""T900""Td900""Td1100" for the near-infrared-transmitting black particles of the present invention can be adjusted by the composition, the content ratio, the polymerization reaction, etc. of the copolymer having the structural unit derived from the compound having the aromatic ring containing a hydroxyl group, the crosslinking agent, and the structural unit derived from the compound containing an amino group.
The near infrared ray transmitting black particles of the present invention preferably contain: a copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group, and a structural unit derived from an amino group-containing compound.
By containing the copolymer, near infrared ray transmitting black particles having high transmittance in the near infrared ray region and low transmittance in the visible ray region can be produced.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Among them, benzene rings and naphthalene rings are preferable.
Examples of the compound having a hydroxyl group-containing naphthalene ring include: 1-naphthol, 2-naphthol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, pentahydroxynaphthalene, and the like. Among them, dihydroxynaphthalene and 1-naphthol are preferable, and among them, 1, 3-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene and 1, 6-dihydroxynaphthalene are preferable.
Examples of the compound having a benzene ring containing a hydroxyl group include: phenol and its derivatives, catechol, resorcinol, hydroquinone and its derivatives, trimellitic phenol, phloroglucinol, pyrogallol and its derivatives, tetrahydroxybenzene and its derivatives, and the like.
The above-mentioned compound having an aromatic ring containing a hydroxyl group is preferably used in combination of plural kinds. In this case, it is preferable to use a combination of different compounds having an aromatic ring containing a hydroxyl group, and it is more preferable to use a combination of a compound having a naphthalene ring containing a hydroxyl group and a compound having a benzene ring containing a hydroxyl group. Thus, it is possible to exhibit a characteristic that it is difficult to coexist the visible light blocking by the naphthalene ring and the near infrared ray transmission by the benzene ring. In addition, a plurality of compounds having a naphthalene ring containing a hydroxyl group may be used in combination.
The hydroxyl group bonded to the aromatic ring exhibits nucleophilicity of the aromatic ring (becomes a starting point of nucleophilic attack of the aromatic ring), and therefore, it is preferable that the hydroxyl group has a hydrogen atom in the ortho-position and/or para-position (ortho-position and/or para-position to the hydroxyl group on the benzene ring substituted with the hydroxyl group in the case of the compound having a naphthalene ring containing a hydroxyl group). Thus, the attack can be thoroughly performed.
Specifically, regarding the naphthalene ring having a hydroxyl group, when the hydroxyl group is one, in the case where the hydroxyl group is substituted based on the 1-position, it is preferable that only the 2-position and/or the 4-position is hydrogen having no substituent; in the case where the hydroxyl group is substituted at the 2-position, it is preferable that only the 1-position and/or the 3-position is hydrogen having no substituent. When two hydroxyl groups are substituted with one hydroxyl group at the 1-position, it is preferable that only the 2-and 4-positions are hydrogen having no substituent, and the second hydroxyl group is substituted at the 5-, 6-, 7-, 8-positions; in the case where a hydroxyl group is substituted at the 2-position, it is preferable that only hydrogen having no substituent is substituted at the 1-position and 3-position, and the second hydroxyl group is substituted at the 5-, 6-, 7-or 8-positions.
Specifically, it is preferable to have any one of the following formulas (4) and (5).
By adopting such a structure, a highly nucleophilic-aggressively state of the aromatic ring derived from the hydroxyl group can be maintained.
[ Chemical formula 1]
In the formulas (4) and (5), R 1、R2、R3、R4 represents hydrogen or an alkyl group having 20 or less carbon atoms.
The compound having a benzene ring containing a hydroxyl group preferably has 1 to 3 hydroxyl groups, and the compound having a naphthalene ring containing a hydroxyl group preferably has 1 to 4 hydroxyl groups. This can maintain general nucleophilic aggressiveness.
The amino group-containing compound has a function as a chromophore of a compound having a hydroxyl group-containing aromatic ring, which provides electrons.
Therefore, the amino group-containing compound may have an ether group, a hydroxyl group, or the like in addition to the amino group.
The amino group-containing compound is not particularly limited as long as it is a compound containing an amino group, and examples thereof include compounds containing a primary amino group, a secondary amino group and a tertiary amino group, but preferably compounds having a primary amino group.
As the amino group-containing compound, a chain aliphatic amine, an alicyclic amine, an aromatic amine, an alkanolamine, or the like can be used in addition to ammonia and hydrazine.
Among them, aromatic amines are preferable.
Examples of the aromatic amine include aromatic monoamines and aromatic polyamines.
Examples of the aromatic monoamine include: aniline, p-toluidine, p-ethylaniline, p-anisidine, alpha-naphthylamine, p-butylaniline, p-aminophenylether, 4-aminophenol and the like. Among them, aniline and p-anisidine are preferable.
Examples of the aromatic polyamine include N, N-dimethyl-1, 4-phenylenediamine, toluenediamine, 4' -diaminodiphenylmethane, and the like.
In particular, in the aromatic polyamine, the first amino group is preferably a primary amino group having no substituent, and the amino group is preferably an alkyl group, an amino group or an alkoxy group having electron donating properties in the ortho-or para-position, more preferably in the para-position. In the case of the second and subsequent amino groups and alkoxy groups substituted at the para position, the alkyl group is preferably substituted without active hydrogen. Specifically, the structure of the following formula (6) is preferable.
[ Chemical formula 2]
In the formula (6), R X represents hydrogen, -OR OR-NR 'R', R, R 'and R' represent an alkyl group having 20 OR less carbon atoms.
Examples of the chain aliphatic amine include: ethylamine, 1-propylamine, 2-propylamine, 1-butylamine, 1-pentylamine, 1-hexylamine, 1-heptylamine, 1-octylamine, 1-laurylamine, 1, 2-ethanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, ethylenetriamine, diethylenetriamine, ethylhydrazine, 1-propylhydrazine, 1-butylhydrazine, 1-pentylhydrazine, 1-hexylhydrazine, 1-heptylhydrazine, 1-octylhydrazine, succinic dihydrazide, terephthalic dihydrazide, guanidine, 1-butylguanidine, 1-cyanoguanidine, dicyandiamide, and the like.
The alicyclic amine may be: cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclopropanediamine, isophoronediamine, cyclobutanediamine, cyclopentanediamine, cyclohexanediamine, bis (4-aminocyclohexyl) methane, piperazine, N-aminoethylpiperazine, and the like.
Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.
The above-mentioned amino group-containing compound preferably has 1 to 3 amino groups. Thus, the amino group and the aromatic ring having a hydroxyl group are sufficiently reacted. In addition, by setting the number of amino groups to 3 or less, the basicity of each amino group can be set to an appropriate level. In addition, from the viewpoint of being less susceptible to steric hindrance of reactivity, the above amino group is preferably present at the end of the molecule.
The copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group and a structural unit derived from an amino group-containing compound preferably contains a color assisting group.
Examples of the color promoting group include thiol group, aldehyde group, carboxyl group, hydroxyl group, and the like, in addition to the amino group. The color assisting groups may be one kind or two or more kinds.
The near infrared ray transmitting black particles of the present invention preferably contain a crosslinking agent.
The copolymer having the structural unit derived from the compound having an aromatic ring containing a hydroxyl group and the structural unit derived from the compound containing an amino group is crosslinked by the crosslinking agent, whereby black particles having excellent resin-made structural elements and excellent handleability can be produced. In this case, the copolymer has a structure including a structural unit derived from a compound having an aromatic ring containing a hydroxyl group, a structural unit derived from a compound containing an amino group, and a structural unit derived from a crosslinking agent.
The crosslinking agent is different from the compound having a hydroxyl group-containing aromatic ring and the compound having an amino group.
The crosslinking agent is preferably an electrophilic reactant which is susceptible to phenolic nucleophilic attack.
Examples of the crosslinking agent include: polyamine-based crosslinking agents, thiourea-based crosslinking agents, thiadiazole-based crosslinking agents, triazine-based crosslinking agents, quinoxaline-based crosslinking agents, bisphenol-based crosslinking agents, organic peroxide-based crosslinking agents, aldehyde-based crosslinking agents, silane-based crosslinking agents, and the like. In addition, a phenolic crosslinking agent such as resol may be used.
Examples of the polyamine-based crosslinking agent include: ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, isopropylenediamine, N' -biscinnamaldehyde-1, 6-hexamethylenediamine, ethylenediamine carbamate, hexamethylenediamine carbamate, and the like.
Examples of the thiourea crosslinking agent include: 2-mercaptoimidazoline (ethylenethiourea), 1, 3-diethylthiourea, 1, 3-dibutylthiourea, trimethylthiourea, and the like.
Examples of the thiadiazole-based crosslinking agent include: 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-1, 3, 4-thiadiazole-5-thiobenzoate, and the like.
Examples of the triazine-based crosslinking agent include: 2,4, 6-trimercapto-1, 3, 5-triazine, 2-hexylamino-4, 6-dimercaptotriazine, 2-diethylamino-4, 6-dimercaptotriazine, 2-cyclohexylamino-4, 6-dimercaptotriazine, 2-dibutylamino-4, 6-dimercaptotriazine, 2-anilino-4, 6-dimercaptotriazine, 2-phenylamino-4, 6-dimercaptotriazine, and the like.
Examples of the quinoxaline crosslinking agent include: 2, 3-dimercaptoquinoxaline, quinoxaline-2, 3-dithiocarbonate, 6-methylquinoxaline-2, 3-dithiocarbonate, 5, 8-dimethylquinoxaline-2, 3-dithiocarbonate, and the like.
Examples of the bisphenol-based crosslinking agent include bisphenol AF and bisphenol S.
Examples of the organic peroxide crosslinking agent include: tert-butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, tert-butyl peroxide, 1, 3-bis (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, benzoyl peroxide, tert-butyl peroxybenzoate and the like.
Examples of the aldehyde-based crosslinking agent include: glyoxal, malondialdehyde, succinaldehyde, maleic dialdehyde, glutaraldehyde, formaldehyde, acetaldehyde, benzaldehyde, 1,3, 5-trioxane, and the like.
The silane-based crosslinking agent may be: alkoxy silanes such as methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and the like.
Among these, polyamine-based crosslinking agents and aldehyde-based crosslinking agents are preferable from the viewpoint of easiness of addition (solvent dissolution) and high reactivity [ carbon atoms adjacent to electron-withdrawing atoms exist in a relatively large space (steric hindrance is small) ].
The near infrared ray transmitting black particles of the present invention contain: in the case of a copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group and a structural unit derived from an amino group-containing compound, the content ratio of the structural unit derived from an amino group-containing compound to the structural unit derived from the compound having an aromatic ring containing a hydroxyl group (structural unit derived from an amino group-containing compound/structural unit derived from a compound having an aromatic ring containing a hydroxyl group) is preferably 0.1 to 50, more preferably 0.5 to 30, still more preferably 0.8 to 10. When the ratio is 0.1 or more, the visible light blocking property can be improved, and when the ratio is 50 or less, the infrared ray transmittance can be improved.
The compound having an aromatic ring containing a hydroxyl group is preferably a combination of a compound having a naphthalene ring containing a hydroxyl group and a compound having a benzene ring containing a hydroxyl group. In this case, the content ratio of the structural unit derived from the compound having a benzene ring containing a hydroxyl group (structural unit derived from the compound having a benzene ring containing a hydroxyl group/structural unit derived from the compound having a naphthalene ring containing a hydroxyl group) is preferably 0.1 to 50, more preferably 0.5 to 30, still more preferably 1 to 10, relative to the structural unit derived from the compound having a naphthalene ring containing a hydroxyl group.
The near infrared ray transmitting black particles of the present invention contain: in the case of a copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group and a structural unit derived from a crosslinking agent, the content ratio of the structural unit derived from a crosslinking agent (structural unit derived from a crosslinking agent/structural unit derived from a compound having an aromatic ring containing a hydroxyl group) to the structural unit derived from a compound having an aromatic ring containing a hydroxyl group is preferably 0.3 to 10, more preferably 0.5 to 5, still more preferably 0.5 to 2.
The effect of the present invention is not improved even if the content is 10 or more, and if the content is 0.3 or less, it becomes difficult to promote solidification.
The copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group and a structural unit derived from an amino group-containing compound is obtained by polymerizing the compound having an aromatic ring containing a hydroxyl group and the amino group-containing compound. That is, the copolymer having a structural unit derived from a compound having an aromatic ring containing a hydroxyl group and a structural unit derived from an amino group-containing compound is a copolymer of a compound having an aromatic ring containing a hydroxyl group and an amino group-containing compound.
In the polymerization reaction, the molar ratio of the amino group-containing compound (amino group-containing compound/hydroxyl group-containing aromatic ring-containing compound) to the hydroxyl group-containing aromatic ring-containing compound is preferably 0.5 to 50, more preferably 0.8 to 10. When the ratio is 0.5 or more, the visible light blocking property can be improved, and when the ratio is 50 or less, the infrared ray transmittance can be improved.
The compound having an aromatic ring containing a hydroxyl group is preferably a combination of a compound having a naphthalene ring containing a hydroxyl group and a compound having a benzene ring containing a hydroxyl group. In this case, the molar ratio of the compound having a benzene ring containing a hydroxyl group (compound having a benzene ring containing a hydroxyl group/compound having a naphthalene ring containing a hydroxyl group) to the compound having a naphthalene ring containing a hydroxyl group is preferably 0.5 to 50, more preferably 1 to 10.
In the polymerization reaction, the molar ratio of the crosslinking agent to the compound having a hydroxyl group-containing aromatic ring (crosslinking agent/compound having a hydroxyl group-containing aromatic ring) is preferably 0.5 to 10, more preferably 0.5 to 2.
The effect of the present invention is not improved even if the content is 10 or more, and if the content is 0.5 or less, it becomes difficult to promote solidification.
The polymerization temperature is preferably 0℃or higher, and more preferably 100℃or lower. The number average particle diameter of the aqueous dispersion can be suitably adjusted within the above range.
In the polymerization reaction, when the amount of the monomer remaining in the reaction liquid is confirmed, 70% by weight or more of the monomer is reacted and polymerized, and the end of the reaction is determined.
The amount of the residual monomer can be confirmed, for example, by: heating the reaction solution to a temperature higher than the volatilization temperature of the compound containing the hydroxyl-containing aromatic ring and drying the compound, and measuring the amount of residual solid components; the measurement was performed by quantitative analysis based on gas chromatography.
In the above polymerization, it is preferable to add an additive.
Examples of the additive include: halogen compounds such as iodine, bromine, and chlorine; proton acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, fluoroboric acid, and phosphinic acid; various salts of these protic acids; lewis acids such as aluminum trichloride, ferric trichloride, molybdenum chloride, antimony chloride, arsenic pentafluoride and antimony pentafluoride; organic carboxylic acids such as acetic acid, trifluoroacetic acid, polyacrylic acid (japanese), formic acid, benzoic acid, and citric acid; various salts of these organic carboxylic acids; phenols such as phenol, nitrophenol, and cyanophenol; various salts of these phenols; sulfosuccinic acids such as di (2-ethylhexyl) sulfosuccinic acid and sulfosuccinic acid; salts of sulfosuccinic acids; high molecular acids such as polyacrylic acid; alkyl phosphates such as propyl phosphate, butyl phosphate, and hexyl phosphate; polyoxyalkylene phosphates such as polyoxyethylene dodecyl ether phosphate and polyoxyethylene alkyl ether phosphate; various salts of alkyl phosphate esters and polyoxyalkylene phosphate esters; sulfuric acid esters such as lauryl sulfate, cetyl sulfate, stearyl sulfate and lauryl ether sulfate; various salts of these sulfuric acid esters, and the like.
Regarding the molar ratio of the compound having an aromatic ring containing a hydroxyl group to the compound having an amino group, the molar amount of the compound having an aromatic ring containing a hydroxyl group is preferably 0.1 to 10 times the molar amount of the compound having an amino group in terms of the compounding ratio. By setting the molar ratio to 0.1 times or more, the compound having an amino group can be collected into particles, and the effect of the present invention can be exhibited. Further, when the molar ratio is 10 times or less, the effect of the compound having an amino group is improved, and the transmittance and barrier change of the light transmittance become clear, which is preferable.
Examples of the method for producing the near infrared ray transmitting black particles of the present invention include: and a method in which a compound having an aromatic ring containing a hydroxyl group, an amino group-containing compound, and a crosslinking agent are mixed and reacted.
Specifically, there may be mentioned: and a method of preparing a solution containing a compound having an aromatic ring containing a hydroxyl group, further, dropping a solution containing a compound containing an amino group to react, and further adding a crosslinking agent solution.
The temperature at the time of the reaction is preferably 0℃or more, and more preferably 100℃or less.
The reaction time is preferably 4 hours or more, more preferably 48 hours or less.
In the above method for producing near infrared ray transmitting black particles, the drying step may be further performed.
The drying temperature in the drying step is preferably 80℃or higher, and more preferably 200℃or lower. The drying time is preferably 1 hour or more, and more preferably 48 hours or less.
The near infrared transmitting black particles of the present invention can be used in applications such as coating films, black paints, black matrices for color filters, and inks for infrared sensors.
In the case of producing a coating film, a black paint, a black matrix for a color filter, an ink for an infrared sensor, or the like using the near infrared ray transmitting black particles of the present invention, the light transmittance thereof is affected by a dispersion medium of the near infrared ray transmitting black particles, a dispersion method, a resin binder for forming a coating film, a particle content, and a coating film thickness, and a hydrophilic to hydrophobic solvent can be selected as the dispersion medium by adjusting the dispersion medium. The particle content may be adjusted to 100 parts by weight or less of the particles relative to 100 parts by weight of the resin binder, and the film thickness may be adjusted to 30 μm or less.
As a method of forming the above-described black matrix, first, the near-infrared-transmitting black particles, the curable compound, and further, if necessary, the curing agent, the solvent, and the like of the present invention are mixed using a stirrer to prepare a composition containing the near-infrared-transmitting black particles.
Then, the composition is applied to a substrate and dried to form a coating film.
The obtained coating film is partially exposed to active energy rays such as ultraviolet rays and excimer lasers through a negative mask, whereby a black matrix having a predetermined pattern shape can be formed.
Further, by performing the operation of the method for forming the black matrix also on the photosensitive resin composition in which the red pigment is dispersed, the photosensitive resin composition in which the green pigment is dispersed, and the photosensitive resin composition in which the blue pigment is dispersed, pixel patterns of respective colors are formed, whereby a color filter can be formed.
The photosensitive resin composition having the red pigment dispersed therein, the photosensitive resin composition having the green pigment dispersed therein, and the photosensitive resin composition having the blue pigment dispersed therein may be conventionally known photosensitive resin compositions.
The color filter may be manufactured by the following method: the ink of each of the colors red, green and blue is ejected from the ink ejection nozzle to each region partitioned by the black matrix, and the accumulated ink is cured by heat or light.
The color filter can be suitably used as a member of a display device such as a liquid crystal display device or an organic electroluminescence display device.
Effects of the invention
According to the present invention, it is possible to provide near-infrared-transmitting black particles having high transmittance in the near-infrared region and low transmittance in the visible region. The transmittance in the near infrared region (wavelength 1100nm or more) on the longer wavelength side can be also made high.
In addition, since the near infrared transmitting black particles of the present invention do not use a carbon-based or metal-based material, electrical insulation can be made high.
In addition, in the case of using the near infrared-transmitting black particles of the present invention, it is not necessary to increase the film thickness of the formed coating film or to increase the amount of particles to be added to a desired amount or more, and the degree of freedom in designing the coating film is increased.
The near infrared transmitting black particles of the present invention can be suitably used for applications such as black paint, coating film, black matrix for color filters, and ink for infrared sensors.
Drawings
Fig. 1 is a graph (horizontal axis: wavelength, vertical axis: transmittance) obtained when total transmittance was measured for the coating films obtained in examples 1 to 5 and comparative examples 1 and 2.
Detailed Description
The following examples illustrate the mode of the present invention in further detail, but the present invention is not limited to these examples.
Example 1
12G (75 mmol) of 1, 5-dihydroxynaphthalene (manufactured by Tokyo chemical industry Co., ltd.) and 37.4g (225 mmol) of t-butylcatechol (manufactured by Tokyo chemical industry Co., ltd.) were added to 3.5L of 2-propanol and stirred, whereby a mixed solution of 1, 5-dihydroxynaphthalene and t-butylcatechol was obtained.
Further, 55.4g (450 mmol) of p-anisole (manufactured by Tokyo chemical industry Co., ltd.) was dissolved in 3.5L of water to obtain an aqueous solution.
The obtained paraanisole aqueous solution is added dropwise to a mixed solution of 1, 5-dihydroxynaphthalene and tert-butylcatechol for mixing.
The obtained mixture was stirred at room temperature (25 ℃) for 8 hours, then heated to 60℃and further stirred for 12 hours, then cooled to room temperature, 210g (150 mmol) of a 10% aqueous solution of hexamethylenetetramine (manufactured by Fuji photo-pure Co., ltd.) was added, stirred at room temperature (25 ℃) for 8 hours, then heated to 80℃and further stirred for 12 hours, and then cooled to room temperature to obtain a particle dispersion.
The obtained particle dispersion was filtered through a 0.1 μm membrane filter, and then dried at 110℃for 3 hours under vacuum to obtain black powder particles.
Since the solid content (weight after drying) contained in the filtrate side was almost absent (equivalent to less than 0.1% of the total solid content), it was confirmed that the additive was almost contained in the black powder particles.
The cyclohexanone was added so that the concentration of the obtained black powder particles became 1% by weight and the concentration of polyvinyl butyral (S-LEC BH-S, manufactured by water chemical industry company) became 9% by weight, and the mixture was stirred to obtain a black particle dispersion (cyclohexanone concentration 90% by weight).
The resulting black particle dispersion was coated on a slide glass with a coater, and dried at 90℃to thereby form a coating film (thickness of coating film after drying: 30 μm) on the slide glass.
Example 2
Black powder particles and coating films were obtained in the same manner as in example 1, except that 24.8g (225 mmol) of hydroquinone (manufactured by fuji photo-pure co.) was used instead of t-butylcatechol.
Example 3
Black powder particles and coating films were obtained in the same manner as in example 1 except that 10.8g (75 mmol) of 1-naphthol (manufactured by Fuji photo-pure Co., ltd.) was used instead of 1, 5-dihydroxynaphthalene.
Example 4
Black powder particles and coating films were obtained in the same manner as in example 1, except that 41.9g (450 mmol) of aniline (manufactured by fuji film and light purity chemical company) was used instead of p-anisole.
Example 5
Black powder particles and coating films were obtained in the same manner as in example 1, except that 43.3g (300 mmol) of 1-naphthol (manufactured by Fuji photo-pure chemical Co., ltd.) was used instead of both 1, 5-dihydroxynaphthalene and t-butylcatechol, 12.2g (90 mmol) of N, N-dimethyl-1, 4-phenylenediamine (manufactured by Tokyo chemical Co., ltd.) was used instead of p-anisidine, and 18.6g (205 mmol) of 1,3, 5-trioxane (manufactured by Tokyo chemical Co., ltd.) was used instead of hexamethylenetetramine aqueous solution.
Examples 6 to 11
Black powder particles and coating films were obtained in the same manner as in example 1, except that the compounds and crosslinking agents shown in table 1 were used.
Comparative example 1
Black powder particles and coating films were obtained in the same manner as in example 1, except that 37.4g (225 mmol) of t-butylcatechol (manufactured by tokyo chemical industry Co., ltd.) was not added and an aqueous solution of p-anisole was not mixed.
Comparative example 2
Black powder particles and coating films were obtained in the same manner as in example 4, except that 12g (75 mmol) of 1, 5-dihydroxynaphthalene (manufactured by tokyo chemical industry Co., ltd.) was not added.
Comparative example 3
The same operations as in example 1 were conducted except that 12g (75 mmol) of 1, 5-dihydroxynaphthalene (manufactured by Tokyo chemical industry Co., ltd.) and 37.4g (225 mmol) of t-butylcatechol (manufactured by Tokyo chemical industry Co., ltd.) were not added, but black powder particles and coating films were not obtained.
(Evaluation)
The black powder particles and the coating films obtained in examples and comparative examples were evaluated as follows. The results are shown in Table 1.
(1) Total light transmittance
The obtained coating film was measured for light transmittance in a wavelength region of 400 to 1200nm using a spectrophotometer (model U-4100, manufactured by Hitachi Ltd.) equipped with an integrating sphere. In the measurement, the total light transmittance was measured by attaching a reflecting plate on the opposite side to the light incident side.
Next, the transmittance T 600 (%) at the wavelength 600nm and the transmittance T 900 (%) at the wavelength 900 were determined, and T 900－T600 was calculated. In addition, the transmittance T 650、T700、T750、T800、T850 (%) at wavelengths 650, 700, 750, 800, 850nm is also shown in table 1.
Further, the transmittance of T 1100 (transmittance at 1100 nm) to T 2000 (transmittance at 2000 nm) was continuously measured, and the transmittance of 90% or more of the intermediate value (T 1550) was determined as "o", and the transmittance of less than 90% was determined as "x". T 1550 represents transmittance at a longer wavelength in the near infrared region.
The graphs of transmittance with respect to wavelength for examples 1 to 5 and comparative examples 1 and 2 are shown in fig. 1.
(2) Diffuse transmittance
The diffuse transmittance in the region of 400 to 1200nm was measured on the same coating film used for the measurement of the total transmittance of (1) by removing the reflecting plate on the opposite side of the spectrophotometer (manufactured by Hitachi Ltd., U-4100 type) with the integrating sphere from the light incident side so that the parallel light ray does not remain in the integrating sphere and only the diffuse light ray remains in the integrating sphere.
Next, the diffuse transmittance Td 600 (%) at the wavelength 600nm, the diffuse transmittance Td 900 (%) at the wavelength 900nm, and the diffuse transmittance Td 1100 (%) at the wavelength 1100nm were determined.
TABLE 1
Industrial applicability
According to the present invention, it is possible to provide near-infrared-transmitting black particles having high transmittance in the near-infrared region and low transmittance in the visible region.
Claims (7)
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| JP2022-003854 | 2022-01-13 | ||
| JP2022003854 | 2022-01-13 | ||
| PCT/JP2022/031226 WO2023022199A1 (en) | 2021-08-18 | 2022-08-18 | Near-infrared light transmitting black particles |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236514A (en) * | 1998-02-20 | 1999-08-31 | Dainichiseika Color & Chem Mfg Co Ltd | Near infrared transmitting dark azo pigment composition |
| KR20110084920A (en) * | 2008-10-15 | 2011-07-26 | 다이니치 세이카 고교 가부시키가이샤 | Azo pigments, coloring compositions, coloring methods and colored articles |
| KR20130108650A (en) * | 2010-12-28 | 2013-10-04 | 다이니치 세이카 고교 가부시키가이샤 | Black azo pigment and process for production thereof, colored composition, coloring method, and colored articles |
| JP2015110691A (en) * | 2013-12-06 | 2015-06-18 | 大日精化工業株式会社 | Near-infrared transmissive black azo pigment, method for producing near-infrared transmissive black azo pigment, coloring composition using these black azo pigments, coloring method for article, and colored article |
| WO2016052641A1 (en) * | 2014-09-30 | 2016-04-07 | 大日本印刷株式会社 | Infrared-light-transmitting ink of dark color, and infrared-light-transmitting sheet obtained using same |
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2022
- 2022-08-18 CN CN202280056080.5A patent/CN118043408A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236514A (en) * | 1998-02-20 | 1999-08-31 | Dainichiseika Color & Chem Mfg Co Ltd | Near infrared transmitting dark azo pigment composition |
| KR20110084920A (en) * | 2008-10-15 | 2011-07-26 | 다이니치 세이카 고교 가부시키가이샤 | Azo pigments, coloring compositions, coloring methods and colored articles |
| KR20130108650A (en) * | 2010-12-28 | 2013-10-04 | 다이니치 세이카 고교 가부시키가이샤 | Black azo pigment and process for production thereof, colored composition, coloring method, and colored articles |
| JP2015110691A (en) * | 2013-12-06 | 2015-06-18 | 大日精化工業株式会社 | Near-infrared transmissive black azo pigment, method for producing near-infrared transmissive black azo pigment, coloring composition using these black azo pigments, coloring method for article, and colored article |
| WO2016052641A1 (en) * | 2014-09-30 | 2016-04-07 | 大日本印刷株式会社 | Infrared-light-transmitting ink of dark color, and infrared-light-transmitting sheet obtained using same |
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