JP2022098705A - Phthalocyanine compound - Google Patents

Abstract

To provide a black matrix resist for color filter, a photo-spacer for LCD, PTP printed matter for medical packaging, a printing ink for food packaging, a film for covering an infrared sensor, a paint for coating automobiles, a top coat for building and paving, and the like by using a compound having transmissibility in the infrared region and high absorbency in the visible region.SOLUTION: The problem could be solved by our finding that a phthalocyanine compound having a specific thiophenol substituent is a compound having high transmissibility in the infrared region and, on the other hand, low transmissibility in the visible region.SELECTED DRAWING: Figure 2

Description

The present invention relates to phthalocyanine compounds.

In recent years, the number of devices, equipment, or materials that require wavelength control in the infrared region has been increasing in a wide range of fields. For example, press-through package (PTP) printing for medical packaging, food packaging, infrared sensor, automobile painting, exterior wall material, road pavement and the like can be mentioned.
In the PTP-printed foreign matter inspection device for pharmaceutical packaging, an infrared sensor is used to detect a foreign matter in a tablet or the package itself. At that time, those having absorption in the infrared region cannot sufficiently reflect the infrared light from the light source from the aluminum which is the base material of the package and are recognized as foreign substances. Therefore, the coloring material is required to have little or little absorption in the infrared region.

In the recycling of food packages, infrared sensors are used to determine whether recycling is possible or to identify materials. Those that have absorption in the infrared region transmit infrared light from a light source or are reflected by some identification devices, but they cannot be used and are identified as non-recyclable products, so the color material is red. There is a demand for a material with low or small absorption in the outer region.

In an infrared sensor, a detector corresponding to the sensor or a light source or the like is not always formed of an element that detects or emits light only in the infrared region, so that detection of only the infrared region or For emission, a material that absorbs or reflects the visible region and transmits only the infrared region is required.

On the other hand, in the black matrix used for color filters such as LCDs and OLEDs and the photo spacers of LCDs, the infrared camera is used for the alignment with the photo mask in the post-baking process, so the alignment is accurate. Is desired to be a material that transmits in the infrared region.

In automobile painting, exterior wall materials, road pavement, etc., it is necessary to prevent the object from rising in temperature due to absorption of sunlight in the hot season. Since this is an important issue not only from the viewpoint of comfortable living but also from the viewpoint of energy saving, a material that transmits light in the near-infrared region having a large degree of contribution to heat is desired. Furthermore, it is also useful for infrared lasers used in recognition of the surrounding environment of autonomous vehicles, which are expected to become widespread in the future, in automobile painting and road pavement.
In the above exemplified use, black color tends to be used in addition to the chromatic color for the appearance for various reasons. PTP printing and food packaging are mainly for character recognition, infrared sensors are mainly for covering the sensor itself, and are popular colors for automobile painting and exterior wall materials, mainly for personal taste. Black, which is an achromatic color for different reasons because the road coating is derived from asphalt, is a basic color used for many purposes, not limited to the above-mentioned applications, along with white.

As described above, the black color material for the above purposes is basically a material that transmits wavelengths in the infrared region. However, carbon black, which is a commonly used black color material, is an alternative to carbon black because it absorbs light in a wide range of wavelengths in the infrared region, including 800 to 1400 nm, which contributes greatly to heat. A black color material is desired.
On the other hand, metallic phthalocyanines are used in a wide range of fields as blue-colored materials and green-colored materials. The phthalocyanine molecule basically has absorption at 600 to 700 nm due to the influence of the conjugated double bond of the cyclic heteropolyene of tetraazaporphyrin, which is the basic skeleton of the phthalocyanine molecule, and the phthalocyanine molecule forms a certain crystal form. By doing so, the absorption range is expanded. From this point of view, metallic phthalocyanines have been developed as a coloring material that absorbs wavelengths in the infrared region.
For example, a soluble near-infrared absorbing compound in which a part of the metallic phthalocyanine is substituted with an aminothiol compound (Reference 1), a sulfonate in which a part of the metallic phthalocyanine is substituted with a sulfonate, and an infrared region in which a part of the metallic phthalocyanine is substituted with an amino group are widely used. Black phthalocyanine compounds having absorption (Reference 2), metallic naphthalocyanine compounds having a specific X-ray diffraction peak, small absorption in the visible region, and strong absorption in the infrared region (Reference 3), etc. Can be mentioned.
However, all of the above are aimed at improving the absorption in the infrared region, and a black color material having a small absorption in the infrared region and a large absorption in the visible region has not been paid attention to.

Japanese Unexamined Patent Publication No. 9-176501 Japanese Unexamined Patent Publication No. 2002-201371 Japanese Unexamined Patent Publication No. 2008-202000

The problem to be solved by the present invention is to utilize a compound having high transparency in the infrared region and high absorbency in the visible region, so that a black matrix resist for a color filter, a photo spacer for an LCD, and a PTP for medical packaging can be used. The purpose of the present invention is to provide printed matter, printing ink for food packaging, film for infrared sensor cover, paint for automobile painting, topcoat paint for construction and pavement, and the like.

As a result of diligent research to solve the above problems, the inventors have found that a phthalocyanine compound having a specific thiophenol substituent is a compound having high transparency in the infrared region and low permeability in the visible region. The inventor was able to solve the above problems.

That is, the present invention includes the following.

[1] A phthalocyanine compound represented by the following general formula (1).

General formula (1)

（式中、Ｘは各々独立に水素原子またはハロゲン原子を表し、ｌは０～１５の整数、ｍ、ｎは、各々独立して０～８の整数を表し、ただし、どちらかが０の場合は、一方は１～８の整数を表し、０．５≦ｍ＋（ｎ／２）≦１０を満たし、Ｍは２価の金属原子、３価あるいは４価の置換金属またはオキシ金属を表す。）
［２］Ｘ線回折スペクトルにおいて、４．２°≦２θ≦５．１°に回折ピークを有する［１］記載のフタロシアニン化合物。
［３］１または２記載のフタロシアニン化合物をウレタンアクリル樹脂に分散した塗膜中の分光透過率が９０５ｎｍにおいて５０～９９％であり、１５００ｎｍにおいて９０～９９．９％であることを特徴とする［１］または［２］記載のフタロシアニン化合物。
［４］［１］～［３］いずれか一記載のフタロシアニン化合物を含有することを特徴とする波長制御剤。

(In the equation, X independently represents a hydrogen atom or a halogen atom, l is an integer of 0 to 15, m and n each independently represent an integer of 0 to 8, except when either is 0. Represents an integer of 1 to 8, satisfying 0.5 ≦ m + (n / 2) ≦ 10, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal or an oxymetal).
[2] The phthalocyanine compound according to [1], which has a diffraction peak at 4.2 ° ≤ 2θ ≤ 5.1 ° in the X-ray diffraction spectrum.
[3] The spectral transmittance in the coating film in which the phthalocyanine compound according to 1 or 2 is dispersed in a urethane acrylic resin is 50 to 99% at 905 nm and 90 to 99.9% at 1500 nm []. The phthalocyanine compound according to 1] or [2].
[4] A wavelength control agent containing the phthalocyanine compound according to any one of [1] to [3].

The novel phthalocyanine compound of the present invention has transparency over the near infrared region of 900 to 2500 nm. In addition, since it has strong absorption over a wide range of 400 to 800 nm, as a wavelength control agent, black matrix resist for color filters, photo pacers for LCDs, PTP printed materials for medical packaging, printing inks for food packages, films for infrared sensor covers, etc. It can be used in a wide range of industrial fields such as automobile paints, construction, and pavement topcoats.

It is a figure which shows the X-ray diffraction spectrum of Example 2. It is a figure which shows the transmission wavelength spectrum of Example 2. It is a figure which shows the transmission wavelength spectrum of the comparative example 1. FIG. It is a figure which shows the transmission wavelength spectrum of the comparative example 2.

The embodiments of the present invention shown below represent only a part of the embodiments of the present invention, and are not limited to the description contents as long as they do not deviate significantly from the gist.

[Pphthalocyanine compound]
In the phthalocyanine compound of the present invention, X independently represents a hydrogen atom or a halogen atom, and examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and a chlorine atom and a bromine atom. , Fluorine atom is preferable, and chlorine atom and bromine atom are particularly preferable.
Further, although l represents an integer of 1 to 15, from the viewpoint of transparency in the infrared region, 3 to 15 is preferable, 4 to 14 is preferable, and 5 to 13 is particularly preferable.
Although m and n each independently represent an integer of 0 to 8, m is preferably 0 to 6, and particularly preferably 0 to 4. n is preferably 1 to 7, and particularly preferably 1 to 5.
Further, in the above-mentioned phthalocyanine compound of the present invention, it is preferable to satisfy 0.5 ≦ m + (n / 2) ≦ 10 from the viewpoint of transparency in the infrared region and absorbability in the visible region, and further 0.5 ≦. It is preferable to satisfy m + (n / 2) ≦ 8, and it is particularly preferable to satisfy 1 ≦ m + (n / 2) ≦ 6.

Examples of those in which M is a divalent metal include Cu (II), Zn (II), Fe (II), Ni (II), Ru (II), Rh (II), Pd (II), Mn ( II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II) Cd (II), Hg (II), Pd (II), Sn (II) and the like. ..

Examples of monovalent trivalent metals with M are Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-I, Ga-Br, In-Cl, In-Br. , In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C6H5, Al-C6H4 (CH3), In-C6 H5, In-C6H4 (CH3), Mn- (OH), Mn- (OC6H5), Mn- [OSi (CH3) 3], Fe-Cl, Ru-Cl and the like can be mentioned.

Examples of those in which M is a disubstituted tetravalent metal include CrCl2, SiCl2, SiBr2, SiF2, SiI2, ZrCl2, GeCl2, GeBr2, GeF2, GeBr2, GeF2, TiCl2, TiBr2, TiF2, Si. Ge (OH) 2, Zr (OH) 2, Mn- (OH) 2, Sn- (OH) 2, TiR2, CrR2, Sn-R2, GeR2 [R is an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof. Represents], Si (OR') 2, Sn- (OR') 2, Ge (OR') 2, Ti (OR') 2, Cr (OR') 2 [R'is an alkyl group or a phenyl group. , Naftyl group, trialkylsilyl group, dialkylalkoxysilyl group and derivatives thereof], Sn-SR ″) 2, Ge (SR'') 2 [R ″ is an alkyl group, a phenyl group, a naphthyl group. , And its derivatives] and the like.

Examples of those in which M is an oxymetal include VO, Mn—O, TiO and the like.
As M, Cu, Al—Cl, TiO, or VO is preferable, and Cu is particularly preferable.

[Manufacturing method of phthalocyanine compound]
The phthalocyanine compound represented by the general formula (1) of the present invention can be produced, for example, by the following production method.

A halogenophthalocyanine compound represented by the following general formula (2).

General formula (2)

（ 式中、Ｙはハロゲン原子を表し、ｚは１～１６の整数を表し、Ｍは２価の金属原子、３ 価あるいは４ 価の置換金属またはオキシ金属を表す。）
に(Ｉ)２ － アミノチオフェノールを反応させる工程、（ＩＩ）反応により得られたフタロシアニン化合物以外の出発原料を除去する工程、（ＩＩＩ）得られたフタロシアニン化合物を洗浄する工程を、この順序で実施することにより製造できる。上記(ＩＩ)の工程と（ＩＩＩ）の工程は順序が入れ替わっても本発明のフタロシアニン化合物を製造することは可能であるが、(ＩＩ)の工程を先に行う方が、目的とする化合物を安定して得ることができる。
以下に、上記各工程ごとに製造法を詳しく説明する。
上記(Ｉ)の工程の反応は、塩基の存在下、好ましくは溶媒を使用して行われる。
一般式（２） のハロゲノフタロシアニン化合物と反応させる２－アミノチオフェノールの量は、ハロゲノフタロシアニン化合物に対して３～２０倍モル量、好ましくは４～１０倍モル量である。

(In the formula, Y represents a halogen atom, z represents an integer from 1 to 16, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal or an oxymetal.)
(I) 2-Aminothiophenol is reacted, (II) a step of removing starting materials other than the phthalocyanine compound obtained by the reaction, and (III) a step of washing the obtained phthalocyanine compound are performed in this order. It can be manufactured by carrying out. Although it is possible to produce the phthalocyanine compound of the present invention even if the order of the above steps (II) and (III) is changed, it is better to carry out the step (II) first to obtain the target compound. It can be obtained stably.
The manufacturing method will be described in detail below for each of the above steps.
The reaction of the above step (I) is carried out in the presence of a base, preferably using a solvent.
The amount of 2-aminothiophenol to be reacted with the halogenophthalocyanine compound of the general formula (2) is 3 to 20 times the molar amount, preferably 4 to 10 times the molar amount, as compared with the halogenophthalocyanine compound.

As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, t-butoxypotassium, sodium acetate, potassium acetate and the like can be used, but potassium carbonate is preferable.

The amount of the base used is preferably about twice the molar amount of 2-aminothiophenol.
Examples of the solvent include dimethylformamide (DMF), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), N-, N-dimethylimidazolidinone (DMI), polar solvents such as sulfolane, ketone solvents such as acetone and methyl ethyl ketone, and toluene. , Xylene, Monochlorobenzene, Dichlorbenzene and other aromatic hydrocarbon solvents are used, but dimethylformamide (DMF) and dimethylacetamide (DMAC) are preferable.

The amount of the solvent used is 1 to 50 times by weight, preferably 5 to 20 times by weight, that of the halogenophthalocyanine compound.
The reaction temperature is 50 to 140 ° C, preferably 100 to 130 ° C.
The reaction time is 1 to 20 hours, preferably 5 to 10 hours.

After cooling the reaction, the mixture is discharged into an alcohol having a weight of 1 to 5 times the amount of the reaction solvent, the precipitate is collected by filtration, and washed with alcohol to remove the crude product of the phthalocyanine compound.

The step (II) is carried out by using alcohol as the crude product of the phthalocyanine compound obtained in the step (I) and stirring the mixture at a temperature from room temperature to a temperature equal to or lower than the boiling point of the alcohol.
As the alcohol, aliphatic alcohols such as methanol, ethanol, 1-propanol and 2-propanol can be used, but methanol is preferable. Further, water may be mixed with alcohol. The amount of alcohol used is preferably 5 to 20 times by weight, more preferably 10 to 15 times by weight, based on the crude product of the phthalocyanine compound.
The step (III) is performed by stirring the phthalocyanine compound obtained in (II) above with water at a temperature of 100 ° C. or lower from room temperature. The amount of water used is preferably 5 to 20 times by weight, more preferably 10 to 15 times by weight, based on the phthalocyanine compound.
The phthalocyanine compound of the present invention can be obtained by drying after the step (III) above, but it can also be used in a hydrous wet cake in a filtered state without being dried.

The product produced according to the above reaction step is a mixture of phthalocyanine compounds represented by the formula (1), which can be used as it is as a compound that transmits in the infrared region, but is pigmented as necessary.
When performing the pigmentation, any known and commonly used method can be used. Specifically, a method of kneading and grinding the phthalocyanine compound of the present invention together with a water-soluble inorganic salt and a water-soluble organic solvent (solvent salt milling method), a method of heating the phthalocyanine compound of the present invention and the phthalocyanine compound in an insoluble solvent. (Solvent method), a method of refining using a pigment grinder or a pigment disperser, and the like can be mentioned.
As a solvent salt milling method, for example, the phthalocyanine compound of the present invention is kneaded and kneaded while heating with a water-soluble inorganic salt such as sodium chloride or sodium sulfate and a water-soluble organic solvent such as diethylene glycol or triethylene glycol. There is a method of washing with water.
When the solvent method is performed, a liquid medium that does not dissolve the phthalocyanine compound of the present invention is selected and used. As this liquid medium, it is preferable to use a liquid medium containing a water-soluble organic solvent as an essential component in order to more stably control the crystals of the phthalocyanine compound of the present invention.
When the method of miniaturization is performed, for example, a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a kneader, a continuous single-screw kneader, a continuous twin-screw kneader, a three-roll, an open roll continuous kneader, etc. Pigment grinders and pigment dispersers can be used. Further, the pigment grinder and the pigment disperser can also be used in the solvent salt milling method.
Table 1 shows specific examples of the phthalocyanine compound represented by the general formula (1) of the present invention.

Conventionally, in phthalocyanine compounds, wavelength control as an application to the industrial field in absorption in the visible region has been developed mainly for absorption in the infrared region. In the present invention, a phthalocyanine compound having a specific aminothiophenol group has been found to have a high transmittance in the infrared wavelength region and a low transmittance in the visible region. By introducing an aminothiophenol group, the main X-ray diffraction peak is in the range of 4.2 ° ± 0.2 ° ≤ 2θ ≤ 5.1 ° ± 0.2 ° in the X-ray diffraction spectrum. It is a feature. It is presumed to be a peak derived from the stacking of phthalocyanine rings. As a result, the distance between the phthalocyanine skeletons increases and the distance between the laminated phthalocyanine rings becomes longer as a whole, so that absorption occurs in the transmission region near 450 to 600 nm, and the transmittance in the visible region decreases. It is thought that it is. Further, it is considered that the crystal state changes depending on the number of substituents of aminothiophenol, which affects the absorption in the infrared region.

By using the phthalocyanine compound of the present invention, black matrix resist for color filters, photo spacers for LCDs, PTP printing inks for medical packaging, printing inks for food packages, various plastic products, films for infrared sensor covers, and automobile coatings. It is possible to provide paints, construction, topcoat paints for paving, and the like. The applications described in detail below are examples, and the phthalocyanine compound of the present invention can be used for any purpose as a wavelength control agent.

In particular, in the case of a black matrix resist for a color filter or a photo spacer of an LCD, it is possible to perform accurate alignment with a photo mask in a post-process after each post-baking. In PTP printed matter for medical packaging, since there is no erroneous recognition as a foreign substance when the foreign substance inspection device is used, it is possible to contribute to the improvement of the yield. For printing inks for food packages and plastic products, it becomes possible to identify them at the time of recycling, and it is possible to sort out black plastics that have been difficult to recycle. In automobile painting, it will be possible to support infrared laser devices used for recognizing the surrounding environment of autonomous vehicles, which are expected to become widespread in the future, and it will also contribute to the thermal management of automobiles. In topcoat coating for construction and pavement, the temperature rise is suppressed to a certain level by reducing the absorption of sunlight, so that it is not necessary to use more air conditioning than necessary, which can contribute to energy saving as a result.

(Paint application)
When the compound of the present invention is used as a paint as a colorant, various resins used as the paint include acrylic resin, melamine resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, and phenol resin.

The solvent used for the paint includes aromatic solvents such as toluene, xylene and methoxybenzene, acetate solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and ethoxyethyl pro. Propionate solvent such as pionate, alcohol solvent such as methanol, ethanol, propanol n-butanol, isobutanol, ether solvent such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, Ketone-based solvents such as cyclohexanone, aliphatic hydrocarbon-based solvents such as hexane, nitrogen compound solvents such as N, N-dimethylformamide, γ-butyrolactam n-methyl-2-pyrrolidone, aniline, and pyridine, γ-butyrolactone and the like. There are lactone solvents, carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate, water and the like. As the solvent, a water-soluble polar solvent such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, and water is particularly suitable.

Further, when a compound additive and / or a compound is dispersed or mixed in a liquid resin to form a resin composition for a paint, ordinary additives such as dispersants, fillers and paint aids are used. Classes, desiccants, plasticizers and / or auxiliary compounds can be used. This is achieved by dispersing or mixing each component, either alone or in combination, collecting all the components, or adding them all at once.

Dispersers for dispersing the composition containing the compound of the present invention prepared as described above include a disper, a homomixer, a paint conditioner, a scandex, a bead mill, an attritor, a ball mill, a double roll, and three. Examples thereof include known dispersers such as the present roll and a pressurized kneader, but the present invention is not limited thereto. The compound is dispersed by adding a resin and a solvent so as to have a viscosity that can be dispersed by these dispersers. The high-concentration paint base after dispersion has a solid content of 5 to 20%, and is further mixed with a resin and a solvent to be used as a paint.

(Inkjet ink application)
The compound of the present invention can be suitably used for ink jet ink, and in particular, it can be suitably used for water-based inkjet ink as an aqueous compound dispersion liquid dispersed by using a compound dispersant or the like. As the aqueous compound dispersion, a high-concentration aqueous dispersion (compound paste) of the condensed polycyclic organic compound of the present invention is prepared, diluted with a water-soluble solvent and / or water, and other additions are made as necessary. It can be prepared by adding an agent.

The method for obtaining a compound paste by dispersing the compound of the present invention in the water-soluble solvent and / or water is not particularly limited, and it is preferable to use a known dispersion method. As the dispersant used at this time, a known compound dispersant may be used to disperse in water, or a surfactant may be used. Aqueous resins are preferable as the compound dispersant, and preferred examples thereof include polyvinyl alcohols, polyvinylpyrrolidones, urethane resins having anionic or cationic groups, and radical copolymers having anionic or cationic groups. Examples include resin. Examples of the radical copolymer resin having an anionic group or a cationic group include acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers. Styline-acrylic resin such as styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene- Examples thereof include a maleic acid copolymer, a styrene-maleic anhydride copolymer, a vinylnaphthalene-acrylic acid copolymer, and a salt of the aqueous resin.

Examples of the compound for forming the salt of the copolymer include alkali metals hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine and di. Examples thereof include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol and morpholin. The amount of the compound used to form these salts is preferably equal to or more than the neutralization equivalent of the copolymer.

Of course, it is also possible to use a commercially available product. As commercially available products, Ajinomoto Fine-Techno Co., Ltd.'s Azispar PB series, Big Chemie Japan's Disperbyk series, BYK-series, BASF Japan's EFKA series, and the like can be used.

Further, as the dispersion method, for example, the following (1) to (3) can be shown.
(1) A method for preparing a compound paste by adding a compound to an aqueous medium containing a compound dispersant and water, and then dispersing the compound in the aqueous medium using a stirring / dispersing device.
(2) The compound and the compound dispersant are kneaded using a kneader such as a two-roll or mixer, the obtained kneaded product is added to an aqueous medium containing water, and the compound is added using a stirring / dispersing device. How to prepare a paste.
(3) After adding the compound to the solution obtained by dissolving the compound dispersant in an organic solvent compatible with water such as methyl ethyl ketone and tetrahydrofuran, the compound is added to the organic solution using a stirring / dispersing device. A method for preparing a compound paste by distilling off the organic solvent after in-phase emulsification using an aqueous medium.

The kneading machine is not particularly limited, and examples thereof include a Henschel mixer, a pressurized kneader, a Banbury mixer, and a planetary mixer. The stirring / dispersing device is also not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, and a nanomizer. One of these may be used alone, or two or more kinds of devices may be used in combination.
The amount of the condensed polycyclic organic compound in the compound paste is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. When the amount of the compound is less than 5% by mass, the water-based ink prepared from the compound paste is not sufficiently colored, and a sufficient image density tends not to be obtained. On the contrary, when it is more than 60% by mass, the dispersion stability of the compound tends to decrease in the compound paste.
Further, since the coarse particles cause nozzle clogging and deterioration of other image characteristics, it is preferable to remove the coarse particles by centrifugation, filtration, or the like before and after ink preparation.

After the dispersion step, an impurity removal step by an ion exchange treatment or an extraneous treatment may be performed, and then a post-treatment may be performed. Ionic substances such as cations and anions (divalent metal ions, etc.) can be removed by ion exchange treatment, and impurity-dissolving substances (residual substances during compound synthesis, excess components in the dispersion liquid composition) can be removed by extraneous treatment. , Resin not adsorbed on organic compounds, foreign substances mixed in, etc.) can be removed. A known ion exchange resin is used for the ion exchange treatment. The ultrafiltration may be performed using a known ultrafiltration membrane and may be either a normal type or a double capacity up type.

After preparing the compound paste, it is appropriately diluted and an additive is added as necessary to obtain an aqueous compound dispersion according to the purpose. When the aqueous compound dispersion is applied to an ink for inkjet recording, a water-soluble solvent and / or water, an anionic group-containing organic polymer compound for the purpose of a binder, etc. are further added, and a wetting agent is added as necessary to obtain desired physical properties. Prepared by adding (drying inhibitor), penetrant, or other additives. After adjusting the ink, a centrifugation or filtration treatment step may be added.

The physical characteristics of the ink are not particularly limited, but the viscosity is preferably 1 to 10 (mPa · s) and the surface tension is preferably 20 to 50 (mN / m) in consideration of the ejection property of the ink jet ink. The compound concentration is preferably 1 to 10% by mass.

The wetting agent is added for the purpose of preventing the ink from drying. The content of the wetting agent for the purpose of preventing drying in the ink is preferably 3 to 50% by mass. The wetting agent used in the present invention is not particularly limited, but one that is miscible with water and has an effect of preventing clogging of the head of an inkjet printer is preferable. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butane. Examples thereof include diol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol and the like. Among them, the inclusion of propylene glycol and 1,3-butyl glycol has safety, and has excellent effects of ink drying property and ejection performance.

The penetrant is added for the purpose of improving the permeability to the recording medium and adjusting the dot diameter on the recording medium. Examples of the penetrant include lower alcohols such as ethanol and isopropyl alcohol, ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
The surfactant is added to adjust ink characteristics such as surface tension. The surfactant that can be added for this purpose is not particularly limited, and examples thereof include various anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Of these, anionic surfactants and nonionic surfactants are preferable.

Examples of the anionic surfactant include alkylbenzene sulfonates, alkylphenylsulfonates, alkylnaphthalene sulfonates, higher fatty acid salts, sulfate ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, and higher alcohol ethers. Sulfate ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates and the like. Specific examples of these include dodecylbenzene sulfonate, isopropylnaphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, dibutylphenylphenol disulfonate and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid ester. , Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers, among which polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene fatty acid. Esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkyrrole amides, acetylene glycols, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers are preferred.

Other surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorosurfactants such as perfluoroalkyl sulfonates, perfluoroalkyl sulfonates, oxyethylene perfluoroalkyl ethers. Biosurfactants such as spicrysporic acid, ramnolipide, lysolecithin and the like can also be used.

These surfactants can be used alone or in combination of two or more. When a surfactant is added, the amount of the surfactant added is preferably in the range of 0.001 to 2% by mass, more preferably 0.001 to 1.5% by mass, and 0. It is more preferably in the range of 01 to 1% by mass. If the amount of the surfactant added is less than 0.001% by mass, the effect of adding the surfactant tends not to be obtained, and if it is used in excess of 2% by mass, problems such as blurring of the image are likely to occur. ..

Further, if necessary, preservatives, viscosity regulators, pH regulators, chelating agents, plasticizers, antioxidants, ultraviolet absorbers and the like can be added.

(Plastic use)
The compound of the present invention can also be used for plastic coloring. In the case of obtaining a colored plastic molded product, for example, a thermoplastic resin (plastic) for thermal molding such as injection molding and press molding such as polyolefin such as polyethylene and polypropylene and polyvinyl chloride resin is used. The compound can be used by kneading into these resins by a conventionally known method.

(Toner application)
The compound of the present invention can also be used for toner coloring.
When obtaining a toner for static charge image development, for example, a thermoplastic resin having a solid film-forming property at room temperature, such as a polyester resin, a polyamide resin, a styrene resin, and an acrylic resin, is used as the dispersion resin.

The static charge image developing toner produced by using the compound of the present invention as a constituent component is a one-component color magnetic toner (color toner for magnetic one-component development) containing a magnetic substance in the toner, and a non-magnetic 1 component containing no magnetic substance. It can be used as a component color toner (color toner for non-magnetic one-component development) or a color toner for a two-component color developer mixed with a carrier (color toner for two-component development).

The one-component color magnetic toner can be composed of, for example, a colorant, a binder resin, a magnetic powder, a charge control agent (CCA), other additives typified by a mold release agent, and the like, in the same manner as those normally used.

The amount of the compound of the present invention to be used in the toner for static charge image development is not particularly limited, but it is preferably used in a ratio of 0.5 to 25 parts by mass with respect to 100 parts by mass of the binder resin, and the colorant itself. It is more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of making the charging performance of the binder more remarkable.

As the binder resin used for the toner for static charge image development, any of the known and commonly used resins exemplified as the thermoplastic resin can be used, but synthetic resins and natural resins that exhibit adhesiveness under the application of heat or pressure, Natural rubber, synthetic rubber, synthetic wax, etc. can be used.

(Use for black matrix photo spacer)
The compound of the present invention can be used for forming a pattern in the black matrix portion of a color filter or for a photo spacer for an LCD by a known method. Typically, a photosensitive composition for pattern formation containing the compound of the present invention and a photosensitive resin as essential components can be obtained.

In order to prepare the photosensitive composition for pattern formation, for example, the compound of the present invention, the photosensitive resin, the photopolymerization initiator, and the organic solvent that dissolves the resin are mixed as essential components. As the production method thereof, a method of preparing a dispersion liquid by using the compound of the present invention, an organic solvent and a dispersant as necessary, and then adding a photosensitive resin or the like to the dispersion liquid is generally used.

If necessary, a yellow compound can be used as the compound of the present invention used in the photosensitive composition for pattern formation. Examples of the dispersant used as needed include Disperbic (DISPERBYK registered trademark) 130, 161 and 162, 163, 170, LPN-6919 and LPN-21116 of Big Chemie. Further, a leveling agent, a coupling agent, a cationic surfactant and the like can also be used.

Examples of the organic solvent include aromatic solvents such as toluene, xylene and methoxybenzene, acetate solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvent, alcohol solvent such as methanol and ethanol, ether solvent such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, fat such as hexane. Group hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam n-methyl-2-pyrrolidone, aniline, pyridine and other nitrogen compound solvents, γ-butyrolactone and other lactone solvents, methyl carbamate and ethyl carbamate There are carbamate esters, water, etc., such as the 48:52 mixture of. As the organic solvent, a water-soluble polar solvent such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, and water is particularly suitable.

Examples of the photosensitive resin that can be used include thermoplastic resins such as urethane resin, acrylic resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, and styrene anhydride maleic acid resin, and examples of 1,6. -Bifunctional monomers such as hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, etc., trimethylolpropane Examples thereof include photopolymerizable monomers such as polyfunctional monomers such as triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.
Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4'-azidobenzal) -2-propane, and 1,3-bis (4'-. Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.
The photosensitive composition for black matrix thus prepared can be formed into a black matrix or spacer by subjecting a pattern exposure to ultraviolet rays through a photomask and then washing the unexposed portion with an organic solvent, alkaline water, or the like. can.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Moreover, "%" in the composition of the following examples means "mass%".

(Example 1)
Chlorinated copper phthalocyanine compound (phthalocyanine green) (manufactured by DIC Co., Ltd.) 10.0 g, 2-aminothiophenol 4.3 g (manufactured by Kanto Chemical Co., Ltd.), potassium carbonate 9.9 g (manufactured by Kanto Chemical Co., Ltd.), N, 200 g of N-dimethylformamide was placed in a four-necked flask equipped with a cooling tube and reacted at 130 ° C. for 5 hours. After the reaction, 150 g of methanol was added while cooling naturally, and the mixture was cooled to room temperature with stirring. The obtained reaction product was further washed with methanol, then washed twice with water, and dried at 100 ° C. for 5 hours to obtain 11.2 g of a phthalocyanine compound.
As a result of fluorescent X-ray measurement, it was found that the phthalocyanine compound was replaced with 2-aminothiophenol by an average of 4 molecules. Moreover, in the X-ray diffraction measurement, the maximum peak was 4.8 °.

[Evaluation 1]
(Hue evaluation)
2.0 g of the obtained compound, urethane acrylic resin (solid content concentration: 40%, solvent: xylene / isobutyl alcohol = 50/50) 8.0 g, xylene 4.0 g, isobutyl alcohol 1.0 g were placed in a glass bottle, and further. Glass beads having a diameter of 3 mm were added, and the compound was dispersed in a paint conditioner for 1 hour. Then, 25.0 g of the urethane acrylic resin was added and the compound was dispersed in a paint conditioner for 10 minutes, and then 8.0 g of the obtained paint, 9.6 g of the urethane acrylic resin, 1.8 g of xylene, and 0.4 g of isobutyl alcohol were obtained. , The glass beads were placed in a glass bottle and dispersed for 10 minutes to obtain the paint of Example 1.
The obtained paint was applied to white art paper with an applicator to obtain a coating film having a film thickness of 25 μm. The obtained coating film was visually black, and as a result of measuring the hue with a spectrophotometer (device name: "DC650" datacolor), L * = 27.3, a * = -3.75, b. * =-0.52. The weight ratio of the phthalocyanine compound of the present invention in the obtained coating film was 5%.
For reference, the black art paper had L * = 30.6, a * = 1.31, and b * = 2.44, so it was confirmed that a black coating film was obtained.

[Evaluation 2]
(Transmittance evaluation)
The paint prepared by the above hue evaluation was applied on a PET film of 188 μm with a bar coater to obtain a coating film of 2 μm. The transmittance in the infrared region of the obtained coating film was measured with a spectrophotometer. The transmittance of the obtained coating film at 905 nm was 77.7%. The transmittance at 1500 nm was 95.9%.

(Example 2)
Chlorinated copper phthalocyanine compound (phthalocyanine green) (manufactured by DIC Co., Ltd.) 10.0 g, 2-aminothiophenol 16.4 g (manufactured by Kanto Chemical Co., Ltd.), potassium carbonate 39.3 g (manufactured by Kanto Chemical Co., Ltd.), N, 200 g of N-dimethylformamide was placed in a four-necked flask equipped with a cooling tube and reacted at 130 ° C. for 5 hours. After the reaction, 150 g of methanol was added while cooling naturally, and the mixture was cooled to room temperature with stirring. The obtained reaction product was further washed with methanol, then washed twice with water, and dried at 100 ° C. for 5 hours to obtain 13.1 g of a phthalocyanine compound.
As a result of fluorescent X-ray measurement, it was found that the phthalocyanine compound was replaced with 2-aminothiophenol by an average of 8 molecules. Moreover, in the X-ray diffraction measurement, the maximum peak was 4.6 °.

[Evaluation 3]
(Hue evaluation)
A coating film having a film thickness of 25 μm was obtained in the same manner as in Evaluation 1 except that the phthalocyanine compound obtained in Example 2 was used. The obtained coating film was visually black, and as a result of measuring the hue with a spectrophotometer (device name: "DC650" datacolor), L * = 26.3, a * = -0.59, b. * = −0.48.

[Evaluation 4]
A coating film having a film thickness of 2 μm was obtained in the same manner as in Evaluation 2 except that the phthalocyanine compound obtained in Example 2 was used. When the transmittance of the obtained coating film in the infrared region was measured with a spectrophotometer, the transmittance at 905 nm was 66.9%, and the transmittance at 1500 nm was 94.2%.

(Example 3)
Brominated copper phthalocyanine compound (phthalocyanine green) (manufactured by DIC Co., Ltd.) 13.3 g, 2-aminothiophenol 16.4 g (manufactured by Kanto Chemical Co., Ltd.), potassium carbonate 39.3 g (manufactured by Kanto Chemical Co., Ltd.), N, 200 g of N-dimethylformamide was placed in a four-necked flask equipped with a cooling tube and reacted at 130 ° C. for 5 hours. After the reaction, 150 g of methanol was added while cooling naturally, and the mixture was cooled to room temperature with stirring. The obtained reaction product was further washed with methanol, then washed twice with water, and dried at 100 ° C. for 5 hours to obtain 9.3 g of a phthalocyanine compound.
As a result of fluorescent X-ray measurement, it was found that the phthalocyanine compound was replaced with 2-aminothiophenol by an average of 10 molecules. Moreover, in the X-ray diffraction measurement, the maximum peak was 4.2 °.

[Evaluation 5]
(Hue evaluation)
A coating film having a film thickness of 25 μm was obtained in the same manner as in Evaluation 1 except that the phthalocyanine compound obtained in Example 3 was used.
The obtained coating film was visually black, and as a result of measuring the hue with a spectrophotometer (device name: "DC650" datacolor), L * = 25.9, a * = -0.24, b. * = -0.74.

[Evaluation 6]
A coating film having a film thickness of 2 μm was obtained in the same manner as in Evaluation 2 except that the phthalocyanine compound obtained in Example 3 was used. When the transmittance of the obtained coating film in the infrared region was measured with a spectrophotometer, the transmittance at 905 nm was 68.4%, and the transmittance at 1500 nm was 93.9%.

(Example 4)
Trichloro copper phthalocyanine compound (phthalocyanine blue) (manufactured by DIC Co., Ltd.) 6.1 g, 2-aminothiophenol 8.4 g (manufactured by Kanto Chemical Co., Inc.), potassium carbonate 19.7 g (manufactured by Kanto Chemical Co., Inc.), N, N -200 g of dimethylformamide was placed in a four-necked flask equipped with a cooling tube and reacted at 130 ° C. for 5 hours. After the reaction, 150 g of methanol was added while cooling naturally, and the mixture was cooled to room temperature with stirring. The obtained reaction product was further washed with methanol, then washed twice with water, and dried at 100 ° C. for 5 hours to obtain 5.6 g of a phthalocyanine compound.
As a result of fluorescent X-ray measurement, it was found that the phthalocyanine compound was replaced with 2-aminothiophenol by an average of 1 molecule. Moreover, in the X-ray diffraction measurement, the maximum peak was 5.1 °.

[Evaluation 7]
(Hue evaluation)
2.0 g of the obtained compound, urethane acrylic resin (solid content concentration: 40%, solvent: xylene / isobutyl alcohol = 50/50) 8.0 g, xylene 4.0 g, isobutyl alcohol 1.0 g were placed in a glass bottle, and further. Glass beads having a diameter of 3 mm were added, and the compound was dispersed in a paint conditioner for 1 hour. Then, 25.0 g of the urethane acrylic resin was added and the compound was dispersed with a paint conditioner for 10 minutes to obtain the paint of Example 4.
The obtained paint was applied to white art paper with an applicator to obtain a coating film having a film thickness of 25 μm. The obtained coating film was visually black, and as a result of measuring the hue with a spectrophotometer (device name: "DC650" datacolor), L * = 26.9, a * = -1.29, b. * = -1.62.

[Evaluation 8]
(Transmittance evaluation)
The paint prepared by the above hue evaluation was applied on a PET film of 188 μm with a bar coater to obtain a coating film of 2 μm.
When the transmittance of the obtained coating film in the infrared region was measured with a spectrophotometer, the transmittance of the obtained coating film at 905 nm was 70.7%, and the transmittance at 1500 nm was 92.8%. Met.

<Comparative Example 1>
Based on the description of Example 3 of WO2006 / 109480, chlorinated copper phthalocyanine compound (phthalocyanine green) (manufactured by DIC Co., Ltd.) 10.0 g, 2-aminothiophenol 8.9 g (manufactured by Kanto Chemical Co., Inc.), carbonic acid. 11.1 g of potassium (manufactured by Kanto Chemical Co., Inc.) and 200 g of N, N-dimethylacetamide were placed in a four-necked flask equipped with a cooling tube and reacted at 160 ° C. for 48 hours. After the reaction, the obtained reaction solution was cooled to 55 ° C., and 400 g of hot water heated to 80 ° C. was added with stirring. The obtained reaction product was further washed once with ion-exchanged water and dried at 100 ° C. for 5 hours to obtain 15.3 g of a phthalocyanine compound.
As a result of fluorescent X-ray measurement, it was found that the phthalocyanine compound was replaced with 2-aminothiophenol by an average of 13 molecules. Moreover, in the X-ray diffraction measurement, the maximum peak was 3.9 °.

[Evaluation 9]
(Hue evaluation)
A coating film having a film thickness of 25 μm was obtained in the same manner as in Evaluation 1 except that the phthalocyanine compound obtained in Comparative Example 1 was used.
The obtained paint was visually black, and as a result of measuring the hue with a spectrophotometer (device name: "DC650" datacolor), L * = 25.8, a * = -1.04, b *. = −0.26.

[Evaluation 10]
(Transmittance evaluation)
A coating film having a film thickness of 2 μm was obtained in the same manner as in Evaluation 2 except that the phthalocyanine compound obtained in Comparative Example 1 was used.
The transmittance in the infrared region of the obtained coating film was measured with a spectrophotometer. The transmittance of the obtained coating film at 905 nm was 46.3%. The transmittance at 1500 nm was 87.3%.

<Comparative Example 2>
A paint was prepared in the same manner as in Evaluation 1 except that carbon black (brand "# 2600" manufactured by Mitsubishi Chemical Corporation) was used.

[Evaluation 11]
(Hue evaluation)
A paint was obtained in the same manner as in Evaluation 1 except that the carbon black of Comparative Example 2 was used. The obtained paint was applied to white art paper with an applicator to obtain a coating film having a film thickness of 25 μm.
The obtained coating film was visually black, and as a result of measuring the hue with a spectrophotometer (device name: "DC650", datacolor), L * = 25.9, a * =-0.01, b. * = -0.79.

[Evaluation 12]
(Transmittance evaluation)
A coating film having a film thickness of 2 μm was obtained in the same manner as in Evaluation 2 except that the carbon black of Comparative Example 2 was used. When the transmittance in the infrared region of the obtained coating film was measured with a spectrophotometer, the transmittance at 905 nm was 31.6%, and the transmittance at 1500 nm was 63.7%.

<Comparative Example 3>
Chlorinated copper phthalocyanine compound (phthalocyanine green) (manufactured by DIC Co., Ltd.) 10.0 g, 2-aminoethanethiol 12.2 g (manufactured by Kanto Chemical Co., Inc.), potassium carbonate 22. 1 g (manufactured by Kanto Chemical Co., Inc.) and 200 g of N, N-dimethylformamide were placed in a four-necked flask equipped with a cooling tube and reacted at 130 ° C. for 5 hours. After cooling the reaction, 150 g of methanol was added, and the mixture was cooled to room temperature with stirring. The obtained reaction product was further washed with methanol, then washed twice with water, and dried at 100 ° C. for 5 hours to obtain 13.2 g of a phthalocyanine black pigment.
As a result of fluorescent X-ray measurement, it was found that the phthalocyanine pigment was replaced with 2-aminoethanethiol by an average of 7 molecules. In addition, no clear peak was detected in the X-ray diffraction measurement.

[Evaluation 13]
(Hue evaluation)
A coating film having a film thickness of 25 μm was obtained in the same manner as in Evaluation 1 except that the phthalocyanine compound of Comparative Example 3 was used. The obtained coating film was visually gray, but as a result of measuring the hue with a spectrophotometer (device name: "DC650" datacolor), L * = 39.3, a * = -0.92, b. * =-6.33.

[Evaluation 14]
(Transmittance evaluation)
A coating film having a film thickness of 2 μm was obtained in the same manner as in Evaluation 2 except that the phthalocyanine compound of Comparative Example 3 was used. When the transmittance in the infrared region of the obtained coating film was measured with a spectrophotometer, the transmittance at 905 nm was 83.1%, and the transmittance at 1500 nm was 93.5%.

(Example 5)
(Photo spacer)
(Synthesis of alkali-soluble resin "A-1" for photo spacers)
In a four-necked flask equipped with a cooling tube and a stirrer, 5.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 g of propylene glycol monomethyl ether acetate, 20 g of methacrylic acid, 25 g of glycidyl methacrylate, and 10 g of styrene. , Methyl methacrylate (15 g) and tricyclomethacrylic acid [5.2.1.02.6] decane-8-yl (20 g), and after substitution with nitrogen, the temperature of the solution was raised to 70 ° C. with gentle stirring to obtain the above temperature. The polymerization reaction was carried out for 4 hours while holding the above. The weight average molecular weight Mw of the obtained copolymer was 8000.

(Photosensitive composition)
As an alkali-soluble resin, 100 g of the obtained alkali-soluble resin A-1, 45 g of Aronix M-400 (manufactured by Toa Synthetic Co., Ltd.) as a polymerizable compound having an ethylenically unsaturated bond, and Irgacure OXE02 (BASF) as a polymerization initiator. ) 7 mass g, Megafuck R-40 (manufactured by DIC Co., Ltd.) 0.1 g by mass as a leveling agent, 0.2 g of p-methoxyphenol as a polymerization inhibitor, 100 g of propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate It was dissolved in 22 g to obtain a resin solution. Next, the obtained resin solution was added to a dispersion consisting of 45 g of the phthalocyanine compound of Example 2, 50 g of the alkali-soluble resin A-1, and 50 g of propylene glycol monomethyl ether acetate, and the mixture was filtered through a membrane filter having a pore size of 0.5 μm. The photosensitive composition of Example 5 was obtained.

(Photo spacer)
The obtained polymerizable composition 5 using a spin coater was applied to the ITO electrode side of a non-alkali glass substrate sputtered with ITO as a transparent electrode, dried at 90 ° C. for 2 minutes, and had a film thickness of 3.0 μm. A coating film was formed.
Subsequently, the obtained coating film was irradiated with ultraviolet light having a light intensity of 30 mW / cm2 at 365 nm for 3.3 seconds through a chrome photomask made of quartz glass having an opening of a circular pattern having a diameter of 10 μm. The distance between the obtained coating film and the photomask was 150 μm.
Next, it was developed with a 0.5 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. and further rinsed with ultrapure water to form a pattern on a glass substrate. Further, it was heated at 230 ° C. for 30 minutes to obtain a photo spacer of Example 5.
A polyimide for vertical orientation was applied to a spin coater on the photo spacer of the obtained glass substrate with a photo spacer, dried at 80 ° C. for 5 minutes, and further fired at 230 ° C. for 30 minutes. On the other hand, a polyimide for vertical orientation was similarly applied to the ITO electrode side of the glass substrate on which ITO was formed with a spin coater, dried at 80 ° C. for 5 minutes, and further fired at 230 ° C. for 30 minutes.
Both of the obtained glass substrates are subjected to rubbing orientation treatment so that the pretilt is 1 to 2 ° with respect to the substrate surface normal direction, and an epoxy resin-based film is applied to the polyimide film on the outer periphery of one of the glass substrates using a dispenser. After applying the sealant, both glass substrates were bonded so that the pretilt angle of the liquid crystal composition after bonding was about 1 °. Then, the sealant was cured at 90 ° C. for 5 minutes and at 150 ° C. for 30 minutes to obtain a cell for evaluation.
The N-type liquid crystal composition (LCN-1, Δn: 0.102, viscosity: 16.8, Δε: -3.8 described in JP-A-2017-95712) was added to the obtained evaluation cell at 60 ° C. It was heated and injected into the glass cell by the vacuum injection method.
After the injection, the glass cell was taken out, and the injection port was sealed with a sealing agent 3026E (manufactured by ThreeBond Co., Ltd.). As a result, a liquid crystal display element in VA mode was obtained. When the prepared cell is placed between two orthogonal polarizing plates, it turns black and the dark field does not change even if the cell is rotated in the azimuth direction, and there is no in-plane phase difference in the photo spacer, or the photo It was confirmed that the optical axis direction of the spacer and the easy axis direction of liquid crystal orientation are the same direction.

(contrast)
White LEDs, polarizing plates, liquid crystal display elements, polarizing plates, and spectroradiometers (SR-LEDW: manufactured by Topcon Technohouse Co., Ltd.) were arranged in this order. The two polarizing plates were arranged so as to form a cross Nicol.
The brightness (OFF brightness) when no voltage is applied to the obtained liquid crystal display element and the brightness (ON brightness) when the voltage is applied to reach the maximum brightness are measured, and the ratio (ON brightness / OFF brightness) was used as the contrast.
The contrast of the obtained liquid crystal display element was as good as 2050. In particular, the decrease in OFF brightness was remarkable.

Claims (5)

A phthalocyanine compound represented by the following general formula (1).
General formula (1)

(In the equation, X independently represents a hydrogen atom or a halogen atom, l is an integer of 0 to 15, m and n each independently represent an integer of 0 to 8, except when either is 0. Represents an integer of 1 to 8, satisfying 0.5 ≦ m + (n / 2) ≦ 10, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal or an oxymetal). The phthalocyanine compound according to claim 1, which has a diffraction peak at 4.2 ° ± 0.2 ° ≤ 2θ ≤ 5.1 ° ± 0.2 ° in the X-ray diffraction spectrum. The claim is characterized in that the spectral transmittance in the coating film in which the phthalocyanine compound according to claim 1 or 2 is dispersed in a urethane acrylic resin is 50 to 99% at 905 nm and 90 to 99.9% at 1500 nm. Item 3. The phthalocyanine compound according to Item 1 or 2. A wavelength control agent comprising the phthalocyanine compound according to any one of claims 1 to 3. The ink, printed matter, paint, coating, plastic, fiber, film, resist for black matrix, resist for photo spacer, and cured product thereof containing the phthalocyanine compound according to claims 1 to 4.

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