JP2023059714A - Molding, resin pellets, and molding production method - Google Patents

Abstract

To provide a molding excellent in temperature rise inhibition and weather resistance, resin pellets, and a production method of the molding.SOLUTION: A molding contains a resin, and a dye comprising a compound represented by formula (1). Also provided are resin pellets and a production method of the molding.SELECTED DRAWING: None

Description

The present disclosure relates to molded articles, resin pellets, and methods for producing molded articles.

Conventionally, black pigments such as carbon black and iron oxide have been widely used when coloring a molded body black, and the above black pigments exhibit black by absorbing light in a wide wavelength range. .

Since the above-mentioned black pigment absorbs light in a wide wavelength range, the molded body is excellent in jet-blackness, while it also absorbs light with a wavelength of 780 nm to 1400 nm. There was a case where the temperature rose.
When the molded article is applied to an electronic device or the like, problems such as a short circuit of the electronic device may occur due to the temperature rise of the molded article, and it is required to suppress the temperature rise of the molded article. ing.

Here, Patent Document 1 discloses an infrared transmission product including a body portion covering an infrared transmission portion and an infrared reception portion in an infrared sensor, wherein the body portion is formed of a transparent resin material having infrared transmission properties. A base material and a black holding layer formed on the rear surface of the base material in the transmission direction of infrared rays from the transmitting part, wherein the black holding layers each have infrared transmittance and become black when mixed. At least two types of dyes and pigments are mixed in a transparent resin to form a coating film layer, and the black pressing layer has a thickness of 5 μm to 50 μm. An infrared transmitting product containing 50 to 150 parts by weight of is disclosed.

JP 2021-56345 A

In Patent Document 1, the black pressing layer contains at least two kinds of dyes and pigments that have infrared transmittance and become black when mixed.
The present inventors have recently found a new problem that when a plurality of dyes and pigments are used to develop a black color, the weather resistance of the molded article may be insufficient.

The problem to be solved by the embodiments of the present disclosure is to provide a molded article, a resin pellet, and a method for producing a molded article that are excellent in temperature rise suppression property and weather resistance.

Specific means for solving the problem are as follows.
<1> A molded article containing a dye containing at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and a resin.

In general formula (1),
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹³ represents a substituent,
m represents an integer from 0 to 5,
R ¹¹ and R ¹² may combine with each other to form a ring.
When m is 2 or more, R ¹³ may be the same or different.

In general formula (3),
R ³¹ and R ³² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ³³ represents a substituent,
n represents an integer from 0 to 5,
R ³¹ and R ³² may combine with each other to form a ring.
When n is 2 or more, R ³³ may be the same or different.
<2> the dye contains at least one of the compounds represented by the general formula (1) and the general formula (3);
m and n represent 0 or 1,
When m and n represent 1, R ¹³ and R ³³ represent a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms, the above <1 >.
<3> The molded article according to <1> or <2> above, wherein the dye contains a compound represented by the general formula (1) and a compound represented by the general formula (3).
<4> The ratio of the content of the compound represented by the general formula (1) to the total mass of the dye to the content of the compound represented by the general formula (3) to the total mass of the dye is 3. 10, the molded article according to <3> above.
<5> The dye contains a compound represented by the general formula (1),
The compound represented by the general formula (1) has R ¹³ at a position ortho to the azo group of the benzene ring to which R ¹³ is bonded, and R ¹³ is a halogen atom, a nitro group, The molded article according to any one of <1> to <4> above, which is a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms.
<6> The dye contains at least one of the compound represented by the above general formula (1) in which R ¹¹ and R ¹² are different and the compound represented by the above general formula (3) in which R ³¹ and R ³² are different. , the molded article according to any one of the above <1> to <5>.
<7> The molded article contains at least one of the dye represented by the above general formula (1) in which R ¹³ is a chlorine atom and the dye represented by the above general formula (3) in which R ³³ is a chlorine atom. The molded article according to any one of <1> to <6> above.
<8> The sum of the content of the dye represented by the general formula (1) and the dye represented by the general formula (3) with respect to the total mass of the dye is 80% by mass to 100% by mass. The molded article according to any one of <1> to <7>.
<9> The molding according to any one of the above <1> to <8>, wherein the average transmittance of the continuous wavelength band A of 15 nm or more included in the wavelength band of 780 nm to 900 nm is 85% or more. body.
<10> The molded article according to any one of <1> to <9>, wherein the resin contains at least one of a thermoplastic resin and a thermosetting resin.
<11> The molded article according to any one of <1> to <10>, wherein the dye further contains a compound having a maximum absorption wavelength in the range of 400 nm to 600 nm.
<12> The molded article according to <11> above, wherein the compound having a maximum absorption wavelength in the range of 400 nm to 600 nm is represented by the following general formula (4).

In general formula (4),
R ¹ and R ² each independently represent SO ₂ R ³ or COR ³ ;
R ³ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
<13> The molded article according to any one of <1> to <12>, wherein the resin contains a thermoplastic resin, and the thermoplastic resin has a melting point of 100°C to 300°C.
<14> The molded article according to any one of <1> to <13> above, wherein the resin has at least one group selected from a carbonyl group, a cyano group and an aromatic group.
<15> A resin pellet containing a dye containing at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and a resin.

In general formula (1),
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹³ represents a substituent,
m represents an integer from 0 to 5,
R ¹¹ and R ¹² may combine with each other to form a ring.
When m is 2 or more, R ¹³ may be the same or different.

In general formula (3),
R ³¹ and R ³² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ³³ represents a substituent,
n represents an integer from 0 to 5,
R ³¹ and R ³² may combine with each other to form a ring.
When n is 2 or more, R ³³ may be the same or different.
<16> A method for producing a molded article according to any one of <1> to <14> above,
The resin is kneaded, at least one of the compound represented by the general formula (1) and the compound represented by the general formula (3) is added to the resin, kneaded, and molded. Production method.

ADVANTAGE OF THE INVENTION According to this indication, the manufacturing method of the molded object, resin pellet, and molded object which are excellent in temperature rise control property and weather resistance can be provided.

FIG. 1 shows the ¹ H-NMR spectrum (in deuterated chloroform) of compound (1-3).

In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.

In the present disclosure, "(meth)acrylic" means at least one of acrylic and methacrylic.

[Molded body]
The molded article of the present disclosure contains a dye containing at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and a resin.

In general formula (1),
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹³ represents a substituent,
m represents an integer from 0 to 5,
R ¹¹ and R ¹² may combine with each other to form a ring.
When m is 2 or more, R ¹³ may be the same or different.

In general formula (3),
R ³¹ and R ³² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ³³ represents a substituent,
n represents an integer from 0 to 5,
R ³¹ and R ³² may combine with each other to form a ring.
When n is 2 or more, R ³³ may be the same or different.

The molded article of the present disclosure is excellent in temperature rise suppression property and weather resistance.

The reason why the above effects are exhibited is presumed as follows, but is not limited thereto.
The dye contained in the molded article of the present disclosure contains at least one of the compound represented by the general formula (1) and the compound represented by the general formula (3), and the dye has a wavelength of 780 nm to 1400 nm. It is presumed that it has excellent light transmittance and can suppress temperature rise when sunlight or the like is irradiated.
In addition, since the compound represented by the general formula (1) or the compound represented by the general formula (3) can express black color by itself, it is not necessary to use a compound for complementary color. , is presumed to have excellent weather resistance.

From the viewpoint of suppressing temperature rise, the molded article of the present disclosure preferably has an average transmittance of 80% or more in a continuous wavelength band A of 15 nm or more, which is included in the wavelength range of 780 nm to 900 nm, and 85%. It is more preferable to be above.

Confirmation of the wavelength band A is performed as follows.
The center of the molded article of the present disclosure is irradiated with light having a wavelength of 300 nm to 900 nm, and a transmission spectrum is obtained with a spectrophotometer.
In the transmission spectrum, the presence or absence of a wavelength band A, which is a continuous wavelength band of 15 nm or more and has an average transmittance of 85% or more, is confirmed.
As a spectrophotometer, U-4100 manufactured by Hitachi High-Technologies Co., Ltd. or a similar device can be used.

(pigment)
The dye contained in the molded article of the present disclosure includes at least one of the compound represented by the general formula (1) and the compound represented by the general formula (3).
From the viewpoint of the jet-blackness of the molded article, the dye preferably contains both the compound represented by the general formula (1) and the compound represented by the general formula (3). In addition, when the dye contains both the compound represented by the general formula (1) and the compound represented by the general formula (3), bleeding out of the dye from the molded article can be suppressed ( Hereinafter, it is also referred to as bleed-out suppressing property.).
Moreover, the dye may contain two or more kinds of compounds represented by general formula (1), and may contain two or more kinds of compounds represented by general formula (3).

From the viewpoint of the jet-blackness of the molded article, the dye preferably further contains a compound having a maximum absorption wavelength in the range of 400 nm to 600 nm.
In addition, the dye may contain two or more compounds having maximum absorption wavelengths in the range of 400 nm to 600 nm.

(Compound represented by general formula (1))
In general formula (1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. Also, R ¹¹ and R ¹² may combine with each other to form a ring.
The alkyl group may be linear, branched, or cyclic.
Although the alkyl group may have a substituent, it is preferably an unsubstituted alkyl group from the viewpoint of production suitability and cost. The number of carbon atoms in the substituent is not included in the 1 to 12 carbon atoms in the alkyl group.

Alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 2-butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclohexyl group and the like.

The substituent is not particularly limited, but may be a hydroxy group, an alkylcarbonyloxy group (preferably an alkylcarbonyloxy group having 2 to 8 carbon atoms), an alkylaminocarbonyloxy group (preferably an alkyl aminocarbonyloxy group), cyano group, carbamoyl group, alkylcarbamoyl group (preferably alkylcarbamoyl group having 2 to 8 carbon atoms), arylcarbamoyl group (preferably arylcarbamoyl group having 7 to 11 carbon atoms, more preferably phenylcarbamoyl group), an aryl group (preferably an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group), and the like.

When R ¹¹ and R ¹² combine with each other to form a ring, R ¹¹ and R ¹² form an alkylene group. The alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
The alkylene group may have a substituent, and the substituent is not particularly limited, and examples thereof include those described above as the substituent that the alkyl group may have.

R ¹¹ and R ¹² are unsubstituted alkyl groups having 1 to 12 carbon atoms or 1 to 12 carbon atoms having one or more substituents selected from a hydroxy group, an alkylcarbonyloxy group and an alkylaminocarbonyloxy group. An alkyl group is preferred. As a result, the heat resistance of the dye can be improved, decomposition during molding can be suppressed, and the jet-blackness of the molded product can be improved.
From the viewpoint of production cost, R ¹¹ and R ¹² are preferably unsubstituted alkyl groups having 1 to 12 carbon atoms, more preferably unsubstituted alkyl groups having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. 5 is more preferably an unsubstituted alkyl group.

In general formula (1), R ¹¹ and R ¹² are preferably different from the viewpoint of jet-blackness and bleed-out suppression properties of the molded article.
For example, it is preferable that one of R ¹¹ and R ¹² is a methyl group and the other is an ethyl group or a propyl group.

In general formula (1), m represents an integer of 0 to 5, preferably 0 or 1.

In general formula (1), R ¹³ is a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, cycloalkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, hydroxy group , a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, or a substituent formed by combining two or more of these, preferably a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group , an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, represents an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or a substituent formed by combining two or more of these, more preferably a halogen atom, a nitro group, a cyano group, or an alkoxycarbonyl group having 2 to 12 carbon atoms or represents an acyl group having 2 to 12 carbon atoms.
The above alkoxycarbonyl group and acyl group may have the above substituent, but unsubstituted alkoxycarbonyl group and unsubstituted acyl group are preferable from the viewpoint of production suitability and cost.

When R ¹³ represents a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like can be mentioned, with a fluorine atom or a chlorine atom being preferred, and a chlorine atom being more preferred.
When R ¹³ represents an alkoxycarbonyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms is preferable, and an alkoxycarbonyl group having 2 to 5 carbon atoms is more preferable.
When R ¹³ represents an acyl group having 2 to 12 carbon atoms, an acyl group having 2 to 8 carbon atoms is preferable, and an acyl group having 2 to 5 carbon atoms is more preferable. Examples of acyl groups having 2 to 12 carbon atoms include alkylcarbonyl groups having 2 to 12 carbon atoms, arylcarbonyl groups having 6 to 12 carbon atoms (eg, benzoyl group, etc.), and the like, and alkylcarbonyl groups having 2 to 12 carbon atoms. groups are preferred.

From the viewpoint of jet-blackness and bleed-out suppression of the molded article, R ¹³ is a fluorine atom, a chlorine atom, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms. more preferably a fluorine atom, a chlorine atom, a nitro group, a cyano group or an acyl group having 2 to 12 carbon atoms, a fluorine atom, a chlorine atom, a nitro group, a cyano group or an alkyl group having 2 to 12 carbon atoms It is more preferably a carbonyl group, particularly preferably a chlorine atom, a cyano group, a nitro group or an alkylcarbonyl group having 2 to 5 carbon atoms, more preferably a chlorine atom, a nitro group, a cyano group or an acetyl group. Particularly preferred, most preferably chlorine.

From the viewpoint of the heat resistance of the dye and the jet-blackness of the molded article, the compound represented by the general formula (1) has R ¹³ at the position ortho to the azo group of the benzene ring to which R ¹³ is bonded. is preferred.

Specific examples of the compound represented by formula (1) are shown below, but are not limited thereto. For example, in the specific examples of the compounds below, the compound has R 13 at the position ortho to the azo group of ^the benzene ring to which R ¹³ is attached, but R ¹³ is at the position meta. and may have R ¹³ at the para-position. Further, in the following compounds, the compounds in which m in the general formula (1) is 1 are shown, but m may be an integer of 0 to 5.
The following compounds (1-25) to (1-30) and compound (1-52) are compounds in which R ¹¹ and R ¹² in general formula (1) are bonded to each other to form a ring. .
In the table, Ph represents a phenyl group.

The method for synthesizing the compound represented by the general formula (1) is not particularly limited, but a step of condensing 1,8-diaminonaphthalene with the ketone compound (X) to synthesize an intermediate (CP) (first step); A step of synthesizing a compound represented by the general formula (2) by coupling a substituted aniline (Y) with 1-naphthylamine after forming a diazonium salt using a diazotizing agent (second step); After forming a diazonium salt of the compound represented by (2) using a diazotizing agent, it is coupled with an intermediate (CP) to synthesize a compound (disazo compound) represented by general formula (1). It is preferable to synthesize by a method including a step (third step) in this order. A specific scheme is shown below.

All raw materials necessary for synthesizing the compound represented by the general formula (1) according to the above scheme are available as reagents.
For example, 1,8-diaminonaphthalene is a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (catalog number 043-00795), 1-naphthylamine is a reagent manufactured by Tokyo Kasei Co., Ltd. (catalog number N0052), ketone compound (X ) are reagents manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. (catalog numbers 037-02316, 066-02122, 143-01505 and A10895, etc.), substituted anilines (Y) are reagents manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ( catalog numbers 037-02316, 060-02125 and 025-02492).

The reaction in the first step may be carried out using a solvent or without a solvent. When using a solvent, water, methanol or ethanol can be preferably used. Moreover, a catalyst may be used for the reaction of the first step, and concentrated sulfuric acid can be preferably used.

Examples of the diazotizing agent that can be used in the reaction of the second step include sodium nitrite, nitrosylsulfuric acid, and nitrous esters (isoamyl nitrite, etc.). From a cost point of view, sodium nitrite is preferred.
Solvents that can be used in the diazotization reaction in the second step include water, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, etc. Water is preferable from the viewpoint of cost.
A strong acid can be used in the diazotization reaction of the second step. Examples of strong acids include hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, etc. Hydrochloric acid or sulfuric acid can be preferably used.
The amount of strong acid to be used is generally 2.1 to 10 molar equivalents, preferably 2.1 to 4 molar equivalents, relative to the number of moles of the substituted aniline.
In the diazotization reaction of the second step, amidosulfuric acid or urea may be used for the purpose of deactivating the unreacted diazotizing agent.

Solvents that can be used in the second step coupling reaction include water, methanol, acetone, tetrahydrofuran, acetonitrile, acetic acid, propionic acid and mixtures thereof. Although different depending on the reaction substrate, acetone, methanol and the like can be preferably used.
In the coupling reaction of the second step, a base may be used in combination to adjust the pH. As a base, sodium hydroxide, sodium acetate, or the like can be used, but the reaction usually proceeds satisfactorily without using a base in combination.

The diazotization agent, diazotization solvent, strong acid necessary for diazotization, deactivator for unreacted diazotization agent, and coupling solvent that can be used in the reaction of the third step are the same as those listed in the second step. can use things.

The compound represented by the following general formula (2), which is used in the production of the compound represented by the general formula (1), will be described below.

In general formula (2), R ¹³ and m are the same as R ¹³ and m in general formula (1), and their description is omitted here.
From the viewpoint of the heat resistance of the dye and the jet-blackness of the molded product, the compound represented by the general formula (2) has R ¹³ at the position ortho to the azo group of the benzene ring to which R ¹³ is bonded. is preferred.

(Compound represented by general formula (3))
In general formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. In addition, R ³¹ and R ³² may combine with each other to form a ring. The alkyl group may be linear, branched, or cyclic.
Although the above alkyl group may have the above substituent, it is preferably an unsubstituted alkyl group from the viewpoint of production suitability and cost. The number of carbon atoms in the substituent is not included in the 1 to 12 carbon atoms in the alkyl group.
Since the alkyl group and the substituent are as described above, their description is omitted here.

When R ³¹ and R ³² combine with each other to form a ring, R ³¹ and R ³² form an alkylene group. The alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
The alkylene group may have a substituent, and the substituent is not particularly limited, and examples thereof include those described above as the substituent that the alkyl group may have.

R ³¹ and R ³² are selected from unsubstituted alkyl groups having 1 to 12 carbon atoms or hydroxy groups, alkylcarbonyloxy groups and alkylaminocarbonyloxy groups, from the viewpoint of the heat resistance of the dye and the jet-blackness of the molded product. It is preferably an alkyl group having 1 to 12 carbon atoms and having one or more substituents.
From the viewpoint of production cost, R ³¹ and R ³² are preferably unsubstituted alkyl groups having 1 to 12 carbon atoms, more preferably unsubstituted alkyl groups having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. 5 is more preferably an unsubstituted alkyl group.

In general formula (3), R ³¹ and R ³² are preferably different from the viewpoint of jet-blackness and bleed-out suppression properties of the molded article.
For example, it is preferable that one of R ³¹ and R ³² is a methyl group and the other is an ethyl group or a propyl group.

In general formula (3), n represents an integer of 0 to 5, preferably 0 or 1.

In general formula (3), R ³³ is a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, cycloalkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, hydroxy group , a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, or a substituent formed by combining two or more of these, preferably a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group , an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, represents an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or a substituent formed by combining two or more of these, more preferably a halogen atom, a nitro group, a cyano group, or an alkoxycarbonyl group having 2 to 12 carbon atoms or represents an acyl group having 2 to 12 carbon atoms.

When R ³³ represents a halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned, with fluorine atom or chlorine atom being preferred, and chlorine atom being more preferred.
When R ³³ represents an alkoxycarbonyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms is preferable, and an alkoxycarbonyl group having 2 to 5 carbon atoms is more preferable.
When R ³³ represents an acyl group having 2 to 12 carbon atoms, an acyl group having 2 to 8 carbon atoms is preferable, and an acyl group having 2 to 5 carbon atoms is more preferable. Examples of acyl groups having 2 to 12 carbon atoms include alkylcarbonyl groups having 2 to 12 carbon atoms and arylcarbonyl groups having 6 to 12 carbon atoms (eg, benzoyl group, etc.). Alkylcarbonyl groups are preferred.

From the viewpoint of the heat resistance of the dye and the jet-blackness of the molded product, R ³³ is a fluorine atom, a chlorine atom, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms. more preferably a fluorine atom, a chlorine atom, a nitro group, a cyano group or an acyl group having 2 to 12 carbon atoms, a fluorine atom, a chlorine atom, a nitro group, a cyano group or an alkyl group having 2 to 12 carbon atoms It is more preferably a carbonyl group, particularly preferably a chlorine atom, a cyano group, a nitro group or an alkylcarbonyl group having 2 to 5 carbon atoms, more preferably a chlorine atom, a nitro group, a cyano group or an acetyl group. Particularly preferred, most preferably chlorine.

From the viewpoint of the heat resistance of the dye and the jet-blackness of the molded product, the compound represented by the general formula (3) has R ³³ at the position ortho to the azo group of the benzene ring to which R ³³ is bonded. is preferred.

Specific examples of the compound represented by formula (3) are shown below, but are not limited thereto. For example, in the specific examples of the compounds below, the compound has R ³³ at the position ortho to the azo group of the benzene ring to which R 33 is attached, but ^{R 33 is} at the position meta. and may have R ³³ at the para position. Also, in the following compounds, the compounds in which n in the general formula (3) is 1 are shown, but n may be an integer of 0 to 5.

The method for synthesizing the compound represented by the general formula (3) is not particularly limited, but using the compound represented by the general formula (2), It can be synthesized by a method similar to the synthesis method.

(Compound having a maximum absorption wavelength at a wavelength of 400 nm to 600 nm)
The dye contained in the molded article of the present disclosure may further contain a compound having a maximum absorption wavelength of 400 nm to 600 nm. By including the above compound in the molded article of the present disclosure, the jet-blackness of the molded article can be further improved.

In the present disclosure, the maximum absorption wavelength of the compound can be measured by using a visible light spectrophotometer.
As a visible light spectrophotometer, a Varian CARY5/UV-visible spectrophotometer or equivalent device can be used.

From the viewpoint of the jet-blackness of the molded article, the compound having a maximum absorption wavelength in the range of 400 nm to 600 nm is preferably represented by the following chemical formula (4).

In general formula (4),
R ¹ and R ² each independently represent SO ₂ R ³ or COR ³ ;
R ³ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

The alkyl group may be linear, branched, or cyclic.
The above alkyl group may have a substituent. The number of carbon atoms in the substituent is not included in the number of carbon atoms of 6 to 18 of the alkyl group.

Alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, 3-heptyl group, octyl group, 2-ethylhexyl group and nonyl group. , decyl group, undecyl group, dodecyl group, tetradecyl group, methoxyethoxyethyl group, ethoxycarbonylethyl group and the like.
From the viewpoint of color purity and heat resistance, the alkyl group is preferably an alkyl group having 4 to 18 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. is more preferable.

Examples of substituents include halogen atoms, alkoxy groups, ester groups, amide groups, sulfonamide groups, and the like.

The aryl group may have a substituent. The number of carbon atoms in the substituent is not included in the 6 to 18 carbon atoms in the aryl group.

Aryl groups include a phenyl group, a 2-methylphenyl group, a 4-ethoxycarbonylphenyl group, a 4-chlorophenyl group, a 3-(2-ethylhexyloxycarbonyl)phenyl group and the like. From the viewpoint of color purity and heat resistance, the aryl group is preferably an aryl group having 8 to 18 carbon atoms, more preferably an aryl group having 10 to 18 carbon atoms.

Examples of substituents include halogen atoms, alkoxy groups, ester groups, amide groups, sulfonamide groups, and the like.

Both R ¹ and R ² preferably represent SO ₂ R ³ or COR ³ from the viewpoint of color purity and heat resistance.
From the viewpoint of color purity and heat resistance, it is more preferable that both R ¹ and R ² represent SO ₂ R ³ and R ³ represents an alkyl group ^{having 8} to 12 carbon atoms. More preferably, R ³ in R ² is the same.

Specific examples of the compound represented by formula (4) are shown below, but are not limited thereto. Among the following compounds, from the viewpoint of color purity and heat resistance, compound Y-1, compound Y-3 and compound Y-6 are preferred, and compound Y-1 and compound Y-3 are more preferred.

From the viewpoint of temperature rise suppression, weather resistance, jet-blackness, etc., the content of the dye with respect to the total mass of the molded body is preferably 0.01% by mass to 10% by mass, and 0.05% by mass to 7% by mass. %, more preferably 0.1% by mass to 5% by mass.

From the viewpoint of temperature rise suppression and weather resistance, the sum of the content of the compound represented by the general formula (1) and the compound represented by the general formula (3) with respect to the total mass of the dye is 50% by mass or more. is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
The upper limit of the sum of the content of the compound represented by the general formula (1) and the compound represented by the general formula (3) with respect to the total mass of the dye is not particularly limited, but is, for example, 100 mass. % or less, and can be 90% by mass or less.

When the dye contains both the compound represented by the general formula (1) and the compound represented by the general formula (3), from the viewpoint of the jet-blackness of the molded article and the bleed-out suppressing property, the total mass of the dye is generally Ratio of the content of the compound represented by the general formula (1) to the total mass of the dye to the content of the compound represented by the formula (3) (content of the compound represented by the general formula (1) / general The content of the compound represented by formula (3)) is preferably 3-10, more preferably 4-7.

When the dye contains a compound having a maximum absorption wavelength at a wavelength of 400 nm to 600 nm, the content of the compound having a maximum absorption wavelength at a wavelength of 400 nm to 600 nm relative to the total mass of the dye from the viewpoint of the jet blackness and weather resistance of the molded product. Is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 22% by mass, even more preferably 3% by mass to 20% by mass, and 5% by mass to 18% by mass. is particularly preferred.

The dye is a compound represented by the general formula (1), a compound represented by the general formula (3), and a compound having a maximum absorption wavelength at a wavelength of 400 nm to 600 nm, which has been conventionally used as a dye. may contain

(resin)
The resin contained in the molded article of the present disclosure is not particularly limited.
From the viewpoint of moldability, the resin preferably contains at least one of a thermoplastic resin and a thermosetting resin.
In the present disclosure, a thermoplastic resin means a resin that softens and exhibits plasticity when heated and hardens when cooled.
In the present disclosure, thermosetting resin means a resin that cures when heated. Further, in the present disclosure, the thermosetting resin includes a resin that forms a crosslinked structure or the like by heating and partially or completely cured.

Thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers, (meth)acrylic resins, saturated polyester resins such as polyethylene terephthalate, acrylonitrile styrene (AS) resins, and acrylonitrile butadiene styrene (ABS) resins. , polyvinylidene chloride resin, polyamide resin, acetal resin, polycarbonate resin, polyphenylene sulfide resin, polyetherimide resin, aromatic polyetherketone resin, polysulfone resin, fluorine resin such as polyvinylidene fluoride, polyamideimide resin, polyetheretherketone (PEEK) resin and the like.
The thermoplastic resin may be used alone or in combination of two or more.

The melting point of the thermoplastic resin is not particularly limited, but from the viewpoint of the heat resistance of the molded article, it is preferably 100° C. or higher, more preferably 110° C. or higher, and 130° C. or higher. is more preferred.
Although the upper limit of the melting point of the thermoplastic resin is not particularly limited, it is preferably 500° C. or less, more preferably 300° C. or less, from the viewpoint of moldability.

The melting point of the thermoplastic resin conforms to JIS K 7121: 2012 and is measured by using a differential scanning calorimeter and heating the thermoplastic resin from 30°C to 600°C at a heating rate of 10°C/min. do.
As a differential scanning calorimeter, DSC7000X manufactured by Hitachi High-Tech Science Co., Ltd. or a similar device can be used.

Thermosetting resins include epoxy resins, phenoxy resins, phenolic resins, polystyrene resins, phenolic resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, polyurethane resins, silicon resins and polyimide resins, polyisoprene rubbers, Examples include polybutadiene rubber, styrene-butadiene copolymer rubber, butyl rubber, acrylonitrile-butadiene rubber, chloroprene rubber, and silicone rubber.
A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of the jet-blackness of the molded article and the ability to suppress bleeding out, the resin preferably has at least one group selected from a carbonyl group, a sulfonyl group, a cyano group and an aromatic group. It is more preferred to have at least one group selected from group groups.

From the viewpoint of suppression of foaming due to water absorption during molding, the resin contained in the molded article of the present disclosure is preferably a water-insoluble resin.
In the present disclosure, a water-insoluble resin means a resin whose solubility in 100 parts by mass of water at 25° C. is less than 5 parts by mass.

The content of the resin with respect to the total mass of the molded article is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 70% by mass or more. More preferably, it is particularly preferably 80% by mass or more.
The upper limit of the resin content is not particularly limited, but can be, for example, 99.9% by mass or less.

(others)
The molded article may contain additives such as a cross-linking agent such as sulfur, a polymerization initiator, an antioxidant, a lubricant such as paraffin oil, and a plasticizer.
Sulfur includes powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, soluble sulfur, etc. These may be used alone or in combination of two or more.

[Resin Pellets]
The resin pellets of the present disclosure contain a pigment containing at least one of the compound represented by the general formula (1) and the compound represented by the general formula (3), and a resin.

From the viewpoint of infrared transmittance (infrared non-absorption), the resin pellets of the present disclosure have an average transmittance of 80% or more in a continuous wavelength band A of 15 nm or more included in the wavelength range of 780 nm to 900 nm. is preferred, and 85% or more is more preferred.

The details of the pigment and resin contained in the resin pellet of the present disclosure are the same as those of the molded article of the present disclosure described above, and therefore descriptions thereof are omitted here.
The resin pellets of the present disclosure may contain the additives described above.

[Method for manufacturing compact]
In the method for producing a molded body of the present disclosure, a resin is kneaded, and a dye containing at least one of the compound represented by the general formula (1) and the compound represented by the general formula (3) is added to the resin. , kneading and shaping.

If a thermoplastic resin is used, the resin may be heated and melt-kneaded prior to addition of the dye. Also, the resin may be heated during kneading with the dye.
The heating temperature of the resin is preferably adjusted appropriately according to the melting point of the thermoplastic resin used, and can be, for example, 80°C to 500°C.

The method of molding the kneaded product obtained by kneading the resin and the pigment is not particularly limited.
Methods for molding the kneaded product include injection molding, extrusion molding, and press molding.
A mold may also be used for molding the kneaded product.

The molding temperature of the kneaded product is preferably adjusted as appropriate according to the type of resin used, and can be, for example, 100°C to 400°C.
In addition, the molding temperature in the present disclosure means the temperature of the resin during molding.

The details of the resin and pigment used are the same as those of the molded article of the present disclosure described above, so the description is omitted here.
The additive may be added to the kneaded product.

EXAMPLES Hereinafter, the above-described embodiment will be specifically described with reference to Examples, but the above-described embodiment is not limited to these Examples.
The unit of numerical values in Table 6 is parts by mass unless otherwise specified.
Also, "o-" means ortho and "p-" means para.

<Example 1>
A twin-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd., 2D25S) having a first raw material supply port arranged on the upstream side and a second raw material supply port arranged on the downstream side was prepared.
Under conditions of a melting temperature of 200 ° C., 200 parts by mass of polypropylene (manufactured by Japan Polypropylene Corporation, Novatec (registered trademark) PP MA-3, thermoplastic resin, melting point 160 ° C.) from the first raw material supply port to the twin screw extruder. It was put in and melt-kneaded.

1.0 parts by mass of the dye consisting of powdered compound (1-3) was fed into the twin-screw extruder through the second raw material supply port, and the melted polypropylene and the dye were kneaded to obtain a melt-kneaded product.

The melt-kneaded product was extruded through a die of a twin-screw extruder to form a strand, and the strand was cut and pelletized to produce a cylindrical resin pellet (3 mm in diameter×3 mm in height).

By injection molding the above resin pellets, a molded body (plate material) having a length of 150 mm, a width of 50 mm, and a thickness of 1 mm was produced.
The injection molding conditions were as follows.
(Injection molding conditions)
・Molding temperature: 210°C
・Mold temperature: 30℃
・Injection speed: 55 mm/sec ・Injection pressure: 1400 kg/cm ²
・Holding pressure: 400 kg/cm ²
・Injection time: 5 seconds ・Cooling time: 20 seconds

<Example 2 to Example 10>
As shown in Table 6, resin pellets and molded bodies were produced according to the same procedure as in Example 1, except that the type and content of pigment, the type of resin, and the molding temperature were changed.
The thermoplastic resin used in Examples 2 to 10 is a (meth)acrylic resin having a carbonyl group (Mitsubishi Chemical Co., Ltd., MF, melting point 160° C.).

<Example 11>
Acrylonitrile-butadiene copolymer (manufactured by JSR Corporation, PNC-48, thermoplastic resin) 152 parts by mass, polypropylene resin (manufactured by SunAllomer Co., Ltd., PX600N, thermoplastic resin, melting point 160 ° C.) 18 parts by mass, paraffin oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-90) 91 parts by mass and styrene-ethylene-ethylene-propylene-styrene copolymer (manufactured by Kuraray Co., Ltd., SEPTON (registered trademark) 4077, thermoplastic resin) 30 mass part, polymerization initiator (NOF Co., Ltd., Perhexa (registered trademark) 25B) 2 parts by mass, antioxidant (BASF Japan Co., Ltd., IRGANOX (registered trademark) 1010) 0.3 parts by mass, powder Using a dye consisting of 0.8 parts by mass of the compound (1-1) and 0.2 parts by mass of the powdered compound (3-1) and a twin-screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd., 2D25S), The mixture was melt-kneaded at a kneading temperature of 180° C. and pelletized to produce resin pellets.
The acrylonitrile-butadiene copolymer is a thermoplastic resin having a cyano group, and the styrene-ethylene-ethylene-propylene-styrene copolymer is a thermoplastic resin having an aromatic group.

By injection-molding the resin pellets, a molded body (plate material) having a length of 130 mm, a width of 130 mm, and a thickness of 2 mm was obtained.
The injection molding conditions were as follows.
(Injection molding conditions)
・Molding temperature: 220°C
・Mold temperature: 30℃
・Injection speed: 55 mm/sec ・Injection pressure: 1400 kg/cm ²
・Holding pressure: 400 kg/cm ²
・Injection time: 5 seconds ・Cooling time: 20 seconds

<Example 12>
200 parts by mass of acrylonitrile-butadiene rubber (thermosetting resin), 0.8 parts by mass of powdered compound (1-1) and 0.2 parts by mass of powdered compound (3-1). The mixture was put into a kneader kneader (Model PNV-1, manufactured by Irie Shokai Co., Ltd.) set at 120° C. and kneaded at a rotation speed of 50 rpm to obtain a kneaded product.

Zinc oxide, stearic acid, sulfur and N-(tert-butyl)-2-benzothiazolesulfenamide are added to the resulting kneaded product, and the product is kneaded using an electrically heated high temperature roll machine manufactured by Ikeda Kikai Kogyo Co., Ltd. It was kneaded and vulcanized under the conditions of room temperature (25° C.) and roll rotation speed of 25 rpm.

By press-molding the kneaded material after the vulcanization treatment, a compact having a length of 15 mm, a width of 15 mm, and a thickness of 2 mm was obtained.
The press molding conditions were as follows.
(Conditions for press molding)
・Molding temperature: 180°C
・Press pressure: 12 kg/cm ²
・Cooling time: 20 seconds

<Example 13>
Silicone rubber (manufactured by Shin-Etsu Chemical Co., Ltd., LPS-3421T / C-3421T (mass ratio of A liquid and B liquid 10: 1), thermosetting resin) 200 parts by mass, powdered compound (1- 1) A dye consisting of 0.8 parts by mass and 0.2 parts by mass of powdered compound (3-1) is kneaded using a vane stirrer at a roll rotation speed of 300 rpm to form a kneaded product. Obtained.
The kneaded product was poured into a mold until the thickness became 2 mm, and heated to 180° C. using a hot plate to obtain a compact of 50 mm long×50 mm wide×2 mm thick.

<Example 14, Example 15, Comparative Example 1 and Comparative Example 2>
As shown in Table 6, resin pellets and moldings were produced according to the same procedure as in Example 11, except that the type and content of the pigment were changed.

The compounds contained in the dyes used in the above Examples and Comparative Examples are as follows.

・ CB: Carbon black ・ Mixture (C-1): Oplus Black 838 manufactured by Orient Chemical Industry Co., Ltd., a pigment prepared by blending two or more primary color synthetic dyes to black

Methods for synthesizing compound (1-3) and the like are described below.

(Synthesis Example 1: Synthesis of compound (1-3))
Compound (1-3) was synthesized according to the following scheme.

[Synthesis of intermediate (CP3)]
158 g (1 mol) of 1,8-naphthalenediamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 1400 mL of methanol are added to a 3-liter three-necked flask, and then concentrated sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd.) is added under ice cooling. 57 g (0.6 mol) of reagent special grade manufactured by the company was slowly added dropwise while maintaining the internal temperature at 40°C or lower.
After injecting 100 g (1.16 mol) of 2-pentanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent first grade) corresponding to the ketone compound (X) into this suspension, the mixture is reacted at an internal temperature of 55° C. for 1 hour. let me
The reaction liquid was cooled to 25° C., and 1500 mL of a 2 mol/L sodium hydroxide aqueous solution was slowly added dropwise to the reaction liquid under water cooling. After stirring at 25 ° C. for 15 minutes, suction filtration is performed, water / methanol = 1/1 (volume ratio) 1000 mL, then water 1000 mL, and finally water / methanol = 1/1 (volume ratio) 1000 mL. The resulting powder was dried in an air drier at 50° C. for 24 hours to obtain a pale brown powder of intermediate (CP3) (yield: 210 g, yield: 93%).

[Synthesis of compound (2-1)]
In a 1 L three-necked flask, 71.4 g (0.56 mol) of o-chloroaniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade) corresponding to the substituted aniline (Y) and 560 mL of water are added, and then Under ice-cooling, 140 mL (1.68 mol) of concentrated hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent special grade) was slowly added dropwise while maintaining the internal temperature at 10°C or lower.
To this solution, an aqueous solution obtained by dissolving 38.64 g of sodium nitrite (manufactured by Fujifilm Wako Pure Chemical Industries, special reagent grade) in 69.6 g of water was slowly added dropwise while maintaining the internal temperature at 0 ° C. to 5 ° C. , at an internal temperature of 0°C to 5°C for 15 minutes.
Add 5.44 g of amidosulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent first grade) to the solution obtained by dropping the aqueous solution and reacting it, reacting at an internal temperature of 0 ° C. to 5 ° C. for 15 minutes, and diazonium salt solution. bottom.
Separately, after adding 1,904 mL of acetone to 76.2 g (0.53 mol) of 1-naphthylamine (manufactured by MAHATME DYE CHEM PVT LTD) in a 3 L three-neck flask, the internal temperature was cooled to 15 ° C. to obtain a solution. rice field.
To the above solution, the previously prepared diazonium salt solution was carefully added dropwise while maintaining an internal temperature of 15°C to 20°C, followed by reaction at an internal temperature of 15°C to 20°C for 30 minutes. Crystals precipitated from the reaction solution were collected by suction filtration and spray-washed with 1000 mL of acetone/water=1/1 (volume ratio).
The wet cake of the above crystals is added to 1500 mL of acetone/ethyl acetate = 1/1 (volume ratio), heated to 45°C to 50°C, stirred for 15 minutes, filtered while hot, and acetone/ethyl acetate = 1. / 1 (volume ratio) 500 mL, and then dried in a blower dryer at 40 ° C. for 6 hours to obtain the hydrochloride of compound (2-1) as dark green crystals (yield: 142 g, yield: 85%).

[Synthesis of compound (1-3)]
In a 1 L three-necked flask, 29.8 g (0.094 mol) of the hydrochloride of the compound represented by formula 2-1, 172 mL of water, acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent special grade) 120 mL, propionic acid ( FUJIFILM Wako Pure Chemical Co., Ltd., reagent special grade) (172 mL) was added, and the internal temperature was cooled to 5°C to obtain a solution.
22.4 mL (0.269 mol) of concentrated hydrochloric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) is carefully added dropwise to the above solution at an internal temperature of 10 ° C. or less, and then sodium nitrite (FUJIFILM Wako Pure Chemical Industries, Ltd. A solution of 6.48 g (0.094 mol) of special reagent grade manufactured by the company dissolved in 25.6 mL of water was slowly added dropwise while maintaining the internal temperature at 0°C to 5°C. After reacting for 1 hour, a diazonium salt solution was obtained.
Separately, in a 2 L three-neck flask, intermediate (CP3) 21.28 g (0.094 mol), amidosulfuric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., reagent first grade), tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., Special grade reagent) (128 mL) and water (128 mL) were added to cool the internal temperature to 5°C. The previously prepared diazonium salt solution was slowly added dropwise while maintaining the internal temperature at 5°C to 10°C, followed by reaction at the internal temperature of 0°C to 10°C for 30 minutes, and then reaction at 15°C to 20°C for 30 minutes. rice field.
576 mL of acetone was added dropwise to the solution after the reaction, and the precipitated crystals were collected by suction filtration and washed with acetone/water=1/1 (volume ratio). The resulting wet cake was added to a mixed solvent of 3000 mL of ethyl acetate and 1200 mL of water, stirred, and neutralized to pH 8 using an aqueous sodium hydrogen carbonate solution. Thereafter, insoluble matter is removed by celite filtration, and only the ethyl acetate layer is concentrated using a rotary evaporator, and the resulting residue is recrystallized with methanol to obtain deep green lustrous crystals of compound (1-3). (30.6 g yield, 64% yield).
MS (mass spectrometry) (m/z): 520 ([M+1] ^<+> , 100%). The melting point of compound (1-3) was 105°C. FIG. 1 shows the ¹ H-NMR spectrum (in deuterated chloroform) of compound (1-3).

(Synthesis Example 2 and Synthesis Example 3: Synthesis of compound (1-1) and compound (1-31))
The compound ( 1-1) was synthesized.
2-pentanone corresponding to the ketone compound (X) is changed to 2-propanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent first grade), and o-chloroaniline is replaced with o-fluoroaniline (Fujifilm Wako Pure Chemical Industries, Ltd. The compound (1-31) was synthesized in the same manner as the synthesis method of the compound (1-3), except that the reagent was changed to a special reagent grade manufactured by the company.

(Synthesis Example 4: Synthesis of compound (3-7))
Compound (3-7) was synthesized according to the following scheme.

[Synthesis of compound (3-7)]
In a 1 L three-necked flask, 29.8 g (0.094 mol) of the hydrochloride of the compound (2-1), 172 mL of water, 120 mL of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), propionic acid (Fujifilm 172 mL of reagent special grade manufactured by Wako Pure Chemical Industries, Ltd. was added, and the internal temperature was cooled to 5° C. to obtain a solution.
22.4 mL (0.269 mol) of concentrated hydrochloric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) is carefully added dropwise to the above solution at an internal temperature of 10 ° C. or less, and then sodium nitrite (FUJIFILM Wako Pure Chemical Industries, Ltd. An aqueous solution of 6.48 g (0.094 mol) dissolved in 25.6 mL of water was slowly added dropwise while maintaining the internal temperature at 0°C to 5°C, and then the internal temperature was 0°C to 5°C. for 1 hour to obtain a diazonium salt solution.
Separately, in a 2 L three-necked flask, 21.28 g (0.094 mol) of the above intermediate (CP3), amidosulfuric acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., reagent first grade), tetrahydrofuran (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. , special grade reagent) and 128 mL of water were added to cool the internal temperature to 5°C. The previously prepared diazonium salt solution was slowly added dropwise while maintaining the internal temperature at 5°C to 10°C, followed by reaction at the internal temperature of 0°C to 10°C for 30 minutes, and then reaction at 15°C to 20°C for 30 minutes. rice field.
After the reaction, 576 mL of acetone was added dropwise to the diazonium salt solution, and the precipitated crystals were collected by suction filtration and spray-washed with acetone/water=1/1 (volume ratio). The resulting wet cake was added to a mixed solvent of 3000 mL of ethyl acetate and 1200 mL of water, stirred, and neutralized to pH 8 using an aqueous sodium hydrogen carbonate solution. After that, insoluble matter was removed by Celite filtration, and only the ethyl acetate layer was concentrated using a rotary evaporator. The resulting residue was applied to a silica gel column to obtain compound (3-7) (5.4 g, 11% yield).
MS (mass spectrometry) (m/z): 520 ([M+1] ^<+> , 100%). The melting point of compound (3-7) was 152°C.
NMR (DMSO- _d6 ): 0.88 (t, 3H), 1.43 (m, 5H), 1.72 (m, 2H), 6.60 (d, 1H), 6.94 (d, 1H), 6.96 (d, 1H), 7.20 (s, 1H), 7.36 (t, 1H), 7.57-7.61 (t, 2H), 7.77 (d, 1H) ), 7.79 (d, 1H), 7.84 (m, 2H), 7.97 (d, 1H), 8.04 (d, 1H), 8.17 (d, 1H), 8.82 (d, 1H), 9.07 (d, 1H), 9.90 (brs, 1H)

(Synthesis Example 5 and Synthesis Example 6: Synthesis of Compound (3-1) and Compound (3-2))
The compound ( 3-1) was synthesized.
2-pentanone corresponding to the ketone compound (X) is changed to 2-propanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent first grade), and o-chloroaniline is replaced with o-fluoroaniline (Fujifilm Wako Pure Chemical Industries, Ltd. The compound (3-2) was synthesized in the same manner as the synthesis method of the compound (3-7), except that the reagent was changed to a special reagent grade manufactured by the company.

(Synthesis Example 7 and Synthesis Example 8: Synthesis of compound (4-1) and compound (4-2))
2-pentanone corresponding to the ketone compound (X) is changed to 2-propanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent first grade), and o-chloroaniline is replaced with p-fluoroaniline (Fujifilm Wako Pure Chemical Industries, Ltd. A compound (4-1) was synthesized in the same manner as for the synthesis of compound (1-3), except that the reagent was changed to a special reagent grade manufactured by the company.
2-pentanone corresponding to the ketone compound (X) is changed to 2-propanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent first grade), and o-chloroaniline is replaced with aniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Compound (4-2) was synthesized in the same manner as for compound (1-3), except that the reagent was changed to special grade).

(Synthesis Example 9: Synthesis of compound (Y-1))
Compound (Y-1) was synthesized according to the following scheme.

[Synthesis of Intermediate A]
The following compound (A) (synthesized by the method described in European Patent Application Publication No. 0571959) was prepared.
According to the above synthesis scheme, a mixed solution of 100 parts by mass of compound (A) and 390 ml of pyridine was cooled to 5°C, and 87 parts by mass of octanesulfonyl chloride was added dropwise thereto at a reaction temperature of 25°C or lower. After the reaction mixture was stirred at room temperature for 2 hours, 2 L of 4N hydrochloric acid aqueous solution was added and the mixture was stirred at 25°C. After stirring, crystals were filtered from the reaction solution. The filtered crystals were washed with 500 ml of methanol and then dried to obtain 153 g of intermediate A (yield 91%).
The results of confirming the structure of the obtained intermediate A by NMR are shown below.
¹ H-NMR (300 MHz, CDCl3) δ 0.8 (t, 3H), 1.0-1.4
(m, 19), 1.6 (m, 2H), 3.2 (t, 2H), 5.6 (s, 1H), 7.3
(d, 2H), 7.9 (d, 2H), 10.2 (s, 1H), 12.9 (s, 1H)

According to the above synthesis scheme, 68 g of ethyl orthoformate was added to a suspension of 110 g of intermediate A and 650 ml of acetic acid at 25° C., and the reaction solution was stirred at 80° C. for 3 hours. 1.1 L of methanol was added to the reaction solution, and after cooling, it was collected by filtration and washed with methanol to obtain 96
g of Y-1 was obtained (yield 88%).
The results of confirming the structure of the obtained Y-1 by NMR are shown below.
¹ H-NMR (300 MHz, CDCl3) δ 0.8 (t, 6H), 1.2-2.0
(m, 41H), 3.3 (t, 4H), 7.3 (d, 4H), 7.6 (br, 2H), 7
. 8 (d, 4H), 8.4 (s, 1H)

<<Measurement of Infrared Transmittance>>
The center of the molded body produced in Example 1 was irradiated with light having a wavelength of 300 nm to 900 nm, and a transmission spectrum was obtained with a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). Next, the average value of the infrared transmittance in the wavelength band of 850 nm to 900 nm (continuous wavelength band A of 15 nm or more) was 88%.
The average values of the infrared transmittance in the above wavelength range were obtained in the same manner for other examples and comparative examples, and are summarized in Table 6.

<<Temperature rise suppression evaluation>>
After the molded article produced in Example 1 was allowed to stand in an environment of 25° C. for 1 hour, the surface temperature was measured with a thermography camera (FLIR T530 manufactured by Ricoh Co., Ltd.).
The molded body was irradiated for 3 hours using an artificial solar lighting lamp XC-100EFSS manufactured by SERIC.
The surface temperature of the molded article immediately after irradiation was measured by the thermography camera, and the temperature rise (°C) of the molded article before and after irradiation was obtained.
In the other examples and comparative examples, the temperature rise of the molded body was obtained in the same manner and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The temperature rise of the molded body was 10°C or less.
B: The temperature rise of the compact was over 10°C.

<<Weather resistance evaluation>>
The molded article produced in Example 1 was subjected to an accelerated weather resistance test for 2000 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd., black panel temperature: 63 ° C., with rain), and discoloration before and after the test. (ΔE) was measured with a color difference meter (Konica Minolta, CM-26dG) and evaluated according to the following evaluation criteria.
In other examples and comparative examples, ΔE was obtained in the same manner and evaluated based on the following evaluation criteria. Table 6 also lists the values of ΔE.
(Evaluation criteria)
A: ΔE was 2.5 or less.
B: ΔE was more than 2.5.

<<Evaluation of jet blackness>>
The L* (lightness) of the molded articles produced in the above Examples and Comparative Examples were measured according to JIS Z 8781-4:2013, and are summarized in Table 6.

<<Evaluation of Bleed-out Suppression>>
5.0 g of the melt-kneaded product used in Example 1 was weighed into a 50 ml glass tube bottle, sealed with a cap, stored in a constant temperature bath at 60 ° C. for 24 hours, and then cooled to room temperature (25 ° C.). It was allowed to stand until it returned to form a solid.
After that, a photograph of the surface of the solid was obtained with an electron microscope (S-4800 type field emission scanning electron microscope manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: Bleeding out of dye was hardly observed.
B: Bleeding out of the dye was observed, but most of the particles were small solids of less than 1 µm.
C: Bleeding out of the dye was observed, and a large solid of 1 μm or more was observed.

From Table 6, it can be seen that the molded articles of Examples containing a dye containing at least one of the compound represented by the general formula (1) and the compound represented by the following general formula (3) do not contain the dye. It can be seen that compared with the molded body of Comparative Example 1, the temperature rise suppression property is excellent.
Further, from Table 6, the molded article of the example containing the dye containing at least one of the compound represented by the general formula (1) and the compound represented by the following general formula (3) has the above dye. It can be seen that the weather resistance is superior to that of the molded article of Comparative Example 2, which instead contains a pigment obtained by blending two or more primary color synthetic dyes so as to give a black color.

Claims (16)

A molded article containing a dye containing at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and a resin.

In general formula (1),
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹³ represents a substituent,
m represents an integer from 0 to 5,
R ¹¹ and R ¹² may combine with each other to form a ring.
When m is 2 or more, R ¹³ may be the same or different.

In general formula (3),
R ³¹ and R ³² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ³³ represents a substituent,
n represents an integer from 0 to 5,
R ³¹ and R ³² may combine with each other to form a ring.
When n is 2 or more, R ³³ may be the same or different. The dye contains at least one of the compounds represented by the general formula (1) and the following general formula (3),
m and n represent 0 or 1,
Claim 1, wherein when m and n represent 1, R ¹³ and R ³³ represent a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms. The molded article described in . The molded article according to claim 1 or 2, wherein the dye contains the compound represented by the general formula (1) and the compound represented by the general formula (3). The ratio of the content of the compound represented by the general formula (1) with respect to the total mass of the dye to the content of the compound represented by the general formula (3) with respect to the total mass of the dye is 3 to 10. 4. The molded article according to claim 3. The dye contains a compound represented by the general formula (1),
The compound represented by the general formula (1) has R ¹³ at a position ortho to the azo group of the benzene ring to which R ¹³ is bonded, and R ¹³ is a halogen atom, a nitro group, The molded article according to any one of claims 1 to 4, which is a cyano group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms. The dye comprises at least one of the compound represented by the general formula (1) in which R ¹¹ and R ¹² are different, and the compound represented by the general formula (3) in which R ³¹ and R ³² are different. The molded article according to any one of claims 1 to 5. wherein the molded article contains at least one of the dye represented by the general formula (1), wherein ^R13 is a chlorine atom, and the dye represented by the general formula (3), wherein ^R33 is a chlorine atom; The molded article according to any one of claims 1 to 6. Claims 1 to 1, wherein the sum of the content of the dye represented by the general formula (1) and the dye represented by the general formula (3) with respect to the total mass of the dye is 80% by mass to 100% by mass. The molded article according to any one of claims 7 to 9. The molded article according to any one of claims 1 to 8, wherein the average transmittance of a continuous wavelength band A of 15 nm or more included in the wavelength region of 780 nm to 900 nm is 85% or more. The molded article according to any one of claims 1 to 9, wherein the resin contains at least one of a thermoplastic resin and a thermosetting resin. The molded article according to any one of claims 1 to 10, wherein the dye further contains a compound having a maximum absorption wavelength in the range of 400 nm to 600 nm. 12. The molded article according to claim 11, wherein the compound having a maximum absorption wavelength in the range of 400 nm to 600 nm is represented by the following general formula (4).

In general formula (4),
R ¹ and R ² each independently represent SO ₂ R ³ or COR ³ ;
R ³ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. The molded article according to any one of claims 1 to 12, wherein the resin contains a thermoplastic resin, and the thermoplastic resin has a melting point of 100°C to 300°C. The molded article according to any one of claims 1 to 13, wherein the resin has at least one group selected from a carbonyl group, a cyano group and an aromatic group. A resin pellet containing a dye containing at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (3), and a resin.

In general formula (1),
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹³ represents a substituent,
m represents an integer from 0 to 5,
R ¹¹ and R ¹² may combine with each other to form a ring.
When m is 2 or more, R ¹³ may be the same or different.

In general formula (3),
R ³¹ and R ³² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ³³ represents a substituent,
n represents an integer from 0 to 5,
R ³¹ and R ³² may combine with each other to form a ring.
When n is 2 or more, R ³³ may be the same or different. A method for producing a molded article according to any one of claims 1 to 14,
A molded body, wherein the resin is kneaded, at least one of the compound represented by the general formula (1) and the compound represented by the general formula (3) is added to the resin, kneaded, and molded. Production method.

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