JPS5986662A - Azo pigment having core composed of silica - Google Patents

Abstract

PURPOSE:To provide the titled pigment which has excellent resistance to solvents, water and heat and transmittance and gives high color density with fastness, by bonding an azo pigment through an aminosilane coupling agent to the surface of a core composed of fine silica powder. CONSTITUTION:An azo pigment having a core composed of silica, such as compd. of formula III or IV, is composed of a core composed of fine silica powder having a particle size of 10mu or below and a coating of a amono- or polyazo dye chemically bonded through an aminosilane coupling agent such as a compd. of formula III or IV to the surface of the core. Azo dyes obtd. by using esterified silica gel have been prepd. in recent years, but they have disadvantages that the yields of the esterification reaction are low, the reaction must be carried out under high-temperature conditions, and the formed ester bond is highly polarized and easily undergoes hydrolysis. By chemically bonding the azo dye through the coupling agent to the core composed of fine silica powder, there can be obtd. a pigment which has good light transmittancy and give high color density with fastness.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new type of azo pigment, more specifically, it is made of silica fine powder Kecoa, and is robust and has excellent properties such as solvent resistance, water resistance, heat resistance, and translucency. This invention relates to an azo pigment with high color density.

Recently, using the reactivity of silanol on the surface of silica gel,
This is esterified with phenol or phenylalkanol to introduce a phenyl group onto the surface of the silica molecule, and then this phenyl group is nitrated, reduced, diazotized, and coupled to form an azo dye on the core of the silica molecule. It has been reported that Sudan 1 is formed (color material, 55 [
5] 280-287.Refer to 1982).

However, azo pigments formed using esterified silica have low yields and require strict conditions in the esterification reaction, and the 1-ester bonds formed are highly polarized and cannot be hydrolyzed. There are various disadvantages such as being susceptible to

Therefore, the Ministry of the Invention and others conducted extensive research aimed at creating an azo pigment with a silica core that does not have the above-mentioned drawbacks, has excellent fastness, high color density, and good translucency.
It has been discovered that the above object can be achieved by chemically bonding the surface of silica fine powder of 0 micron or less and the azo dye cliff via an aminosilane caglyreg agent, and has completed the present invention. It's arrived.

According to the present invention, the core is composed of a fine silica powder core having a particle size of 10 microns or less, and a mono- or polyazo dye sample chemically bonded to the surface of the core through an aminosilane coupling agent. An azo pigment having a silica core is provided.

The azo pigment of the present invention has a structure in which the surface silanol group of a fine silica powder and the residue of a mono- or tetra-lyazo dye are chemically bonded to each other using an aminosilane coupling agent as an intermediary, and its basic structure is shown schematically. A specific example is as follows.

(Ebo-si-RI-z-D < 1) where,
Q represents fine silica powder; RI represents a lower alkylene group which may contain -NH- or -NHCO- in the chain; Z represents -NHCO-
, -NH-Cfl, -C7no.

H −N=(Jl−, −Nl no Cfl, −, −NI4SO
,.

-NH-CH, -CH, -C-, etc. amino bridge 'tif#
i Negative Ge 1 Representation; D represents a mono- or polyazo dye residue.

In this specification, the term "lower" refers to the group or compound to which this term is attached to have less than 6 carbon atoms, preferably less than 4 carbon atoms.

In the above formula (1), the "lower alkylene group which may contain -NH- or -NHCO- in the chain" represented by RI includes those having 3 to 6 carbon atoms, such as , -CJi2CH2C11°-CD,
CH, CH, CH2-, -CH, CH, CH, -NH-
Examples include CH2CHt-, -CH, CH, CB, -NHCO-, and the like.

The residue of the mono- or polyazo dye represented by D includes, for example, those represented by the following general formula.

-Ar'-N=N-Ar"
fl)-Ar'-N=N-Ar"-N=N-Ar"
(2)-Ar'-NHCO-Ar'-N=
N-Ar'(31-Ar'-CONH-
Ar"-N=N-Ar6-N=N-Ar" 14)-
Ar"-CONII-Ar"-N-Ar"-N=N-A
r2+51O In each of the above formulas, Ar', Ar", Ar', Ar" and Ar6 each independently represent a phenylene or naphthylene group which may be ablated; A? ″ represents a group of a coupling component.

The substituent that may exist on the benzene or naphthylene group in the [optionally substituted phenylene or naphthylene group] represented by Ar'-Ar6 above is any group that can be commonly found in the field of azo dye chemistry. For example, lower alkoxy groups such as methoxy, 5-ethoxy; methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobuty A/,
(lk class alkyl groups such as 88C-buty/l/, tart-butyl; halogen atoms such as chlorine, bromine, fluorine; mono- or di(lower alkyl) amine groups such as methylamino, ethylamino, trimethylamino, diethylamino, etc.) ;Nitro groups etc. are removed.

As specific examples of the above-mentioned optionally substituted phenylene or naphthylene group, the following can be exemplified.

6- Such.

On the other hand, the group -1 of the coupling component represented by Ar2 includes the group of the coupling component of Ninkura found in ordinary azo dyes, and representative examples thereof are V, f T ” As written.

In the formula, 41 represents a group which together with the benzene ring forms a polynuclear aromatic group such as a naphthalene salt or anthracene, or a ↑η group such as an indole ring, a carbazole ring, a benzofuran ring; All and As each represents a hydrogen atom, or an optionally substituted alkyl, cycloalkyl, aryl, aralkyl, or heterocyclic group; A 5- or 6-membered search ring group may be formed, which may be a 5- or 6-membered cyclic group.

〔example〕

In the formula, BI is a halo-9-key atom such as chlorine, odorant, or fluorine; a lower alkyl group such as methyl, ethyl, or propylbutyl; a lower alkoxy group such as methoxy, ethoxy, or propoxybutoxy; a nitro group, or a cyano group. group, a phenyl group which may be mono-substituted, di-substituted or tri-substituted by a xyl group, a sulfonic acid residue, a sulfonic acid residue, or an aromatic ring such as a naphthalene group, a carbazole ring, a benzofuran ring, a pyridine ring, etc. , or represents a phenyl-lower alkyl group or a chloro-lower alkyl group.

2 In the formula, B2 and B3 are a halogen atom such as halogen or bromine; a lower alkyl group such as methyl or ethyl; or a group optionally substituted with a lower alkoxy group such as methoxy or ethoxy. =R group, or 1d, represents a lower alkyl group such as methyl, ethyl, globyl, etc.

More specifically, the following are exemplified.

11- (b) Ar' In the formula, A4 represents a lower alkyl group, a carboxyl group, or a lower alkoxycarponyl group; Ar? ↑H represents an optionally substituted phenyl or naphthyl group.

〔example〕

In the formula l2, A11 represents a hydrogen atom, a lower alkyl group, or an optionally substituted phenyl group; Ar'' represents an optionally substituted phenyl or naphthyl group.

〔example〕

C0CH.

14-(A6 1 ) In the formula, A6 represents a water atom, a lower alkyl group, a hydroxy lower alkyl group, or a lower social alkoxy lower argyl group.

c, /711o C2//, c2H
sC, ji, OCHs In the azo pigment of the present invention, the surface of the silica fine powder that is attached to the core is treated with an aminosilane coupling agent in advance to introduce an amino group onto the surface of the silica fine powder, and then the amino group is It can be produced by bonding residues of mono- or polyazo dyes as shown in formulas (1) to (5) above according to a conventional method.

Hereinafter, the method for producing the azo-based wholesale material of the present invention will be explained in more detail.

The fine silica powder that forms the core of the azo reed material of the present invention has an average particle size of 10 microns or less. The suitable particle size depends on the use of the final product, but in general, smaller particle sizes are easier to handle and are advantageous when mixed with other materials, etc. Therefore, the fine silica powder is preferably Suitable particles have an average particle size of 5 microns or less, preferably 0.1 microns or less. Specific examples of such silica powders include dry process silica available under trade names such as "Aerosil" (manufactured by Nippon Aerosil Co., Ltd.);
“Thyroid” (manufactured by Fuji Davison Chemical Co., Ltd.), “Mizukasil” (manufactured by Mizusawa Chemical Industry Co., Ltd.), “Tokusil” (@Sansoten)
Wet process silica, etc. available under trade names such as
As mentioned above, preferably 1 piece/1oon'' or more is good.

Here, the surface OHe degree is determined by first heating a 1 gram sample from 15017-℃ to 1000℃1, and measuring the decrease in weight (burning deenergization) when heating. Sample light...F-1 is generated from two adjacent silanol groups of 1 and 7
2 X 6 XIO”
/18, further divided by the separately measured B hr T specific surface area (n?/?), and the unit is (pieces/loo, 4”)
It means 11K converted to .

The fine silica powder mentioned above! However, depending on your safety, it may be used after previously surface-treating it with an acid such as sulfur, salt, or an alkali such as caustic soda or caustic potash.

Such fine silica powder is first mixed with an aminosilane coupling agent. In this JJl, the aminosilane coupling agent that has been used in the past is represented by the following formula (1): In the formula, R1 has the above-mentioned Kurami. 2 represents a lower alkyl group; 18-83 represents a hydrogen atom or a lower alkyl group; is an integer of 1 to 3; n is 0.1 or 2; preferred are the types shown below. It is.

In the above formula (1), R2 and l? The "lower alkyl group" represented by " may be either linear or branched, for example, methyl, ethyl, n-propyl, isoglogyl, n-butyl, isobutyl, 8eC -butyl, tert-butyl, etc., and the "lower alkylene group which may not contain -Nil- or -NHCO- in lead" represented by RI has a total of 3 to 6 carbon atoms. For example, -C112CII, CH, -, -CPI, CH
, CH, C1l, -.

-CI-J, C1l, CI-J, -NH-Cfl, CH
2-, -CH, CH, CH, -NHCO-, etc. are included.

Therefore, as the aminosilane coupling formula 11 that can be used in the present invention, for example, (C,H,O)
,5i-CD,ClIC11,-NH,.

(CB, O), (CR3) S i -CH, CH,
CH, -NH-CH, CH, -NH,.

(CH, (J), 5i-CH, Cll2CH, -NH-
CB, C11,-NH,.

(C,H,0)3Si-CH,CJI,CH,-NHC
O-Nl/l.

(CH, 0), 5i-CH, CH, CH, -NH2゜(
C, H, O)t (CH,) S i -CJI, CB
, CFI, -N I.

(CH, 0) (CFI, ), 5i-CH, C11CH
,CH,-NH2゜(Ct鵡C)) (Cfl, ),
Si-CH, CH, CH, -NPi.

Examples include.

Treatment of fine silica powder with such an aminosilane coupling agent can usually be carried out by contacting the fine silica powder with an aminosilane coupling agent in a suitable liquid medium. Examples of the liquid medium include water; alcohols such as methanol, ethanol, and pronosonol; or a mixture of water and these alcohols.
The treatment temperature is generally room temperature to the reflux temperature of the die, preferably the reflux temperature. The amount of the aminosilane coupling agent used is not strictly limited, but it is generally advantageous to use it at least 0.5 tons per 100 tons of silica powder, preferably 5 to 20 tons. It is.

By treating the silica fine powder with the aminosilane coupling agent in this way, the surface silanol groups of the silica fine powder and the alkoxy groups of the aminosilane coupling agent (
RIrJ), a condensation reaction (coupling reaction) occurs, and fine silica powder coated with an aminosilane coupling agent is obtained.

In addition, when the aminosilane coupling agent has two or more alkoxy groups (R'0)f, in parallel with the above condensation reaction, the molecules of the aminosilane coupling agent also react to form a siloxane bond. is generated, and a compound having a structure in which the aminosilane coupling agent is three-dimensionally cross-linked on the silica fine powder is formed.

The silica fine powder treated with the aminosilane coupling agent in this way has a general structure shown in the following formula (in which → and R1 have the above meanings), which can be optionally treated with alcohol or the like. After normal post-treatments such as washing and drying, the above formula (1
) to (5) for introducing residues of mono- or polyazo dyes. Hereinafter, introduction of each mono- or polyazo dye residue of formulas (11 to (5)) will be explained in more detail.

[1] Introduction of monoazo dye group of formula (1): 22- (Vl) (1-1) In the above formula, @, R', Ar', Ar" and Z have the above meanings; Y represents a functional group that reacts with the amino group; Q represents a hydrogen atom, a nitro group, or a protected amino group that is bonded to a carbon atom of the aromatic ring other than the carbon atom adjacent to the carbon atom to which Y is bonded; XO represents C1O, BrO, EF?, etc., t 7 f.

In the introduction of the monoazo dye residue of formula (11), first, the silica fine powder [formula (1)] treated with an aminosilane coupling agent as described above is reacted with the compound of formula (Iv). f.

In formula (IV), Y is a functional group that reacts with the terminal amino group of the aminosilane coupling agent, and examples include groups such as I. Here, Hal represents a location atom (eg, C1, Iir, etc.); 1-4 represents a lower argyl group (eg, methyl, ethyl, etc.). On the other hand, Q is bonded to a carbon atom of an aromatic ring other than the carbon atom adjacent to the carbon atom to which the group Y is bonded, so for example, when Ar' represents an optionally substituted phenylene group, , Q should be meta-added to the base Y!
eyes (present in the vertebral position).

represents a hydrogen atom, a nitro group, or a protected amine group, and the protecting group for the amino group is usually an amino protecting group that can be easily removed by hydrolysis, such as an acyl group such as acetyl, propionyl, benzoyl, etc. I'll meet you there.

Therefore, as specific examples of the compound of the above formula (IV), the following can be used.

25- And.

The reaction of the hexasilica fine powder treated with an aminosilane coupling agent 4/I with the compound of formula (IV) above is generally carried out in a suitable organic solvent, such as methanol, ethanol, n
-Alcohols such as propatool; ethers such as ether ether and tetrahydrofuran; benzene, toluene,
Inert % aromatic solvents such as xylene; ketones such as acetone, methyl ethyl ketone, diethyl ketone; dimethyl sulfoside, N,N-trimethylformamide, sulfolane,
Room temperature or rapid flow of reaction mixture in hexamethylphosphortriamide, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, etc.? This can be done in N[. In this reaction (c), it is desirable to carry out the reaction in the presence of a reaction accelerator depending on the type of group Y in the compound of formula (IV). For example, when Y is -COHa l
, -CH2Ha 18O, Flalf Table 26
In the case of amine n (e.g. triethylamine,
It is preferable to carry out the reaction in the presence of an acid binder such as a tertiary amine (such as gylysine), and if Y is -COOR4
1%, such as sodium alkoxide,
It is advantageous to carry out the reaction in the presence of 1W groups.

The amount of the compound of formula (V) to be used in the silica fine powder treated with the aminosilane coupling agent can vary widely depending on the type of the aminosilane coupling agent and/or the compound of formula (IV). , generally, the M
], per 100 parts by weight of processed silica fine powder, formula (IV
), preferably at least 5 parts by weight, preferably 1. <is lO~
It is suitable for use within the range of 20 heavy metropolitan areas and is small.

Thus, in the following h1 formula, ○, R', Z, Ar' and Q do not have the meaning of gi+.

(ii) When Q is a hydrogen atom fH, the 14i group in the above formula (V) is nitrated, multi-elemented and diazotized, and (ii) Q has a nitro group. When expressed, the above formula (Vl
When Q represents a protected amine group, the intermediate of formula (V) is diazotized to give the following formula: In, ■, R', Z, Ar' and XO do not have the above meanings, and are changed to a duazonium salt represented by the above nitration,
Each unit reaction of reduction and diazotization is a well-known reaction in the technical field, and can be carried out by a method known per se.

Therefore, nitration is, for example, Nippon Kagaku Kinsen, "New Experimental Chemistry Course", Vol. 14 (1), 1266-1286w (October 1, 1978), published by Maruzen Co., Ltd., co-authored by Kenzo Konishi and Nobuhiko Kuroki, " It can be carried out according to the method described in the literature such as "Chemistry of Synthetic Dyes", pp. 27-37 (March 15, 1972) published by Makikoten. “New Experimental Chemistry Course” Volume 14 [-], 1133
3-1341 pages October 1, 1978) Published by Marusaki Co., Ltd. and co-authored by Kenzo Konishi and Nobuhiko Kuroki, "Chemistry of synthetic materials",
62-72 Wataru (March 15, 1972) published by Maki Shoten, etc. Diazotization can be carried out according to the method described in the literature, such as Nippon Kagaku Kinsen, "Shin Jikken Kagaku FFt,"
Volume 114, 29- [-], pp. 11565-1573 (October 1, 1973), published by Kujo Co., Ltd., co-authored with Kenzo Konishi and Nobuhiko Kuroki, [Chemistry of synthetic dyes - pp. 1,145-149 (1972)
It can be carried out according to the method described in the literature published by Makigoten (March 15, 2013).

The soazonium base obtained in this way can be converted to the formula (4) by reacting with a coupler represented by the formula
The azo pigment of the present invention into which the monoazo dye residue of 1) is introduced can be obtained.

The above coupling reaction can be carried out using a method known per se, for example, Nippon Kagaku Kinsen, "Shinjikyo Kagaku Koza" Vol. 14 [■], 1
pp. 525-1528 (10/1, 1975) Published by Maruzen Co., Ltd., co-authored by Marizo Konishi and Nobuhiko Kuroki, "Chemistry of Combined Hy Dyes", 150-156 (March 15, 1972)
It can be carried out according to the method described in the 30-literature published by Makibagten, for example, water; alcohol such as methanol and ethanol; zomethylnurphogide, N,N-dimethylformamide, hexamethylphosphorotriamide In a solvent such as pH
It can be carried out under mildly alkaline conditions of about 7 to about 9° C. and at relatively low temperatures of about θ to about 10° C.

The amount of the coupler to be used relative to the soazonium salt is not particularly limited, but in general the coupler is used in an amount of 0.05 to 0.05 parts per 100 parts of the soazonium salt, preferably 0.2 to 0.3 parts per 100 parts of the soazonium salt. It can be used in the proportion of

The composite azo pigment thus obtained is separated from the reaction mixture by a method such as filtration or centrifugation17, and then subjected to treatments such as acid treatment, washing with water, washing with acetone, and drying to obtain the desired azo pigment. .

It will be done.

[1] Introduction of disazo dye group of formula (2): (Vl
) (IX) (Ml) Yin (1-2) J3Uho○, R", Ar', Ar", Ar" and Z have the above meanings; G represents an optionally protected amino group .

When introducing the disazo dye group of formula (2) onto the silica fine powder treated with an aminosilane coupling agent, the formula (Vl) produced as described in [11] above is used.
An amino group-containing coupler as represented by formula (Vl) is reacted with the diazonium increase.

The amino group present in the coupler of formula (Vlll) may be optionally protected, and examples of the amino group include those that are easily separated by hydrolysis, such as acyl groups such as acetyl, globionyl, and benzoyl. Ru. Therefore, examples of the amino group-containing coupler of formula (Vl) include the following.

33 A diazonium salt as shown in formula (Vl) and a diazonium salt as shown in formula (Ill)
) The reaction with an amino group-containing coupler as shown in
Methods known per se (for example, Nippon Kagaku Kinsen, [New Experimental Chemistry Course J14 volume [(e)], pages 1525-152B (
October 1, 1971) Published by Maruzen Co., Ltd. and co-authored by Kenzo Konishi and Nobuhiko Kuroki, "Chemistry of Synthetic Dyes", 150-156
page (March 15, 1970) (see literature published by Maki Shoten, etc.)
θ to about lθ℃ under acidic conditions with a pH of about 5 to 7 according to
It can be carried out at relatively low temperatures. Furthermore, the ratio of the amino group-containing coupler of the formula (Vllll) to the diazonium salt is not strictly limited and can be varied across Buddhist artists; however, in general, the proportion of the amino group-containing coupler of the formula ( Vl!l) couplers are 002-0.3 double limbus, preferably 101-02
can be used in proportions of ii parts.

The thus obtained Hikari formula (IX) in which G represents an amino group
) can be used as is, and when G represents a protected amino group, the substances of formulas (1 to ') can be treated by removing the eriamino protecting group by, for example, hydrolysis. All amine groups are diazotized. The diazotization can be carried out by a method known per se, for example, as described in Nihon Kagakusen, "New Experimental Science PJ1".
4 outside [-], 1565-1573'! n (1978
October 1) Published by Maruzen Co., Ltd. and co-authored by Kenzo Konishi and Nobuhiko Kuroki, "Chemistry of Synthetic Dyes", pp. 145-149 (1977)
(March 15, 2013) This can be done according to the method described in the literature published by Maki-kianten, etc.

The generated diazonium salt is reacted with a coupler of formula (Vli) in the same manner as described in [I] above, and is then deposited on a silica powder cleaved with an aminosilane coupling agent (i↑(611 formula (2)). ) can be introduced into the disazo base material residual fund.

[Non] Introduction of monoazo dye group of formula (3): (Xl
) NHCO-Ar'-Q (Xlll) In the above formula, @, R", Ar", Ar', Q
.

XO and Y do not have the above meaning; Q' represents a protected amino group bonded to carbon 19 of the aromatic ring other than the carbon atom adjacent to the carbon atom to which Y is bonded; Yl is -COIlal Matake-COOR4q-H, where Hal and R4 have the same taste as above.

In the introduction of the monoazo dye group of formula +31, first, fine silica powder treated with an aminosilane coupling agent as shown in formula (1) above is combined with the fine silica powder of formula (IV
) is reacted with the compound of formula (X) in the same manner as described in N) above. This results in
Something like the one shown by the above formula (Xl)! What is produced? After removing the amino group by a conventional method such as hydrolysis, it is reacted with the compound of the above formula (Xll). This reaction 37- can also be carried out in the same manner as described in section 13 above regarding the reaction between 1p'R of formula (1) and the compound of formula (IV), and thereby The substance shown is obtained. Then, the same $: group Q in this substance is replaced with the above [
11 to the diazonium salt and the formula (XI
By using a diazonium salt represented by V) and reacting the diazonium salt with a coupler of formula (Vli) as described in @11, the formula (3) is formed on silica fine powder treated with an aminosilane coupling agent. The monoazo dye residue represented by formula (1-3) can be introduced.

(IV) Introduction of azo dye groups of formulas (4) and (5) (XVI) 38- CON II -A r" -L-A r6- Q(X
~Q11) (XIX) Ar"-N=N-Ar" (1-4) Q, Y, Y' and Z have the above deprivations l-; L is -N-
N- or -NH-f; M is -N-N- or -N-
represents.

O In introducing the azo dye groups of formulas (4) and (5) above, first, fine silica powder treated with an aminosilica/coupling agent as shown in formula (It) above is combined with a compound of formula (XV). Forced to react. β-silica fine powder and formula (XV
) The reaction between the silica fine powder and the compound of formula (IV) can be carried out in the same manner as described in [1] above, whereby the reaction of the above formula (x tq )
A substance as shown in is obtained.

This substance of formula (XVI) is then converted into the substance of the above formula (X Vll
) is reacted with the compound. This formula (X Vll
) can be used as an example of the compound Vj such as J'JT.

The reaction of such a compound of formula (XVII) with a substance of formula (X Vj ) can be carried out in a suitable inert solution, for example, a ketone such as acetone, methyl ethyl ketone, soethyl ketone; an ether such as ethyl ether, tetrahydrofuran; dichloromethane; In a solvent such as chloroform, halogenated hydrocarbons such as tetranomized carbon 1, etc., in the presence of amines such as triethylamine, pyridine, etc., at 15° C.
06° in the case of torture at ~90°C, the formula (X Vl ) +7) proboscis W K ? l f formula (X
Vl) (7) Compound usage ratio r:
Although it is possible to vary λ over a range of 100% and 100%, in general, the formula (XVI) per 1 oonV part of the substance
about 0.05 to about 0.7 parts of a compound with
Preferably, it is used in a proportion of about 0.2 to about 0.3 parts by weight, which is about 15 parts by weight.

The product of the formula (X Vll ) thus obtained +'? ? J is then converted into an azo dye of the formula (4) or (5) by converting the 177 substituent Q in the substance into a diazonium salt group and then reacting it with a cazole of the formula (1) as described above. The compound of formula (1-4) into which the group is introduced is i(1.).

In addition, when L in the above formula (X Vm ) is -NFI-, this group is converted into an -N- group by O during the diazotization reaction.

42- Representative examples of the azo pigment of the present invention produced as described above include the following, excluding those shown in Examples below.

43-494--44= The azo-based material provided by the present invention has excellent brightness, and since it contains a core of blown silica fine powder, the brightness is strong, and the color reduction group 2 ( As a coloring material suitable for layering), ft
It can be used as a natural color toner in electrostatic and photographic casting materials.

In addition, the azo-based pigment of the present invention has excellent melting stiffness, heat resistance, water resistance, etc., is strong, and has a high degree of color to the eyes, and can be advantageously used as a coloring agent in various paints. .

Next, the present invention will be explained in more detail with reference to Shishio 11.

Example 1 Silica Dull (flat particle size 3.5 microns) 202'frγ
-Aqueous solution of aminopropyltriethoxysilane 2
002 and heated in a mold for 16 hours (80-90℃
)did. After the reaction, centrifugation and water washing were repeated three times, and the sample was thoroughly dried in a vacuum desiccator.

This was placed in 20 G ml of chloroporum solution ME containing 2t (001 moles) of p-nitrobenzoyl chloride and 1y (o,ot moles) of triethylamine and refluxed for 1 hour. . After the reaction, the sample was washed three times with chloroform and dried (hereinafter referred to as "acylated sample A").

Two acylated samples A were added to a 1% aqueous solution of sodium dithionite (400°C) and heated (80 to 90°C) for 1 hour. After reaction 3
Washed with water twice and dried.
”.

A 2N-HCI aqueous solution 200° C. was maintained at 5° C., in which hair aminated sample A1f was dispersed, and a sodium nitrite aqueous solution 40+r/f of 2Af was added dropwise with stirring. At this time, the entire reactor was wrapped in aluminum foil to prevent the liquid V from exceeding 10° C. and to avoid exposure to light. After reaction, 1
Wash twice with water] Separately, do not dry the washed items! 1
This will be used in the next reaction and will hereinafter be referred to as "diazotized sample A."

2-Hydroxy-(#-(a-morpholinoglovir)
]-]3-naphthalinide 4.7F0.015 mol) f
l Dissolved in 00 ml of N,N-trimethylformamide
11% sodium acetate aqueous solution was added to this to prepare a coupling solution, which was then cooled to 5 to 10°C. Diazotized sample A was dispersed in 100% water and gradually added to the coupling solution. After the reaction, the mixture was left for a while to make the liquid slightly acidic (pf 15-6). Part 1 - Rinse with water (2
(times), N, A/-47-methylformamide washing (once), acetone washing (once),
(times) in this order, and after each house was thoroughly dried using a direct air digitizer. In this way, 205v of an entirely orange pigment (Kaansashiya 1) having the structure shown in the above title was obtained.

(1) Appearance: Red-orange fine powder +21 Characteristic absorption band of infrared absorption spectrum Nearan coupling sample 2930 am ' J-CH, -1560□
-1'FNH.

1470α-1'\CH, - Disappearance of absorption of rs*-or-r in 960G-1 Acylated sample 1640 Yen-I V>C=0 1530 cm-IJ asNo.

1345cTn-1\ and ≧sNO.

48- Aminated sample 1630 (WcI lN-H Pigment shoulder 1 1640g1': /C=0 Example 2 Repeating the same method as in Example 1 using the corresponding starting 1 skewer) The pigments shown in Table 1 were produced according to the method shown below.

In addition, the above pigments A24, 27, 30, 32.34 and 3
The snoring convergence zone of the infrared absorption spectrum of No. 7 is as follows.

pigment 424 1650cWL-IJC=0 Pigment flat 30 1650 cru-1:>C=0 60- 159= Pigment A32 1650 side -1V? ',mark 1650~40□-1V) C=N Pigment A34 1650cm-1”JC=0 Pigment A37 1650 儂-’　　　　　　　c=.

Example 3 61- Disperse the soazotization reagent 'J4A 2 Of of CI) above in 100 l of water to obtain a diazotization solution. 2.5-Somethoxyaniline x, 5f (o, ot mol) was dissolved in 1N-hydrochloric acid, 11% aqueous sodium acetate solution was added thereto to adjust pFl to 5, and the solution was cooled to 5 to 10°C. The diazotization liquid was gradually added to this. After the reaction, the reaction value was allowed to rise for a while, and the mixture was filtered, washed with acetone, and washed with water, and then subjected to the next reaction without drying.

A 2N-HCI aqueous solution (200 m/m) was maintained at 5°C, the above sample was dispersed therein, and 40 m/m/271/m of a sodium nitrite water bath solution was added dropwise while stirring. At that time, the liquid groove is 1
The entire reactor was wrapped in aluminum foil to prevent the temperature from exceeding 0°C and to reduce the amount of light irradiation. After the reaction, the sample was washed once with water and centrifuged (I7), and used for the first reaction without drying, and hereinafter referred to as "soazotized sample B".

2-Hydroxy-11H-benzo(d)carbazole-
3-Carbogycy p-anisidide 5.7t (0,015
mol) k Dissolved in 100 ml of N,N-trimethylformamide, and added 50 ml of 11% sodium acetate aqueous solution to this.
m/(i plus coupling solution and 17, which is 5 to 1
Cooled to 0°C. Diazotized sample B was dispersed in 100 g of water and gradually added to the coupling solution. After the reaction, the solution was left to stand for a while and the liquid was made weakly acidic (pHs ~ 6). Then, washing with water (twice), washing with N,N-methylformamide (once), and washing with acetone (once) were carried out in this order, and the pieces were thoroughly dried in a vacuum desiccator. In this way, a blueish p1 color pigment (pigment 440), 18.9f, having the structure shown in the above-mentioned Shigamo was obtained.

Characteristic absorption band of infrared absorption spectrum: 1 6 4 0 crn-' N
>C=r Example 4 By repeating the same method as in Example 3 above but using the corresponding starting materials, M types shown in Section 2P below were produced.

64- The infrared absorption bands of the pigment layers 41 and 44 are as follows.

Pigment layer 41 Pigment A44 Example 5 Aminated sample of [I] 47'-nitropene 68- Chloroform solution containing 2f (o, ot mol) of diyl chloride and 1r (o, ot mol) of triethylamine 200
The mixture was poured into a broth and refluxed for 1 hour. After washing [i:5], it was washed three times with chloroform and dried (hereinafter referred to as "acylated sample B").

The acylated sample Bfr- was added to 400 ml of sodium dithionite 1-chloride aqueous solution and heated (80 to 90°C) for 1 hour.

The reactor was washed three times with water and dried (this is referred to as aminated sample c-1 under J!J).

A 2N-HC1* solution 200° C. was maintained at 5° C., and the hair aminated sample C was dispersed therein, and 40 ml of a 2M aqueous sodium nitrite solution was added dropwise from each stirring step. At that time, the entire reactor was wrapped in aluminum foil to prevent the liquid temperature from exceeding 10"C and to avoid light irradiation. After the reaction, 1
After washing twice with water and centrifuging, the sample was used for the next reaction without being dried.Hereafter, this will be referred to as "Soazotized sample C").

69-2-Hydroxy-(A7-(a-morpholinozolobyl)]-]3-nanotalinide 47 g 0.015 mol) f
Tears at l 00 rn/'s N,N-trimethylformamide? ,-,l,, knead 11 vinegar in thorium water bath solution 5
Add 0m/ to make a coupling solution, and add 5 to 10
Cooled to ℃. Diazotization sample O'C was dispersed in 100% water and gradually added to the coupling solution. After the reaction, let it stand for a while and make the layer property weakly acidic (71H5-6).
Then, washing with water (twice), washing with N,N-trimethylformamide (lro+), and washing with acetone (once) were carried out in this IIN order, and after being separated from the furnace, it was thoroughly dried in an oil-air desiccator. In this way, a reddish-orange pigment (pigment A s 2 ) 19,2f having the structure shown in the title above was obtained.

Inertial absorption band of infrared absorption spectrum 1640 pull-IJc=.

Example 6 J! using the corresponding quantity valve and raw material for one cycle! Case 5 of the above-mentioned case outside J
By repeating the same method as above, pigments shown in Table 1 and 3 were manufactured.

Example 7 Silane coupler test of [1] above, terephthaloyl chloride 2r (0.01 mol), triethylamine 1p
(0.01 mol) into a chloroform solution 200-
Reflux for 1 hour. Then 1.8 t (o, o 1 mol) of 4-amituduphenylamine, 1.8 t of triethylamine. sy (o, 015 mol) was added and allowed to simmer for an additional hour. After the reaction, it was washed three times with chloroform and dried.

This sample was placed in 150 +++ liters of mixed acid (1:1),
Nitration was carried out by reacting at about 60°C for 20 minutes. After the reaction 74- 73-, the mixture was washed with water until it became neutral. .

Subsequently, this sample was mixed with 40% of an aqueous solution of 1 tb of sodium dithionite.
0 mN and heated once (go-9oC). After the reaction, it was washed with water three times and dried.

2N-HCI aqueous solution 200m/! While maintaining the temperature at 5°C, the sample was dispersed therein, and 2J/40ml of an aqueous solution of sodium nitrite was added dropwise while stirring. At that time, the entire reactor was wrapped in aluminum foil to prevent the liquid temperature from exceeding 10° C. and to avoid light irradiation.

After the reaction, wash once with water and centrifuge for 17 minutes without drying.
It was used as it was in the next reaction (hereinafter referred to as "diazotized sample D").

2-Hydroxy-[N-(3-morpholinopropyl)
]-]3-naphthalinide 4.7f (0,015 mol)
F4 was dissolved in N,N-dimethylformamide of f:100-, and 50 moss of a 11% aqueous sodium acetate solution was added thereto to prepare a coupling solution, which was cooled to 575-10°C. Soazotized sample Dfr: 100 t
Dispersed in nl of water and gradually added to the coupling solution and released for a while after 10 reactions [7, liquid total weak H/strong CpH]
5-6). Then, washing with water (twice), washing with N,N-trimethylformamide (once), and washing with acetone (once).
This was done in this order and thoroughly dried in a vacuum desiccator. In this way, 168v of a mauve pigment (pigment A38) having the structure shown in the above title was obtained.

Manufacturable absorption band of infrared absorption spectrum 1560cm-' JNO 1640 Shin-1◇c=.

Example 8 The pigments shown in Table 4 below were produced by repeating the same method as in Example 7 except that the corresponding raw materials were used.

The characteristic absorption bands of the infrared absorption spectrum of the pigment plate 59 are as follows.

Pigment A39 1630□-t　　　Jc=.

Reference Example 1 (Measurement of Translucency) =80- Azo pigment A having silica as a core (Synthesis example j = a S
) and the above +ll-like Sosuazo Facial Sting B, which has a similar chemical structure, were dispersed and mixed in Vylon 200 (polyester resin, manufactured by Toyobo Co., Ltd.) and 1" HF (tetrahydrofuran) solution according to the following formulation, and several types of wires were mixed in each. A brass cloth was placed on a butron film (50 μm) using a parr.

<Formulation 1><Formulation1> Pigment 1 part by weight 1v part pylon 200 10 parts by weight 2o-1 part 'I'HF
Apply 100 parts to 200 parts of the film [1. Samples with the same film thickness for comparison.

These were measured using a densitometer (Kura densitometer MO manufactured by Konishiroku Photo Industry Co., Ltd.).
The transmittance was measured using DEL 1)DA-65). The results are shown in Table 5.

81- Table 5 Transmission coefficient of azo pigment A with silica as a core and similar azo pigment B (*inverse logarithm of light transmittance) As shown in Table 5, A is clearly more transparent. expensive.

Table 6 shows the results of measuring the visible spectral transmittance of the two films of Experiment A3 in Table 5 above. For measurement, Hitachi 1
A Model 24 double beam spectrophotometer was used.

Table 6 As is clear from Table 6, A has a higher light transmittance.

Reference Example 2 (Water resistance and solvent resistance test) Azo pigment A having a silica core and a sosazo pigment B having a similar property to rM were treated with water, acetone, toluene, N,
The mixture was dispersed in N-methylformamide, diethyl ether and methanol and stirred for 3 hours and 11 hours. Thereafter, the supernatant was centrifuged and the degree of coloration of the supernatant was examined, as shown in Table 7.

Table 7 As can be seen from the results shown in Table 7, azo pigment A having silica as a core has much better water resistance and solvent resistance.

Reference Example 3 (Heat resistance test) Azo pigment A having a silica core and organic disazo pigment B similar to 5s4 were each heated to 200'C and then cooled to room temperature. However, carbonization of B had progressed and it no longer had any properties as a purifying agent. From this, the heat resistance of the azo material A having silica as its core was clarified.

85-

Claims (1)

[Claims] An azo with a silica core characterized by comprising a core of fine silica powder with a particle size of 10 microns or less and a coating of mono- or polyazo dye chemically bonded to the surface of the core through an aminosilane coupling agent. pigment.