JP2017165834A - Organic colorant having silver gloss and coloring composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic colorant having a silver gloss.SOLUTION: An organic colorant having a silver gloss comprises a stilbene compound represented by the following formula.SELECTED DRAWING: None

Description

  The present invention relates to an organic colorant having a silvery luster composed of a stilbene compound, and a coloring composition containing the organic colorant.

Those with metallic luster have many opportunities to see in every scene of daily life because they give people a glittering impression. Although the design property may be imparted using the metal itself, the design property is often imparted by coating the base material with a colored composition having a metallic luster.
As a coating method, a method of printing by various printing methods using a printing ink containing a pigment having a glittering property, or a method of transferring foil by an adhesive or heat fusion has been used.
Among metallic lusters, gold is a symbol of wealth, and has been loved by people since ancient times, and is an indispensable color for celebrations such as New Years. On the other hand, silver is also popular because of its calm texture and is often found in various situations. In addition, silver is different from gold and can be used to express various metallic luster colors including gold by mixing with coloring compositions of other colors, so it is more versatile than gold and has industrial utility value. high.

Conventionally, pigments used in a coloring composition having a silver metallic luster include aluminum fine particles and silver powder, but aluminum fine particles are widely used due to cost problems. However, since the aluminum fine particles have a high specific gravity, they are difficult to exist stably in the coloring composition, and there is a problem that the aluminum fine particles settle with time, adhere in some cases, and form a hard cake.
In order to reduce the environmental burden, coloring compositions such as printing inks are successively replaced with water-based ones that do not use organic solvents as much as possible. However, aluminum particles react with water to generate hydrogen gas. In addition, since aluminum is changed to alumina, there is a problem that the metallic luster is lost.

  In recent years, due to the development of ink jet printing technology, there has been an increasing demand to obtain printed matter having metallic luster even in ink jet printing. For example, as in Patent Document 1, a commercially available scaly aluminum pigment or titanium oxide-coated mica pigment Etc. have been studied for use in inkjet inks as bright pigments. However, since the maximum particle diameter of the bright pigment in the ink is as large as several tens of μm, there are problems that nozzle clogging occurs and the pigment settles with time. Therefore, for example, as in Patent Document 2, it has been studied to perform a treatment in which the scaly aluminum pigment does not easily settle in the ink, and although a certain effect is obtained, it is still insufficient. Further, the problem of generating hydrogen gas by reacting with water has been studied, for example, in Patent Document 3, but water-resistant aluminum pigments have not been solved yet.

Therefore, in order to solve such various problems, organic dye materials having metallic luster have been widely developed (for example, Patent Documents 4 to 6). Since the organic pigment material has a very low specific gravity compared to a metal, if it can be dispersed appropriately, the risk of sedimentation in the coloring composition can be greatly reduced. In addition, it is possible to stably exist even in an aqueous system by appropriately designing the structure of the organic dye material.
However, although organic pigment materials having metallic luster have been developed little by little, an organic pigment material having silver gloss, which is the most versatile key color, has not been developed yet.

An object of the present invention is to provide an organic colorant having a silvery luster.
In general, the metallic luster refers to a gloss or luster peculiar to a metal, and includes, for example, a matte metallic luster having a low luster. Specifically, the regular reflectance is measured to determine the presence or absence of metallic luster. If the regular reflectance is 10% or more, it is determined that metallic luster is present. If the regular reflectance is less than 10%, the matte color tone becomes stronger and it may be difficult to say that the metallic luster is.
On the other hand, the silver gloss in the present invention is when the regular reflectance is 10% or more and the a value and b value in the color values (L, a, b) are both -3.5 or more and 3.5 or less. Point to. Outside this range, it is difficult to say silver because it is yellowish or bluish. The regular reflectance of silver origami is 38%.

上記式中、Ｒ_１〜Ｒ_２は、それぞれ独立に、炭素数が６〜２０のアルキル基、炭素数が１〜２０のアルケニル基、置換基を有してもよいフェニル基、置換基を有してもよいナフチル基、−（ＣＨ_２）ｎ−ＣＯＯ−Ｒ_３、−（ＣＨ_２）ｎ−Ｒ_４、−（ＣＨ_２）ｎ−ＣＯＮＨ−Ｒ_５、−ＣＲ_６Ｒ_７−ＣＯＯ−Ｒ_８、又は−（ＣＨ_２）ｎ−ＯＣＯＣＨ_３で表される基を表し、Ｒ_３は、水素原子、又は炭素数が１〜２のアルキル基を表し、Ｒ_４は、水酸基、炭素数が１〜２のアルコキシ基、炭素数が２〜５のアルケニルオキシ基、ＳＯ_３Ｎａ基、ＯＳＯ_３Ｎａ基、置換基を有してもよいフェニルアルキル基（アルキル部分の炭素数が１〜３）、又は置換基を有してもよいナフチルアルキル基（アルキル部分の炭素数が１〜３）を表し、Ｒ_５は、炭素数が１〜２０のアルキル基、炭素数が１〜２０のアルケニル基、又は炭素数が１〜１２のヒドロキシアルキル基を表し、Ｒ_６は、水素原子、又はメチル基を表し、Ｒ_７は、炭素数が１〜４のアルキル基を表し、Ｒ_８は、炭素数が１〜５のアルキル基を表し、ｎは１〜１２の整数を表す。 The present inventors have found that a stilbene-based compound having a specific structure exhibits a silvery luster, and have reached the present invention. That is, the above problem is solved by the following invention 1).

1) An organic colorant having a silvery luster composed of a stilbene compound represented by the following general formula (1).

General formula (1)

In the above formula, each of R _{1 and} R ₂ independently has an alkyl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, or a substituent. a naphthyl group which may _{be, - (CH 2) n-} COO-R 3, - (CH 2) n-R 4, - (CH 2) n-CONH-R 5, -CR 6 R 7 -COO-R ₈ or a group represented by — (CH ₂ ) n —OCOCH ₃ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₄ represents a hydroxyl group and 1 carbon atom. ˜2 alkoxy group, C 2-5 alkenyloxy group, SO ₃ Na group, OSO ₃ Na group, phenylalkyl group which may have a substituent (carbon number of alkyl part is 1 to 3), Or a naphthylalkyl group (the alkyl part has 1 to 3 carbon atoms) which may have a substituent. And, _{R 5} is an alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl group of the alkenyl group having 1 to 20 carbon atoms, or carbon atoms 1 to 12, _{R 6} is a hydrogen atom, or a methyl group R ₇ represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 12.

  According to the present invention, an organic colorant having a silvery gloss can be provided.

Hereinafter, the present invention 1) will be described in detail, but the following 2) to 4) are also included in the embodiment of the present invention 1), and these will be described together.
2) The substituent is at least one selected from an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxyl group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxyl group, an alkoxycarbonyl group, and an amino group. 1) The organic colorant having a silvery luster according to 1).
3) The organic colorant having silvery luster according to ₁ ), wherein R _{1 to} R ₂ are — (CH ₂ ) ₂ —OH.
4) A colored composition having a silvery gloss, comprising the organic colorant having a silvery gloss described in any one of 1) to 3), water and a solvent.

In order for the stilbene compound represented by the general formula (1) to exhibit silver gloss, a basic skeleton other than R ₁ and R ₂ is important. On the other hand, R ₁ and R ₂ can be variously selected as long as the characteristics of the basic skeleton are not adversely affected.
Further, it is important for the silver gloss to be a trans isomer, and a pure cis isomer does not exhibit a silver gloss. Therefore, although the trans isomer is shown as the general formula (1), even if the cis isomer is mixed to some extent, the silver gloss is not greatly affected. Therefore, the cis isomer may be mixed as long as the silver gloss is not affected. . However, when synthesized by a general method as shown in the examples, a trans form is almost obtained.

Examples of the alkyl group having 6 to 20 carbon atoms in R _{1 to} R ₂ of the general formula (1) include a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a tert-octyl group, and a cyclohexyl group. Although it is mentioned, it is not limited to these. When the number of carbon atoms is 5 or less, the lipophilicity of the compound is insufficient and the solubility in an organic solvent is inferior, and since there is no bulky substituent in the compound, the dispersibility in an organic solvent is also inferior, which is not preferable as a colored composition. On the other hand, the upper limit of the number of carbons is 20 considering the crystallinity of the compound and the ease of developing silvery luster.

The alkenyl group having 1 to 20 carbon atoms in R _{1 to} R ₂ of the general formula (1) may have a plurality of carbon-carbon double bonds in the structure. Specific examples thereof include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4 -Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclo Examples thereof include, but are not limited to, a pentadienyl group. Considering the crystallinity of the compound and the ease of developing silvery luster, the upper limit of the carbon number is 20.

The phenyl group or naphthyl group in R _{1 to} R ₂ of the general formula (1), and the phenyl group or naphthyl group when R ₄ is a phenylalkyl group or a naphthylalkyl group have an adverse effect on the appearance of silvery luster, etc. You may have a substituent in the range which is not given. Examples thereof include an alkyl group, alkenyl group, hydroxyalkyl group, hydroxyl group, alkoxy group, alkenyloxy group, cyano group, cyanoalkyl group, carboxyl group, alkoxycarbonyl group, amino group and the like. In addition, it is better that the carbon number of the alkyl part in a substituent is not so many, and it is about 1-6.

Examples of the alkyl group having 1 to 20 carbon atoms of R _{5 in} the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert -An octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, However, It is not limited to these. Considering the crystallinity of the compound and the ease of developing silvery luster, the upper limit of the carbon number is 20.
Examples of the alkenyl group having 1 to 20 carbon atoms of R _{5 in} the general formula (1) include the same as those in the case where R _{1 to} R ₂ are alkenyl groups, and the upper limit of the carbon number is the same. 20 for reasons.

In R _{1 to} R ₂ of the general formula (1), n is an integer of 1 to 12. When it exceeds 12, the crystallinity of the compound is remarkably deteriorated, so that it may be difficult to develop silver gloss.

  Specific examples of the stilbene compound of the present invention include the following, but are not limited thereto. All of these have a silvery luster.

(Compound group a)

(Compound group b)

(Compound group c)

(Compound group d)

(Compound group e)

(Compound group f)

(Compound group g)

(Compound group h)

(Compound group i)

(Compound group j)

By mixing the stilbene compound having a silvery luster of the present invention with water and a solvent, the colored composition having the silvery luster of the present invention can be obtained.
Applications of the colored composition include paints, printing inks, plastic colorants, color toners, inkjet inks, and the like.
The colored composition of the present invention can be dispersed together with a dispersion medium and the like by a known disperser. The dispersion medium here is water or a solvent that is being dispersed by a disperser. That is, even in the same water or solvent as in the mixing, it is called a “dispersion medium” for the convenience of dispersion treatment.
Moreover, you may use various adjuvants and stabilizers, such as a dispersion | distribution wetting agent, an anti-skinning agent, a ultraviolet absorber, and antioxidant, as needed.

  Varnish for offset ink is a polymer resin component such as rosin-modified phenolic resin, petroleum resin, alkyd resin, or resins such as these dry oil-modified resins, and if necessary, linseed oil, tung oil, soybean oil, etc. Of vegetable oil and a solvent such as n-paraffin, isoparaffin, aromatec, naphthene, α-olefin, etc., and the mixing ratio thereof is resin: vegetable oil: solvent = 20-50 parts: 0 by weight. -30 parts: The range of 10-60 parts is preferable. There are also varnishes containing acrylic esters. Furthermore, you may mix | blend well-known additives, such as an ink solvent, a drier, a leveling improver, a thickener, as needed.

The vehicles of gravure printing ink and flexographic printing ink refer to those containing a plurality of additives such as resins, solvents, and plasticizers. Examples of the resin include one or more resins selected from acrylic resins, nitrocellulose resins, polyamide resins, urethane resins, vinyl acetate resins, rosin resins, and the like.
Examples of the solvent include one or more solvents selected from aromatic hydrocarbons, esters, ketones, alcohols, and the like. Specific examples include toluene, xylene, ethyl acetate, butyl acetate, methyl butyl ketone, methyl ethyl ketone, isopropyl alcohol, methanol, ethanol and the like.

The vehicle for paint refers to one containing a plurality of solvents, resins, additives and the like. Examples of resins include alkyd resins, modified alkyd resins, acrylic resins, alkyd-melamine resins, acrylic-melamine resins, phenolic resins, polyamide resins, and epoxy, regardless of whether they are curable or not. Resins, urethane resins, vinyl acetate resins and the like can be mentioned.
Examples of the solvent include one or more solvents selected from aromatic hydrocarbons, esters, ketones, alcohols, and the like. Specific examples include water, toluene, xylene, ethyl acetate, butyl acetate, methyl butyl ketone, methyl ethyl ketone, isobutyl alcohol, normal butanol, and cyclohexanone.

  Examples of resins used as plastic colorants include poly (meth) acrylate, polystyrene, ABS resin, AS resin, polyolefins such as polyethylene and polypropylene, polyamides, polyacetals, polycarbonates, polyesters such as PET and PBT, and modified polyphenylene ethers. However, the present invention is not limited to this.

  Examples of the resin for the color toner include styrene such as styrene, vinyl toluene, α-methyl styrene, and amino styrene and derivatives thereof; methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, and butyl methacrylate; acrylic acid, Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; dienes such as butadiene and isoprene; acrylonitriles; maleic acid, maleic anhydride, maleic acid esters; vinyl such as vinyl ether and vinyl acetate Compounds: Homopolymers and copolymers of olefins such as ethylene and propylene, and polyesters, polyamides, and polyurethanes can be used alone or in combination. If necessary, add known materials such as charge control agents such as salicylic acid metal salts, metal-containing azo compounds, niglycine, quaternary ammonium salts, and offset inhibitors such as low molecular weight polypropylene, low molecular weight polyethylene, and wax. May be.

The proportion of the stilbene compound in the colored composition is preferably 70% by weight or less, and particularly preferably in the range of 0.01 to 50% by weight. The balance is a dispersion medium.
Since the dispersion conditions vary depending on the dispersion medium and the disperser, the dispersion temperature and dispersion time cannot be specified, but the dispersion temperature is preferably room temperature to 240 ° C., more preferably room temperature to 150 ° C., and the dispersion time is preferably within 120 hours. More preferably, it is within 5 hours.
The colored composition is mixed with other additives, pigments, dyes and the like as necessary, and used as a final paint, printing ink, inkjet ink, plastic, color toner, recording agent, and the like.
Dispersers that disperse pigments when producing a pigment dispersion include known dispersers such as dispersers, homomixers, bead mills, ball mills, two rolls, three rolls, a pressure kneader, and an ultrasonic disperser. But is not limited to these

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

窒素下で、二口ナスフラスコにチタノセンジクロリド（２．９９ｇ、１２．０ｍｍｏｌ）と亜鉛粉末（１．５７ｇ、２４．０ｍｍｏｌ）を入れた後、安定剤無添加の脱水したテトラヒドロフラン（以下「脱水ＴＨＦ」という）を３５ｍＬ加え、室温で溶液の色が赤から緑になるまで撹拌した。この溶液を７０℃で１５分間加熱還流させた後、４−（２−ヒドロキシエトキシ）ベンズアルデヒド（１．６６ｇ、１０．０ｍｍｏｌ）を含有する脱水ＴＨＦ１５ｍＬを３０分かけて滴下した。反応系を１９時間加熱還流させた後、ｔｅｒｔ−ブチルメチルエーテル２５ｍＬを２０分かけて滴下した。溶媒を減圧除去し残渣を氷冷メタノール５０ｍＬで２回洗浄した後、クロロホルム５０ｍＬで２回洗浄した。次いで、６０℃の温メタノール６００ｍＬに粗生成物を溶解させ、吸引ろ過して亜鉛粉末を除去した。最後に、ろ液から溶媒を減圧除去し減圧乾燥して生成物を得た（収率２７．４％）。得られた生成物０．０５ｇとメタノール７０ｍＬを１００ｍＬのサンプル瓶に入れ、６３℃まで加熱して完全に溶解させた後、室温で３時間静置した。析出した結晶を吸引濾過して円形のろ紙上（直径２１ｍｍ）に積層させ、スチルベン系化合物（ｆ１）の銀色光沢結晶薄膜体を得た。
ｆ１のＮＭＲの測定値及び元素分析の結果は次のとおりである。
^１Ｈ ＮＭＲ（４００ＭＨｚ；ジメチルスルホキシド−ｄ_６（ＤＭＳＯ−ｄ_６））：δ ３．７１（ｔｒｉｐｌｅｔ（ｔ），４Ｈ），３．９９（ｔ，４Ｈ），４．８７（ｓｉｎｇｌｅｔ（ｓ），２Ｈ），６．９２（ｄｏｕｂｌｅｔ（ｄ），４Ｈ），７．０２（ｓ，２Ｈ），７．４８（ｄ，４Ｈ）；^１３Ｃ ＮＭＲ（１００ＭＨｚ；ＤＭＳＯ−ｄ_６）：δ ５９．６，６９．５，１１４．７，１２５．８，１２７．４，１３０．０，１５８．１
元素分析値 Ｃ：７１．９８、Ｈ：６．７１、Ｏ：２１．３１ Example 1 (Synthesis of stilbene compound f1)
(Reaction formula)

Under nitrogen, titanocene dichloride (2.99 g, 12.0 mmol) and zinc powder (1.57 g, 24.0 mmol) were placed in a two-necked eggplant flask, and then dehydrated tetrahydrofuran without a stabilizer (hereinafter “dehydrated THF”). ) Was added and stirred at room temperature until the color of the solution changed from red to green. The solution was heated to reflux at 70 ° C. for 15 minutes, and then 15 mL of dehydrated THF containing 4- (2-hydroxyethoxy) benzaldehyde (1.66 g, 10.0 mmol) was added dropwise over 30 minutes. The reaction system was heated to reflux for 19 hours, and then 25 mL of tert-butyl methyl ether was added dropwise over 20 minutes. The solvent was removed under reduced pressure, and the residue was washed twice with 50 mL of ice-cold methanol and then twice with 50 mL of chloroform. Next, the crude product was dissolved in 600 mL of warm methanol at 60 ° C., and suction filtered to remove the zinc powder. Finally, the solvent was removed from the filtrate under reduced pressure and dried under reduced pressure to obtain the product (yield 27.4%). 0.05 g of the obtained product and 70 mL of methanol were put into a 100 mL sample bottle, heated to 63 ° C. to completely dissolve, and then allowed to stand at room temperature for 3 hours. The precipitated crystals were suction filtered and laminated on a circular filter paper (diameter 21 mm) to obtain a silvery glossy crystal thin film of a stilbene compound (f1).
The measured values of f1 NMR and the results of elemental analysis are as follows.
¹ H NMR (400 MHz; dimethyl sulfoxide-d ₆ (DMSO-d ₆ )): δ 3.71 (triplet (t), 4H), 3.99 (t, 4H), 4.87 (singlet (s), 2H), 6.92 (doublet (d), 4H), 7.02 (s, 2H), 7.48 (d, 4H); ¹³ C NMR (100 MHz; DMSO-d ₆ ): δ 59.6, 69.5, 114.7, 125.8, 127.4, 130.0, 158.1
Elemental analysis value C: 71.98, H: 6.71, O: 21.31

還流管を取り付けた１００ｍＬナスフラスコに４−ヒドロキシベンズアルデヒド７．０ｇ（５７．４ｍｍｏｌ）と炭酸カリウム１４．２ｇ（１０２．７ｍｍｏｌ）を入れた後、窒素雰囲気下で、溶媒のアセトニトリル５０ｍＬを加えた。反応系を７５°Ｃに加温し、１−ブロモ−４−メチルペンタン８．４ｇ（５０．９ｍｍｏｌ）を加え、２４時間還流させた。反応終了後、反応混合物中の炭酸カリウムを濾過で除去し、アセトニトリルを留去した。生成物を酢酸エチルに溶解させ、２５ｗｔ％水酸化ナトリウム（２×１００ｍＬ）と飽和食塩水（２×１００ｍＬ）で分液した。有機層を硫酸マグネシウムで乾燥させた後、留去して、透明な液体（ａ１の中間体；収率９８％）を得た。
次に、還流管を取り付けた１００ｍＬナスフラスコに、チタノセンジクロライド３．９ｇ（１５．７ｍｍｏｌ）と亜鉛粉末２．０ｇ（３１．５ｍｍｏｌ）を入れ、窒素雰囲気下で脱水ＴＨＦ（安定剤無添加）を６５ｍＬ加えて、室温で溶液の色が赤から緑になるまで撹拌した。次いで、溶液を還流させ始め、前記中間体を２．０ｇ（１１．６ｍｍｏｌ）加えた。反応混合物を８時間還流させ、室温まで冷却した後、ｔｅｒｔ−ブチルメチルエーテルで反応を停止し、得られた溶液をろ過した。溶媒を減圧留去した後、残渣をクロロホルムで溶解させた。得られたクロロホルム溶液を１Ｎ塩酸と飽和食塩水で分液洗浄し、硫酸マグネシウムで乾燥させ、減圧留去した。得られた白色固体をエタノールで２回再結晶し、析出した結晶を吸引濾過して円形のろ紙上（直径２１ｍｍ）に積層させ、スチルベン系化合物（ａ１）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 2 (Synthesis of stilbene compound a1)
(Reaction formula)

Into a 100 mL eggplant flask equipped with a reflux tube, 7.0 g (57.4 mmol) of 4-hydroxybenzaldehyde and 14.2 g (102.7 mmol) of potassium carbonate were added, and 50 mL of acetonitrile as a solvent was added under a nitrogen atmosphere. The reaction system was heated to 75 ° C., 8.4 g (50.9 mmol) of 1-bromo-4-methylpentane was added, and the mixture was refluxed for 24 hours. After completion of the reaction, potassium carbonate in the reaction mixture was removed by filtration, and acetonitrile was distilled off. The product was dissolved in ethyl acetate and partitioned between 25 wt% sodium hydroxide (2 × 100 mL) and saturated brine (2 × 100 mL). The organic layer was dried over magnesium sulfate and then evaporated to obtain a transparent liquid (intermediate of a1; yield 98%).
Next, 3.9 g (15.7 mmol) of titanocene dichloride and 2.0 g (31.5 mmol) of zinc powder were placed in a 100 mL eggplant flask equipped with a reflux tube, and dehydrated THF (no stabilizer added) was added under a nitrogen atmosphere. 65 mL was added and stirred at room temperature until the color of the solution changed from red to green. The solution then began to reflux and 2.0 g (11.6 mmol) of the intermediate was added. The reaction mixture was refluxed for 8 hours, cooled to room temperature, quenched with tert-butyl methyl ether, and the resulting solution was filtered. After the solvent was distilled off under reduced pressure, the residue was dissolved in chloroform. The obtained chloroform solution was separated and washed with 1N hydrochloric acid and saturated brine, dried over magnesium sulfate, and evaporated under reduced pressure. The obtained white solid was recrystallized twice with ethanol, and the precipitated crystals were suction filtered and laminated on a circular filter paper (21 mm in diameter) to obtain a silvery luster crystal thin film of a stilbene compound (a1). In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを２−ブロモエチルメチルエーテル１０．７ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にしてスチルベン系化合物（ｆ２）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 3 (Synthesis of stilbene compound f2)
(Reaction formula)

A silvery shiny crystalline thin film of a stilbene compound (f2) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 10.7 g (50.9 mmol) of 2-bromoethyl methyl ether. It was. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、２−ブロモエチルエチルエーテル７．７９ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｆ４）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 4 (Synthesis of stilbene compound f4)
(Reaction formula)

A silvery glossy crystal thin film of a stilbene compound (f4) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 7.79 g (50.9 mmol) of 2-bromoethyl ethyl ether. Got. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

還流管を取り付けた１００ｍＬナスフラスコに４−ヒドロキシベンズアルデヒド７．０ｇ（５７．４ｍｍｏｌ）と炭酸カリウム１４．２ｇ（１０２．７ｍｍｏｌ）を入れた後、窒素雰囲気にして溶媒のアセトニトリル５０ｍＬを加えた。反応系を７５℃に加温し、２−ブロモエタンスルホン酸ナトリウム１０．７４ｇ（５０．９ｍｍｏｌ）加えて２４時間還流させた。反応終了後、反応混合物中の炭酸カリウムを濾過で除去し、アセトニトリルを留去した。生成物を酢酸エチルに溶解させ、２５ｗｔ％水酸化ナトリウム（２×１００ｍＬ）と飽和食塩水（２×１００ｍＬ）で分液した。有機層を硫酸マグネシウムで乾燥させた後、留去することにより、透明な液体（ｆ５の中間体；収率９８％）を得た。
次に、還流管を取り付けた１００ｍＬナスフラスコに、チタノセンジクロライド３．９ｇ（１５．７ｍｍｏｌ）と亜鉛粉末２．０ｇ（３１．５ｍｍｏｌ）を入れ、窒素雰囲気にした後、脱水ＴＨＦを６５ｍＬ加え、室温で溶液の色が赤から緑になるまで撹拌した。次いで溶液を還流させ始め、前記中間体を２．０ｇ（１１．６ｍｍｏｌ）加えた。反応混合物を８時間還流させ、室温まで冷却した後、ｔｅｒｔ−ブチルメチルエーテルで反応を停止させ、混合溶液をろ過した。ろ液の溶媒を減圧留去した後、残渣をクロロホルムで溶解させ、１Ｎ塩酸と飽和食塩水で分液洗浄し、硫酸マグネシウムで乾燥させ減圧留去した。得られた白色固体をエタノールで２回再結晶し、析出した結晶を吸引濾過して円形のろ紙上（直径２１ｍｍ）に積層させ、スチルベン系化合物（ｆ５）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 5 (Synthesis of stilbene compound f5)
(Reaction formula)

Into a 100 mL eggplant flask equipped with a reflux tube, 7.0 g (57.4 mmol) of 4-hydroxybenzaldehyde and 14.2 g (102.7 mmol) of potassium carbonate were added, and 50 mL of acetonitrile as a solvent was added under a nitrogen atmosphere. The reaction system was heated to 75 ° C., and 10.74 g (50.9 mmol) of sodium 2-bromoethanesulfonate was added and refluxed for 24 hours. After completion of the reaction, potassium carbonate in the reaction mixture was removed by filtration, and acetonitrile was distilled off. The product was dissolved in ethyl acetate and partitioned between 25 wt% sodium hydroxide (2 × 100 mL) and saturated brine (2 × 100 mL). The organic layer was dried over magnesium sulfate and then distilled off to obtain a transparent liquid (intermediate of f5; yield 98%).
Next, in a 100 mL eggplant flask equipped with a reflux tube, 3.9 g (15.7 mmol) of titanocene dichloride and 2.0 g (31.5 mmol) of zinc powder were put, and after making a nitrogen atmosphere, 65 mL of dehydrated THF was added, The solution was stirred until the color of the solution changed from red to green. The solution was then started to reflux and 2.0 g (11.6 mmol) of the intermediate was added. The reaction mixture was refluxed for 8 hours, cooled to room temperature, quenched with tert-butyl methyl ether, and the mixed solution was filtered. After the solvent of the filtrate was distilled off under reduced pressure, the residue was dissolved with chloroform, washed with 1N hydrochloric acid and saturated brine, dried over magnesium sulfate and evaporated under reduced pressure. The obtained white solid was recrystallized twice with ethanol, and the precipitated crystals were suction filtered and laminated on a circular filter paper (diameter 21 mm) to obtain a silvery lustrous crystal thin film of a stilbene compound (f5). In the same manner as in Example 1, it was identified by elemental analysis and NMR.

前記化合物ｆ１（２．１ｇ、７ｍｍｏｌ）、三酸化硫黄／ピリジン錯体（２．３８ｇ、１５．０ｍｍｏｌ）及びピリジン２０ｍＬの反応混合物を５０℃で２４時間撹拌した後、水酸化ナトリウム（１．２ｇ、３０ｍｍｏｌ）を含む水溶液１０ｍＬを加えて１０分間撹拌した。ピリジンと水を減圧除去した後、残渣にメタノールを加えて生成物をメタノール抽出した。次いでメタノールにヘキサンを加えて生成物の結晶を析出させ、この結晶を吸引濾過して円形のろ紙上（直径２１ｍｍ）に積層させ、スチルベン系化合物（ｆ６）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 6 (Synthesis of stilbene compound f6)
(Reaction formula)

A reaction mixture of the compound f1 (2.1 g, 7 mmol), sulfur trioxide / pyridine complex (2.38 g, 15.0 mmol) and pyridine 20 mL was stirred at 50 ° C. for 24 hours, and then sodium hydroxide (1.2 g, 10 mL of an aqueous solution containing 30 mmol) was added and stirred for 10 minutes. After removing pyridine and water under reduced pressure, methanol was added to the residue to extract the product with methanol. Next, hexane was added to methanol to precipitate product crystals. The crystals were suction filtered and laminated on a circular filter paper (21 mm in diameter) to obtain a silvery lustrous crystal thin film of a stilbene compound (f6). In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、ベンジルブロミド８．７ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｆ８）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 7 (Synthesis of stilbene compound f8)
(Reaction formula)

A silvery luster crystal thin film of a stilbene compound (f8) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 8.7 g (50.9 mmol) of benzyl bromide. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１−（ブロモメチル）ナフタレン１１．３ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｆ１２）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 8 (Synthesis of stilbene compound f12)
(Reaction formula)

A silvery glossy crystal thin film of a stilbene compound (f12) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 11.3 g (50.9 mmol) of 1- (bromomethyl) naphthalene. Got. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、４−メチルベンジルブロミド９．４ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｆ９）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 9 (Synthesis of stilbene compound f9)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 9.4 g (50.9 mmol) of 4-methylbenzyl bromide, a silvery glossy crystal thin film of the stilbene compound (f9) was obtained. Obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１２−ブロモ−１−ドデカノール１３．５ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｆ１４）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 10 (Synthesis of stilbene compound f14)
(Reaction formula)

A silvery glossy crystal thin film of a stilbene compound (f14) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 13.5 g (50.9 mmol) of 12-bromo-1-dodecanol. Got the body. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを１−ブロモオクタデカン１７．０ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ａ２）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 11 (Synthesis of stilbene compound a2)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 17.0 g (50.9 mmol) of 1-bromooctadecane, a silvery lustrous crystal thin film of a stilbene compound (a2) was obtained. . In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１−ブロモウンデカン１２．０ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ａ３）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 12 (Synthesis of stilbene compound a3)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 12.0 g (50.9 mmol) of 1-bromoundecane, a silvery glossy crystal thin film of a stilbene compound (a3) was obtained. It was. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１−ブロモ−３，７−ジメチルオクタン１１．３ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ａ４）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 13 (Synthesis of stilbene compound a4)
(Reaction formula)

The silver of the stilbene compound (a4) was similarly obtained except that 1-bromo-4-methylpentane in Example 2 was changed to 11.3 g (50.9 mmol) of 1-bromo-3,7-dimethyloctane. A glossy crystal thin film was obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１−ブロモ−３−メチル−２−ブテン７．６ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｂ２）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 14 (Synthesis of stilbene compound b2)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 7.6 g (50.9 mmol) of 1-bromo-3-methyl-2-butene, the stilbene compound (b2) A silvery luster crystal thin film was obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１８−ブロモ−１−オクタデセン１６．８７ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｂ３）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 15 (Synthesis of stilbene compound b3)
(Reaction formula)

A silvery glossy crystal thin film of a stilbene compound (b3) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 16.87 g (50.9 mmol) of 18-bromo-1-octadecene. Got the body. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、ブロモベンゼン８．０ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｃ１）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 16 (Synthesis of stilbene compound c1)
(Reaction formula)

A silvery glossy crystal thin film of a stilbene compound (c1) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 8.0 g (50.9 mmol) of bromobenzene. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、４−ブロモ安息香酸１０．２ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｃ３）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 17 (Synthesis of stilbene compound c3)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 10.2 g (50.9 mmol) of 4-bromobenzoic acid, a silvery glossy crystal thin film of the stilbene compound (c3) was obtained. Obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、２−ブロモナフタレン１１．３ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｄ１）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 18 (Synthesis of stilbene compound d1)
(Reaction formula)

A silvery glossy crystalline thin film of a stilbene compound (d1) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 11.3 g (50.9 mmol) of 2-bromonaphthalene. It was. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、６−ブロモ−２−ナフトエ酸１２．８ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｄ７）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 19 (synthesis of stilbene compound d7)
(Reaction formula)

A silvery glossy crystal of a stilbene compound (d7) was obtained in the same manner except that 1-bromo-4-methylpentane in Example 2 was changed to 12.8 g (50.9 mmol) of 6-bromo-2-naphthoic acid. A thin film body was obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、３−ブロモプロピオン酸７．８ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｅ１）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 20 (Synthesis of stilbene compound e1)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 7.8 g (50.9 mmol) of 3-bromopropionic acid, a silvery luster crystal thin film of the stilbene compound (e1) was obtained. Obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、３−ブロモプロピオン酸メチル８．５ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にしてスチルベン系化合物（ｅ２）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 21 (Synthesis of stilbene compound e2)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 8.5 g (50.9 mmol) of methyl 3-bromopropionate, a silvery glossy crystal thin film of the stilbene compound (e2) was obtained. Obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、３−ブロモプロピオン酸エチル９．２１ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にしてスチルベン系化合物（ｅ３）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 22 (Synthesis of stilbene compound e3)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 9.21 g (50.9 mmol) of ethyl 3-bromopropionate, a silvery glossy thin film of stilbene compound (e3) was obtained. Obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、１１−ブロモウンデカン酸１３．５ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｅ５）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 23 (Synthesis of stilbene compound e5)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 13.5 g (50.9 mmol) of 11-bromoundecanoic acid, a silvery glossy crystalline thin film of the stilbene compound (e5) was obtained. Obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

二口ナスフラスコに４−ヒドロキシベンズアルデヒド（０．１ｇ、０．８ｍｍｏｌ）と炭酸カリウム（０．１７ｇ、１．２ｍｍｏｌ）を入れた後、アセトン１０ｍＬを加えた。得られた溶液を室温で３０分間撹拌し、ブロモ酢酸エチル（０．１４ｇ、０．８ｍｍｏｌ）を滴下した。反応系を４時間還流させた後、吸引ろ過して炭酸カリウムを除去した。ろ液から溶媒を減圧留去し、オイル状の残渣を水で洗浄した。最後にカラムクロマトグラフィにより精製して、オイル状の生成物（ｇ１の中間体１）を得た。
次に、窒素雰囲気下、二口ナスフラスコにチタノセンジクロリド（３．００ｇ、１２．０ｍｍｏｌ）と亜鉛粉末（１．５７ｇ、２４．０ｍｍｏｌ）を入れ、脱水ＴＨＦを５０ｍＬ加えて、室温で溶液の色が赤から緑になるまで撹拌した。更に溶液を７０℃で３０分間還流させ、前記中間体１（２．１０ｇ、１０．０ｍｍｏｌ）を加えた。薄層クロマトグラフィーで確認しつつ中間体１が消費されるまで反応混合物を還流させ、ｔｅｒｔ−ブチルメチルエーテルで反応を停止させた。吸引ろ過して反応液から亜鉛粉末を除去し、ろ液を１Ｎ塩酸及び飽和食塩水で洗浄した後、硫酸マグネシウムで脱水した。更に溶媒を減圧除去し、残渣をヘキサンで洗浄した後、エタノールで再結晶してｇ１の中間体２を得た。
次に、前記中間体２（１．００ｇ、２．６０ｍｍｏｌ）と脱水ＴＨＦ（３０ｍＬ）を二口ナスフラスコに入れ、７０℃で還流させ始めたところで、０．５ｗｔ％水酸化ナトリウム水溶液を５０ｍＬ加えた。反応系を２時間還流させた後、減圧留去により溶媒を除去し、残渣に水を１００ｍＬ加えた。吸引ろ過により水不要物を除去した後、ろ液が酸性になるまで希塩酸を滴下し粗生成物を析出させた。粗生成物をアセトン３０ｍＬで洗浄しｇ１の中間体３を得た。
次に、窒素雰囲気下、前記中間体３（０．５０ｇ、１．５２ｍｍｏｌ）を入れた二口ナスフラスコに塩化チオニルを８ｍＬ加えた。反応系を８０℃で５時間還流させた後、未反応の塩化チオニルを減圧除去し、ｇ１の中間体４を得た。
次に、前記中間体４にクロロホルムを１０ｍＬ加え、氷浴で０℃まで冷却した後、０℃の２．４ｗｔ％水酸化ナトリウム水溶液５ｍＬとイソプロピルアミン（０．８９ｇ、１５．１ｍｍｏｌ）を加えた。得られた溶液を９０分間撹拌した後、吸引ろ過して円形のろ紙上（直径２１ｍｍ）に積層させ、最後にメタノール３０ｍＬで洗浄し、スチルベン系化合物（ｇ１）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 24 (synthesis of stilbene compound g1)
(Reaction formula)

4-Hydroxybenzaldehyde (0.1 g, 0.8 mmol) and potassium carbonate (0.17 g, 1.2 mmol) were added to a two-necked eggplant flask, and then 10 mL of acetone was added. The resulting solution was stirred at room temperature for 30 minutes and ethyl bromoacetate (0.14 g, 0.8 mmol) was added dropwise. The reaction system was refluxed for 4 hours and then suction filtered to remove potassium carbonate. The solvent was removed from the filtrate under reduced pressure, and the oily residue was washed with water. Finally, purification by column chromatography gave an oily product (g1 intermediate 1).
Next, under a nitrogen atmosphere, put titanocene dichloride (3.00 g, 12.0 mmol) and zinc powder (1.57 g, 24.0 mmol) in a two-necked eggplant flask, add 50 mL of dehydrated THF, and color the solution at room temperature. Was stirred until the color changed from red to green. Further, the solution was refluxed at 70 ° C. for 30 minutes, and the intermediate 1 (2.10 g, 10.0 mmol) was added. While confirming by thin layer chromatography, the reaction mixture was refluxed until the intermediate 1 was consumed, and the reaction was stopped with tert-butyl methyl ether. The zinc powder was removed from the reaction solution by suction filtration, and the filtrate was washed with 1N hydrochloric acid and saturated brine, and then dehydrated with magnesium sulfate. Further, the solvent was removed under reduced pressure, and the residue was washed with hexane and then recrystallized with ethanol to obtain an intermediate 2 of g1.
Next, when the intermediate 2 (1.00 g, 2.60 mmol) and dehydrated THF (30 mL) were put into a two-necked eggplant flask and started to reflux at 70 ° C., 50 mL of 0.5 wt% sodium hydroxide aqueous solution was added. It was. After the reaction system was refluxed for 2 hours, the solvent was removed by distillation under reduced pressure, and 100 mL of water was added to the residue. After removing unnecessary water by suction filtration, dilute hydrochloric acid was added dropwise until the filtrate became acidic to precipitate a crude product. The crude product was washed with 30 mL of acetone to obtain Intermediate 3 of g1.
Next, 8 mL of thionyl chloride was added to the two-necked eggplant flask containing the intermediate 3 (0.50 g, 1.52 mmol) under a nitrogen atmosphere. The reaction system was refluxed at 80 ° C. for 5 hours, and then unreacted thionyl chloride was removed under reduced pressure to obtain g1 intermediate 4.
Next, 10 mL of chloroform was added to the intermediate 4 and cooled to 0 ° C. in an ice bath, and then 5 mL of a 2.4 wt% sodium hydroxide aqueous solution at 0 ° C. and isopropylamine (0.89 g, 15.1 mmol) were added. . The obtained solution was stirred for 90 minutes, and then filtered by suction, laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery luster crystal thin film of a stilbene compound (g1). . In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２４で得られたｇ１の中間体４にクロロホルムを１０ｍＬ加え、氷浴で０℃まで冷却した後、０℃の２．４ｗｔ％水酸化ナトリウム水溶液５ｍＬとヘプタデシルアミン（３．８３ｇ、１５．０ｍｍｏｌ）を加えた。得られた溶液を９０分間撹拌した後、吸引ろ過して円形のろ紙上（直径２１ｍｍ）に積層させ、最後にメタノール３０ｍＬで洗浄し、スチルベン系化合物（ｇ２）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 25 (Synthesis of stilbene compound g2)
(Reaction formula)

After adding 10 mL of chloroform to the intermediate 4 of g1 obtained in Example 24 and cooling to 0 ° C. in an ice bath, 5 mL of a 2.4 wt% aqueous sodium hydroxide solution at 0 ° C. and heptadecylamine (3.83 g, 15 0.0 mmol) was added. The obtained solution was stirred for 90 minutes, then suction filtered and laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of a stilbene compound (g2). . In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２４で得られたｇ１の中間体４にクロロホルムを１０ｍＬ加え、氷浴で０℃まで冷却した後、０℃の２．４ｗｔ％水酸化ナトリウム水溶液５ｍＬとオレイルアミン（４．０１ｇ、１５．０ｍｍｏｌ）を加えた。得られた溶液を９０分間撹拌した後、吸引ろ過して円形のろ紙上（直径２１ｍｍ）に積層させ、最後にメタノール３０ｍＬで洗浄し、スチルベン系化合物（ｇ３）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 26 (Synthesis of stilbene compound g3)
(Reaction formula)

After adding 10 mL of chloroform to the intermediate 4 of g1 obtained in Example 24 and cooling to 0 ° C. in an ice bath, 5 mL of a 2.4 wt% sodium hydroxide aqueous solution at 0 ° C. and oleylamine (4.01 g, 15.0 mmol) were obtained. ) Was added. The obtained solution was stirred for 90 minutes, and then filtered by suction, laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of a stilbene compound (g3). . In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２４で得られたｇ１の中間体４にクロロホルムを１０ｍＬ加え、氷浴で０℃まで冷却した後、０℃の２．４ｗｔ％水酸化ナトリウム水溶液５ｍＬと２−アミノエタノール（０．９０ｍＬ、１５．０ｍｍｏｌ）を加えた。得られた溶液を９０分間撹拌した後、吸引ろ過して円形のろ紙上（直径２１ｍｍ）に積層させ、最後にメタノール３０ｍＬで洗浄し、スチルベン系化合物（ｇ４）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 27 (Synthesis of stilbene compound g4)
(Reaction formula)

After adding 10 mL of chloroform to the intermediate 4 of g1 obtained in Example 24 and cooling to 0 ° C. with an ice bath, 5 mL of 2.4 wt% sodium hydroxide aqueous solution at 0 ° C. and 2-aminoethanol (0.90 mL, 15.0 mmol) was added. The resulting solution was stirred for 90 minutes, and then suction filtered and laminated on a circular filter paper (diameter 21 mm), and finally washed with 30 mL of methanol to obtain a silvery glossy crystal thin film of a stilbene compound (g4). . In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２４で得られたｇ１の中間体４にクロロホルムを１０ｍＬ加え、氷浴で０℃まで冷却した後、０℃の２．４ｗｔ％水酸化ナトリウム水溶液５ｍＬと１２−アミノ−１−ドデカノール（３．０２ｇ、１５．０ｍｍｏｌ）を加えた。この溶液を９０分間撹拌した後、吸引ろ過して円形のろ紙上（直径２１ｍｍ）に積層させ、最後にメタノール３０ｍＬで洗浄し、スチルベン系化合物（ｇ６）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 28 (Synthesis of stilbene compound g6)
(Reaction formula)

After adding 10 mL of chloroform to the intermediate 4 of g1 obtained in Example 24 and cooling to 0 ° C. with an ice bath, 5 mL of a 2.4 wt% aqueous sodium hydroxide solution at 0 ° C. and 12-amino-1-dodecanol (3 0.02 g, 15.0 mmol) was added. After stirring this solution for 90 minutes, it filtered by suction, was laminated | stacked on the circular filter paper (diameter 21mm), and finally it wash | cleaned with 30 mL of methanol, and obtained the silvery luster crystal thin film body of the stilbene type compound (g6). In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２４で得られたｇ１の中間体４にクロロホルムを１０ｍＬ加え、氷浴で０℃まで冷却した後、０℃の２．４ｗｔ％水酸化ナトリウム水溶液５ｍＬと３−アミノプロピレン（０．８６ｇ、１５．０ｍｍｏｌ）を加えた。この溶液を９０分間撹拌した後、吸引ろ過して円形のろ紙上（直径２１ｍｍ）に積層させ、最後にメタノール３０ｍＬで洗浄し、スチルベン系化合物（ｇ７）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 29 (Synthesis of stilbene compound g7)
(Reaction formula)

After adding 10 mL of chloroform to the intermediate 4 of g1 obtained in Example 24 and cooling to 0 ° C. with an ice bath, 5 mL of a 2.4 wt% sodium hydroxide aqueous solution at 0 ° C. and 3-aminopropylene (0.86 g, 15.0 mmol) was added. After stirring this solution for 90 minutes, it filtered by suction, was laminated | stacked on the circular filter paper (diameter 21mm), and finally it wash | cleaned with 30 mL of methanol, and obtained the silvery luster crystal thin film body of the stilbene type compound (g7). In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、２−ブロモプロピオン酸エチル９．２ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にしてスチルベン系化合物（ｈ２）の銀色光沢結晶薄膜体の薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 30 (Synthesis of stilbene compound h2)
(Reaction formula)

In the same manner as in Example 2, except that 1-bromo-4-methylpentane was changed to 9.2 g (50.9 mmol) of ethyl 2-bromopropionate, a silvery glossy crystalline thin film of the stilbene compound (h2) was obtained. A thin film body was obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例２における１−ブロモ−４−メチルペンタンを、酢酸−２−ブロモエチル８．５ｇ（５０．９ｍｍｏｌ）に変えた点以外は同様にしてスチルベン系化合物（ｉ１）の銀色光沢結晶薄膜体の薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 31 (Synthesis of stilbene compound i1)
(Reaction formula)

A thin film of silvery lustrous crystalline thin film of stilbene compound (i1) except that 1-bromo-4-methylpentane in Example 2 was changed to 8.5 g (50.9 mmol) of 2-bromoethyl acetate. Got the body. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

還流管を取り付けた１００ｍＬナスフラスコに、チタノセンジクロライド３．９ｇ（１５．７ｍｍｏｌ）と亜鉛粉末２．０ｇ（３１．５ｍｍｏｌ）を入れ、窒素雰囲気下で脱水ＴＨＦ（安定剤無添加）を６５ｍＬ加えて、室温で溶液の色が赤から緑になるまで撹拌した。次いで、溶液を還流させ始め、４−（２−ヒドロキシエトキシ）ベンズアルデヒド（１．６６ｇ、１０．０ｍｍｏｌ）と、ｇ１の中間体（２．１０ｇ、１０．０ｍｍｏｌ）を加えた。反応混合物を８時間還流させ、室温まで冷却した後、ｔｅｒｔ−ブチルメチルエーテルで反応を停止し、得られた溶液をろ過した。溶媒を減圧留去した後、残渣をクロロホルムで溶解させた。得られたクロロホルム溶液を１Ｎ塩酸と飽和食塩水で分液洗浄し、硫酸マグネシウムで乾燥させ、減圧留去した。得られた白色固体をエタノールで２回再結晶し、析出した結晶を吸引濾過して円形のろ紙上（直径２１ｍｍ）に積層させ、スチルベン系化合物（ｊ１）の銀色光沢結晶薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 32 (Synthesis of stilbene compound j1)
(Reaction formula)

A 100 mL eggplant flask equipped with a reflux tube was charged with 3.9 g (15.7 mmol) of titanocene dichloride and 2.0 g (31.5 mmol) of zinc powder, and 65 mL of dehydrated THF (without stabilizer) was added under a nitrogen atmosphere. The solution was stirred at room temperature until the color of the solution changed from red to green. The solution then began to reflux and 4- (2-hydroxyethoxy) benzaldehyde (1.66 g, 10.0 mmol) and g1 intermediate (2.10 g, 10.0 mmol) were added. The reaction mixture was refluxed for 8 hours, cooled to room temperature, quenched with tert-butyl methyl ether, and the resulting solution was filtered. After the solvent was distilled off under reduced pressure, the residue was dissolved in chloroform. The obtained chloroform solution was separated and washed with 1N hydrochloric acid and saturated brine, dried over magnesium sulfate, and evaporated under reduced pressure. The obtained white solid was recrystallized twice with ethanol, and the deposited crystals were suction filtered and laminated on a circular filter paper (diameter 21 mm) to obtain a silvery glossy crystal thin film of a stilbene compound (j1). In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例３２における４−（２−ヒドロキシエトキシ）ベンズアルデヒドを、ｆ２の中間体１．８ｇ（１０．０ｍｍｏｌ）に変えた点以外は同様にしてスチルベン系化合物（ｊ２）の銀色光沢結晶薄膜体の薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 33 (synthesis of stilbene compound j2)
(Reaction formula)

A thin film of silvery lustrous crystal thin film of stilbene compound (j2) in the same manner except that 4- (2-hydroxyethoxy) benzaldehyde in Example 32 was changed to 1.8 g (10.0 mmol) of the intermediate of f2. Got the body. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

実施例３２における４−（２−ヒドロキシエトキシ）ベンズアルデヒドを、ｆ１４の中間体３．０６ｇ（１０．０ｍｍｏｌ）に変えた点以外は同様にして、スチルベン系化合物（ｊ１０）の銀色光沢結晶薄膜体の薄膜体を得た。実施例１と同様に、元素分析とＮＭＲにより同定した。 Example 34 (Synthesis of stilbene compound j10)
(Reaction formula)

In the same manner as in Example 32, except that 4- (2-hydroxyethoxy) benzaldehyde was changed to 3.06 g (10.0 mmol) of the intermediate of f14, a silvery glossy thin film of the stilbene compound (j10) was obtained. A thin film body was obtained. In the same manner as in Example 1, it was identified by elemental analysis and NMR.

<Silver Gloss Evaluation of Stilbene Compounds>
About each said stilbene type compound, the regular reflectance and the color value were measured, and silvery glossiness was evaluated.
That is, a large integrating sphere device (JASCO ILN-472 large integrating sphere device color diagnostic program) was attached to the UV-visible spectrophotometer (JASCO V-570 UV / VIS / NIR Spectrophotometer), and the light trap reflector was removed. In this state, the diffuse reflectance of each stilbene compound crystal set in the sample holder was measured. Next, an optical trap reflector was inserted to measure the total reflectance, and the regular reflectance was calculated by the formula “regular reflectance = total reflectance−diffuse reflectance”. Further, each color value was calculated from the measurement result of total reflectance. Table 1 shows the results of the regular reflectance and the color values obtained, determined according to the following criteria.
If the regular reflectance and the color values (a value, b value) are both rank 1 or higher, it can be said that the organic colorant has a practical silver gloss.

<Regular reflectance>
Rank 3: 20% ≤ Regular reflectance Rank 2: 15% ≤ Regular reflectance <20%
Rank 1: 10% ≦ regular reflectance <15%

<Color value (a value)>
Rank 3: -1.5 ≦ a ≦ 1.5
Rank 2: −2.5 ≦ a <−1.5 or 1.5 <a ≦ 2.5
Rank 1: −3.5 ≦ a <−2.5 or 2.5 <a ≦ 3.5

<Color value (b value)>
Rank 3: -1.5 ≦ b ≦ 1.5
Rank 2: −2.5 ≦ b <−1.5 or 1.5 <b ≦ 2.5
Rank 1: −3.5 ≦ b <−2.5 or 2.5 <b ≦ 3.5

表１から、本発明に係るスチルベン系化合物は、いずれも、実用可能な銀色光沢を有する有機着色剤であることが判る。

From Table 1, it can be seen that any of the stilbene compounds according to the present invention is a practical organic colorant having a silvery luster.

Example 41 (Coloring composition 1 containing a stilbene-based compound)
Using a vial, materials of the following formulation were mixed uniformly, irradiated with ultrasonic waves (600 W) at room temperature for 1 hour, and then filtered through a 5.0 μm filter to obtain Colored Composition 1.
-Silver lustrous crystal thin film of stilbene compound f1 5.0 parts by weight-Ion-exchanged water 5.0 parts by weight-Dehydrated THF 88.8 parts by weight-Dispersant (DISPERBYK-190, manufactured by Big Chemie) 0.2 parts by weight

Examples 42 to 74 (coloring compositions 2 to 34 containing a stilbene compound)
Colored compositions 2 to 34 were obtained in the same manner as in Example 41 except that f1 in Example 41 was changed to stilbene compounds shown in the respective columns of Examples 2 to 34 in Table 1.

The obtained colored compositions 1 to 34 were applied to glass media and color paper as described below, and the silver glossiness of the printed matter was measured and evaluated. The results are shown in Table 2. As long as both the regular reflectance and the color value (a value, b value) are rank 1 or more, it can be said that it is a coloring composition having a practical silver gloss.

(In the case of glass media)
Using a bar coater (manufactured by Daiichi Rika Co., Ltd .: NO.22), each colored composition was applied to a 25 mm × 75 mm glass substrate having a thickness of 1.0 mm so as to have a thickness of 50 μm to obtain a printed matter. It was. Next, the silver glossiness of the printed material was evaluated in the same manner as in the above-described <Silver gloss evaluation of stilbene-based compound>.

(For color paper)
Each colored composition was applied to a color paper (Nagatoya Shoten, Color Paper A4 Medium Thick Mouth) using a bar coater (Daiichi Rika Co., Ltd .: NO.22) to a thickness of 50 μm. Got. Next, the silver glossiness of the printed material was evaluated in the same manner as in the above-described <Silver gloss evaluation of stilbene-based compound>.

上記表２から、本発明の着色組成物１〜３４を用いると、いずれも実用可能な銀色光沢を有する印刷物が得られることが判る。

From Table 2 above, it can be seen that when the colored compositions 1 to 34 of the present invention are used, a printed matter having a practical silvery gloss can be obtained.

Japanese Patent Laying-Open No. 2005-036079 JP 2011-52041 A JP, 2014-074127, A JP 2013-203785 A JP 2009-132641 A International Publication No. 2014-021405 Pamphlet

Claims (4)

An organic colorant having a silvery luster composed of a stilbene compound represented by the following general formula (1).

General formula (1)

In the above formula, each of R _{1 and} R ₂ independently has an alkyl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, or a substituent. a naphthyl group which may _{be, - (CH 2) n-} COO-R 3, - (CH 2) n-R 4, - (CH 2) n-CONH-R 5, -CR 6 R 7 -COO-R ₈ or a group represented by — (CH ₂ ) n —OCOCH ₃ , R ₃ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₄ represents a hydroxyl group and 1 carbon atom. ˜2 alkoxy group, C 2-5 alkenyloxy group, SO ₃ Na group, OSO ₃ Na group, phenylalkyl group which may have a substituent (carbon number of alkyl part is 1 to 3), Or a naphthylalkyl group (the alkyl part has 1 to 3 carbon atoms) which may have a substituent. And, _{R 5} is an alkyl group having 1 to 20 carbon atoms, a hydroxy alkyl group of the alkenyl group having 1 to 20 carbon atoms, or carbon atoms 1 to 12, _{R 6} is a hydrogen atom, or a methyl group R ₇ represents an alkyl group having 1 to 4 carbon atoms, R ₈ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 12.   The substituent is at least one selected from an alkyl group, an alkenyl group, a hydroxyalkyl group, a hydroxyl group, an alkoxy group, an alkenyloxy group, a cyano group, a cyanoalkyl group, a carboxyl group, an alkoxycarbonyl group, and an amino group. The organic colorant having a silvery luster according to claim 1. The organic colorant having a silvery luster according to claim _1, wherein R _{1 to} R ₂ are — (CH ₂ ) ₂ —OH.   A colored composition having a silvery gloss, comprising the organic colorant having a silvery gloss according to any one of claims 1 to 3, water and a solvent.