CN100543180C - The pattern formation method of organic semiconductor film - Google Patents
The pattern formation method of organic semiconductor film Download PDFInfo
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- CN100543180C CN100543180C CNB2005101166556A CN200510116655A CN100543180C CN 100543180 C CN100543180 C CN 100543180C CN B2005101166556 A CNB2005101166556 A CN B2005101166556A CN 200510116655 A CN200510116655 A CN 200510116655A CN 100543180 C CN100543180 C CN 100543180C
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Abstract
A kind of pattern formation method of organic semiconductor film, it is characterized by, utilize the solution that printing will contain bicyclic compound at least to be imparted to desirable position on the base material, part in the two ring skeletons is broken away from from described bicyclic compound, expand pi-conjugated system, described bicyclic compound is transformed into organic semiconductor material, and retro Di takes place in selected position on this base material thus, thereby desirable position forms organic semiconductor film on base material.
Description
The application be that March 6, application number in 2003 are 03119235.1 the applying date, denomination of invention divides an application for the application of " new compound, its preparation method and use ".
Technical field
The present invention relates to a kind of compound and preparation method thereof, can change this molecular structure of compounds, thereby can change its solubleness in solvent by retro Di; The invention still further relates to the ink, print cartridge, recording unit, ink-jet recording device, recording method, the recording medium that are used for devices such as ink-vapor recording; The invention still further relates to the pattern formation method and the liquid composition that is used for this method that are used to prepare the DNA chip, detect article whether through the environment resume detection method of heating etc. and article that can the testing environment resume.
Background technology
According to circumstances controlling the solubleness of compound in solvent is the technology of urgently being expected in the multiple technologies field.
For example: with the ink-vapor recording is example, considers from the stability of ink for inkjet, and preferred tinting material is present in this ink with dissolved state, promptly is present in the solvent with single molecules level.And consider from forming the first-rate quality pattern aspect, preferably after this ink is imparted on the recording medium,, make it to rest on recording medium surface or near surface immediately with tinting material and solvent release.Last performance can realize that back one performance can realize by so-called paint ink, but be difficult to make both to realize simultaneously by so-called dye ink.Though proposed in recent years to make pigment have the multiple technologies schemes such as character of dyestuff, improved leeway in fact in addition by with the pigment miniaturization or in measures such as surface of pigments introducing water dispersible functional groups.In addition, in recent years along with the increasing substantially of ink jet printer performance, ink-jet printer singly is not that literal or pattern form instrument, also be suggested as the device with fine pattern for example the preparation facilities of DNA chip etc. use.
Summary of the invention
Inventors of the present invention think that after studying repeatedly on the basis of above-mentioned technical background the following compound of exploitation is effective to further developing of ink-jet technology: can make ink keep stable dissolved state in solvent, in a single day ink is imparted into the solvability of promptly losing behind the recording medium this solvent, rests on this recording medium surface or near surface.Particularly, for example in ink-vapor recording,, can according to circumstances change the compound of dyestuff and pigment property at the tinting material in the ink.
Therefore the purpose of this invention is to provide and a kind ofly can control it with respect to new compound of solvent solubility and preparation method thereof.
Another object of the present invention provides a kind of ink, and this ink can carry out high quality record, can also to article predict these article through the functions such as environment resume detection of environment resume.
Another object of the present invention provides a kind of print cartridge and recording unit that can obtain the ink-jet recording device of high quality printing product and can be used for this device.
Another object of the present invention provides a kind of recording method and recording medium that can obtain high quality record thing.
Another object of the present invention provides a kind of liquid composition, this liquid composition can be used for the high quality record or give article multiple function, for example: can predict these article through the environment resume measuring ability of environment resume, the function of multifrequency natures such as the reaction responsiveness of fastness that can the controlling recording thing, concentration, brightness and the molecular element that makes up by record, electroconductibility.
Another object of the present invention provides a kind of pattern formation method that can accurately form millimicro meter level or slight meter level microgram case.
Further, another object of the present invention provide a kind of detect article through the method for environment resume and the article that can carry out above-mentioned detection.
Further, another object of the present invention provides a kind of compound, it is characterized in that: this compound has the solvophilic group to the regulation solvent, dissolve in this solvent, can this solvophilic group be broken away from by retro Di, thereby irreversibly reduce the solubleness of this compound this solvent.
This compound preferably has the tetraazatetradecane porphyrin skeleton.
Further, has the compound that the compound of tetraazatetradecane porphyrin skeleton preferably has structure shown in following formula (I)～formula (II).
(in formula (I) and the formula (II), R
1And R
2Represent this solvophilic group respectively, M is the coordination atoms metal of 2～4 valencys, and Y is halogen atom, Sauerstoffatom or hydroxyl, and n represents 0～2)
Above-claimed cpd preferably has the compound of porphyrin skeleton.
Further, has the compound that the compound of porphyrin skeleton preferably has structure shown in following formula (III)～formula (IV).
(in formula (III) and the formula (IV), R
1And R
2Represent this solvophilic group respectively, M is the coordination atoms metal of 2～4 valencys, and Y is halogen atom, Sauerstoffatom or hydroxyl, and n represents 0～2)
In addition, the invention provides a kind of synthetic method with compound of tetraazatetradecane porphyrin skeleton, this tetraazatetradecane porphyrin skeleton has and can break away from and the regulation solvent is had solvophilic group by retro Di, and this synthetic method is characterised in that and comprises following step:
(i) having this solvophilic group maybe can become the substituent cyclohexadiene of this solvophilic group and as the dicyano compound generation diels-alder reaction of dienophilic compound, form the step of compound shown in the following formula V; With,
(in the formula V, R
3And R
4Represent independently that respectively the solvophilic group maybe can become the group of solvophilic group)
Make atoms metal coordinate step in this phthalocyanine frame after (ii) 4 times of cyclisation of the compound shown in the above-mentioned formula V being formed the tetraazatetradecane porphyrin skeleton.
Further, the invention provides a kind of synthetic method with compound of porphyrin skeleton, this porphyrin skeleton has and can the reversed reaction by diels-alder reaction breaks away from and the regulation solvent is had the group of solvophilic, and this synthetic method is characterised in that and comprises following step:
(i) have that this solvophilic group maybe can become the substituent cyclohexadiene of this solvophilic group and as the benzene sulfonyl compound generation diels-alder reaction of dienophilic compound, form shown in following formula (VI) and the formula (VII) at least a step in the compound;
(in formula (VI) and the formula (VII), R
3And R
4Represent independently that respectively this solvophilic group maybe can become the group of this solvophilic group)
At least a and CNCH shown in (ii) above-mentioned formula (VI) and the formula (VII) in the compound
2COOR
5(R
5Expression C
1-4The straight or branched alkyl) shown in isonitrile generation addition cyclization, form the step of compound shown in the following formula (VIII); With,
(in the formula (VIII), R
3And R
4Represent independently that respectively the solvophilic group maybe can become the group of solvophilic group, R
5Expression C
1-4The straight or branched alkyl)
Make atoms metal coordinate step in this porphyrin skeleton after (iii) four times of cyclisation of compound shown in the above-mentioned formula (VIII) being formed the porphyrin skeleton.
The invention provides a kind of ink, it is characterized in that containing above-mentioned arbitrary compound and solvent.
The invention provides a kind of ink, it is characterized in that containing above-mentioned arbitrary compound and solvent, also comprise other compound as tinting material.
Above-mentioned ink is preferred for ink-jet.
The invention provides a kind of print cartridge, it is characterized in that having the ink accommodation section that holds above-mentioned ink.
The invention provides a kind of recording unit, it is characterized in that having ink accommodation section that holds above-mentioned ink and the ink gun that sprays this ink.
Further, the invention provides a kind of ink-jet recording device, it is characterized in that having ink accommodation section that holds above-mentioned ink and the ink gun that sprays this ink.
The invention provides a kind of recording method, it is characterized in that having following step:
(i) give the step of the above-mentioned ink of recording medium; With,
The (ii) step of this contained compound generation retro Di in the ink on this recording medium.
The invention provides a kind of liquid composition, it is characterized in that containing above-claimed cpd and solvent.
This liquid composition is preferred for spraying by ink jet method.
The invention provides a kind of pattern formation method, it is characterized in that having following step:
(i) give regioselectivity base material aforesaid liquid composition step and,
(ii) contained this compound generation retro Di in the liquid composition on this base material makes it to be insoluble to the step of this contained in this liquid composition solvent.
The invention provides a kind of article, it is characterized in that being attached with the retro Di product of above-claimed cpd or above-claimed cpd.
Further, the invention provides a kind of environment resume detection method of article, it is characterized in that having and detect the article that surface attachment has above-claimed cpd, confirm whether this compound the step of retro Di takes place.
The invention provides a kind of recording medium, it is characterized in that having the surface of the retro Di product that comprises above-claimed cpd or above-claimed cpd.
Description of drawings
Fig. 1 represents the synthetic route chart of porphyrins involved in the present invention.
Fig. 2 represents the synthetic route chart of tetraazatetradecane porphyrin compounds involved in the present invention.
Fig. 3 represents the profile oblique drawing of ink-jet printer involved in the present invention.
Summary of the invention
[compound involved in the present invention]
Compound involved in the present invention is with the group that the regulation solvent is had solvophilic, and is solvable In this solvent, and this solvophilic group by retro Diéls Alder reaction from this compound branch Break away from the son, consequently reduce this compound to the solubility of this solvent.
For example: when the regulation solvent be water or by water and hydrophilic organic solvent (such as alcohols solvent, second Glycolic solvents and glycerine etc.) form aqueous solvent the time, introduce in the water solubility (25 ℃) extremely Reach less the above solvophilic group of 1 quality %, i.e. hydrophilic radical is such as hydroxyl, sulfonic group, carboxylic Base or amino etc. Above-mentioned hydrophilic radical breaks away from from molecule by retro Diéls Alder reaction, Thereby can make almost vanishing of solubility. Hydrophilic radical herein is not limited to above-mentioned hydroxyl or sulfonic group Deng, also can be for containing polar substituent at least a in oxygen atom, nitrogen-atoms and the sulphur atom.
When the regulation solvent is non-aqueous or during the slightly water-soluble organic solvent, be introduced in solubility in the above-mentioned solvent (25 ℃) and reach at least the above lipophilic group of 1 quality %, such as alkyl or alkoxyl, preferred C4Above alkyl or alkoxyl. Above-mentioned group by retro Diéls Alder reaction from molecule The middle disengaging, thus the solubility in non-aqueous or slightly water-soluble organic solvent is almost become Zero.
Describe this compound in detail with concrete example below.
As mentioned above, by retro Diéls Alder reaction the solvophilic group is broken away from, thus can Effectively the examples of compounds of its solubility in solvent of control comprises following formula (I)～(II) institute Porphyrin compound shown in the tetraazatetradecane porphyrin compound that shows or the following formula (III)～(IV).
Or
In the formula (I)～(IV), R1And R2Represent respectively the solvophilic group, when solvent is water-based During solvent, preferably contain polar substituent at least a in oxygen atom, nitrogen-atoms and the sulphur atom, Particularly, comprise hydroxyl, sulfonic group, carboxyl or amino etc., wherein more preferably hydroxyl. Work as solvent During for non-aqueous or slightly water-soluble organic solvent, lipophilic group comprises methyl, ethyl, propyl group, fourth The alkoxyls such as the alkyl such as base or methoxyl group, ethyoxyl, propoxyl group, preferred C4Above alkyl or alkane The oxygen base.
In the formula, M represents the coordination metal of 2～4 valencys, specifically comprise Zn, Cu, Fe, Mg, Al, Ga, Ti and Sn etc. Y represents halogen atom, oxygen atom and the hydroxyls such as chlorine, bromine, iodine, n It is 0～2 integer.
[compound with porphyrin skeleton, this porphyrin skeleton comprises water soluble group]
The following describes the related porphyrin compound that can change solubility in its water of above-mentioned formula (IV) Object lesson.
Porphyrins shown in the following structural formula contains hydroxyl as hydrophilic radical, at this hydroxyl Effect under this compound can be dissolved in aqueous solvent (in the water under 25 ℃ solubility be 1 quality % with On), by retro Diéls Alder reaction this hydroxyl is broken away from from this compound molecule, from And reduce this compound to the solubility of aqueous solvent.
In general, the porphyrin skeleton part flatness height of porphyrins, most because π-π Overlap action and be insoluble in solvent (for example: solubility is less than 1 quality % in the water under 25 ℃), But two ring [2,2,2] the octadiene skeleton contracting rings that are connected with hydroxyl shown in the above-mentioned formula (IX) form Porphyrin is because the existence of large volume two ring [2,2,2] octadiene skeletons and hydroxyl makes its water soluble The property solvent. When the compound generation retro Diéls Alder reaction shown in the above-mentioned formula (IX), bridge Ethene on the key breaks away from, and adds that hydroxyl breaks away from and volume reduces, and causes molecule overlapping, thus chemical combination The solubility of thing in aqueous solvent reduces, and for example: 25 ℃ lower insoluble or hardly water-soluble. With (IV) for example illustrates porphyrins of the present invention, zinc is as central metal usefulness, the hydroxyl conduct The solvent affinity groups, but the invention is not restricted to this. As mentioned above, also can be to not having the parent Consider with the aspects such as polarity of the solvent of property, suitably select. Beyond the dezincification, central metal also comprises Copper, magnesium and aluminium etc. Can also be with the electronic state of necessary compound, show that the constant of structure (inhales Receive spectrum etc.) be adjusted into object, with this end in view, consider from aspects such as synthetic complexity degree, Suitably select. The substituting group that can change solvophilic does not have particular restriction, for example: from synthetic difficult Easily the aspect such as degree degree is considered, hydroxyl etc. is become ether or ester group after, just can become long-chain alkane The various substituting groups such as base, ethylene glycol.
[synthetic method of porphyrins]
The following describes the synthetic method of the porphyrins that the present invention relates to.
The compound with porphyrin skeleton that the present invention relates to can be synthetic by following step, and this porphyrin skeleton is with the group that can break away from and the regulation solvent is had by retro Diéls Alder reaction solvophilic:
(i) maybe can become the substituent cyclohexadiene of this solvophilic group with this solvophilic group As diene with as the benzene sulfonyl compound generation diels-alder reaction of dienophilic compound, shape Become shown in following formula (VI) and the formula (VII) at least a step in the compound;
(in formula (VI) and the formula (VII), R3And R4Represent independently that respectively the solvophilic group maybe can become the group of solvophilic group)
(ii) at least a in the compound shown in above-mentioned formula (VI) and the formula (VII) and, CNCH2COOR
5(R
5The straight or branched alkyl of expression C1～4) isonitrile shown in adds Become cyclization, form the step of compound shown in the following formula (VIII); With,
(in the formula (VIII), R5Expression C1-4The straight or branched alkyl)
(iii) make metal after four times of cyclisation of the compound shown in the above-mentioned formula (VIII) form the porphyrin skeleton The step of atom coordination in this porphyrin skeleton. Above-mentioned formula (VI) and (VII) in, R3And R4Expression solvophilic group is namely with the middle R of above-mentioned formula (I)～(IV)1And R2Identical group, or Can become the group of solvophilic group. The group that can become the solvophilic group comprises R1、R
2The protection attitude, for example in the building-up process of porphyrin compound, for preventing R1And R2Middle at least one party's complete reaction is protected R with blocking group1And R2 Describe below porphyrin shown in the above-mentioned formula (IX) in detail The synthetic method of compound. Can synthesize this compound by route shown in Figure 1. Among the figure, chemical constitution Formula with this structural formula of symbolic representation shown in the sequence number of compound, arrow institute signed representation step Sequence number.
At first, under the condition that acetone, dimethoxy propane and p-methyl benzenesulfonic acid exist, make 3,5-cyclohexadiene-1, the 2-glycol reacts, and obtains the shielded compound 2 of hydroxyl (i). Under the condition that toluene exists, compound 2 and as the 2-nitro of dienophilic compound-1-benzenesulfonyl second Alkene generation diels-alder reaction gets compound 3a, 3b (ii). Replacing at nitrogen will under the environment Gained compound 3a, 3b are dissolved in anhydrous THF (oxolane), the anhydrous isocyanide of ice-cooled lower adding Behind the guanidine-acetic acid ethyl ester, add again anhydrous 1,8-diaza-bicyclo-[5,4,0] 11 carbon-7-alkene (below Claim " DBU "), by the reaction of improvement Barton-Zard method, get porphyrin precursor compound 4 (iii).
Improvement Barton-Zard method described herein is as more diversified aromatic ring construction method And establish, as N.Ono, H.Hironaga, K.Ono, S.Kaneko, T.Murashima, The J.Chem.Soc.Perkin Trans. that T.Ueda, C.Tsukamura and T.Ogawa etc. show 1, disclosed in 1996,417, improvement is by nitroolefin, aromatic nitro compound and isocyano group second Acetoacetic ester forms the construction method of pyrrole ring. By successfully synthesizing in conjunction with diels-alder reaction Have the compound of new function, thereby finish the present invention. The Barton-Zard method is so far known Alkyl substituted azole framework construction method, but the present invention adopts improvement Barton-Zard method can make up aromatic ring Replace the reaction of precursor (aryl replacement precursor) pyrrole skeleton. Particularly, pass through Di Ersi-A Deer reaction synthetic initiation material---the substituted sulfonyl compound of solvophilic group and nitre The base sulfonyl compound with both and isocyano acid B ester reaction, makes up the precursors pyrrole ring.
Under nitrogen protection compound 4 is dissolved in anhydrous THF, ice-cooled lower adding lithium aluminium hydride reduction makes Reaction, get the tetraploid of compound 4---have the compound 5 (iv) of porphyrin skeleton. To change Compound 5 and slaine (for example zinc acetate) are dissolved in together in the chloroform-methanol equal solvent and react, and make Metallic element coordination in the porphyrin skeleton gets compound 6 (v). Then, compound 6 is carried out Hydroxyl breaks away from protective reaction, gets compound 7 (vi) shown in the above-mentioned formula (IX). Under 25 ℃, gained The solubility of compound 7 in 1g methyl alcohol is 1.4g, and the solubility in the 1g isopropyl alcohol is 2.55g, Solubility in 1g water/isopropyl alcohol mixed solvent is 0.8g.
Retro Diéls Alder reaction takes place in compound 7, obtains breaking away from the compound 8 of hydroxyl. Under 25 ℃, compound 8 is dissolved in aqueous solvent hardly.
[diels-alder reaction and retro Diéls Alder reaction]
Diels-alder reaction refers to the chemical combination of the two keys of the Isosorbide-5-Nitrae position addition of conjugated double bond or triple bond Thing forms the reaction of 6 yuan of hydrogenation aromatic rings. Retro Diéls Alder reaction refers to Di Ersi-A De The back reaction of your reaction. For example: the chemical combination with two ring [2,2,2] octadiene skeleton contracting loop sections Thing generation retro Diéls Alder reaction can make the ethene on the bridged bond break away from. At this ethene position Connect the group that increases this compound solubility, can control its solubility thus. In addition, the present invention The retro Diéls Alder reaction that passes through that relates to makes the result of ethene disengaging be: when compound has π During conjugated system, preferably make up following molecule result: pi-conjugated system causes molecule by steric hindrance The structure of big stereochemical structure becomes flat structures. Can control thus this compound take place contrary Di Ersi-Compendency or the concentration of A Deer reaction gained compound.
For reaching above-mentioned preferred condition, preferably behind retro Diéls Alder reaction, intermolecular establishing Meter increases intermolecular interaction by hydrogen bond, Fan Dehuali, electrostatic interaction and polarity System. In the prior art, though gather state increase cause in the restive system also passable Effectively control compendency and concentration by the character of compound before and after the design reaction.
Extremely stable by the bridged bond substituting group that retro Diéls Alder reaction breaks away from, therefore can with The compound that the present invention relates to becomes stable material. In other words, decision design does not take place being System consists of the reaction system of dysgenic reversible reaction or side reaction. In general, anti-from heat release Answer between (diels-alder reaction) and the endothermic reaction (retro Diéls Alder reaction) Balanced reaction learn the diels-alder reaction of diolefin compound and dienophilic compound compound Be reversible reaction. Disclose in the Unexamined Patent 11-349877 communique this point has been used for the control ink jet ink The example of water carrier viscosity and temperature. But the reaction of adopting in this invention is reversible reaction, the people Think that this reaction is used under the state that solubility reduces, again causing after the cooling when of the present invention Cyclization, solubility increases once again. In addition, under the retro Diéls Alder reaction state because Situation with unstable diolefin compound and dienophilic compound compound exists, and may cause that oxidation is secondary anti-Should, therefore it is believed that to be not suitable for the present invention. Further, Unexamined Patent 10-31275 public affairs Following example is disclosed in the newspaper: utilize ultraviolet heat to cause that the decomposition of three propene and methane compounds is anti-Should or the photo-thermal invertibity compound such as photochromic compound control polarity (dissolubility, compendency). Yet the used Polarity Control of the present invention partly is free radical cracking decomposing system, so may produce Give birth to non-reversible state, the accessory substance instability causes the autothermic cracking reaction, causes harmful effect. In addition Outward, photochromic reactions is visual ultraviolet light and hot reversible reaction, therefore is difficult to keep a kind of State it is believed that not fit into the present invention.
Therefore, the following reaction system of decision design of the present invention: pass through retro Diéls Alder reaction The compound that breaks away from from precursor and the compound that produced by precursor with cause once again Di Ersi-A De The diene of your reaction and the irrelevant reaction system of dienophilic compound. In this state, by contrary Di Ersi-The constant one-tenth dienophilic compound of compound (1,2-ethylene glycol) that the A Deer reaction breaks away from. In addition, 1, 2-ethylene glycol self instability becomes glycollic aldehyde in reaction system. Therefore, reaction system In do not have the compound that again reacts with non-water-solubleization compound 8, thereby make contrary Di Ersi-A Deer reaction irreversibility ground carries out. Like this, from making the retro Diéls Alder reaction can not Contrary property ground carries out the aspect and considers preferred following reaction system: pass through retro Diéls Alder reaction The compound that breaks away from does not contain reactive double bond, Di can not be taken place because oxidation, reduction, isomerization become The material of Er Si-A Deer reaction.
[retro Diéls Alder reaction]
Make the compound that the present invention relates to for example make the compound 7 in Fig. 1 route that contrary Di Ersi takes place The concrete grammar of-A Deer reaction comprises from the irradiation of heating, light, electromagnetic wave or radioactive ray extremely Few choosing is a kind of energy etc. that provides then.
[compound with tetraazatetradecane porphyrin skeleton, this tetraazatetradecane porphyrin skeleton comprises water soluble group]
Other example of compound involved in the present invention comprises four azepine porphins shown in the following formula (X) Quinoline compound etc.
The same with compound shown in the above-mentioned formula (IX), because connecting on two ring [2,2,2] octadiene skeletons Hydroxyl is arranged, and this compound keeps the dissolubility to aqueous solvent, and is anti-by contrary Di Ersi-A Deer Should make ethene break away from this compound molecule, therefore forfeiture is to the good solubility of aqueous solvent.
[synthetic method of tetraazatetradecane porphyrin compounds]
The following describes the synthetic method of the tetraazatetradecane porphyrin compounds that the present invention relates to.
The compound with tetraazatetradecane porphyrin skeleton that the present invention relates to can be synthetic by following step, This tetraazatetradecane porphyrin skeleton be with breaking away from by retro Diéls Alder reaction, and molten to stipulating Agent has the group of solvophilic.
(i) has the substituent cyclohexadiene that this solvophilic group maybe can become this solvophilic group Dicyano compound generation diels-alder reaction with as dienophilic compound forms following formula The step of compound (V); With,
(in the formula (V), R3And R4Represent independently that respectively the solvophilic group maybe can become the group of solvophilic group)
(ii) the compound cyclisation shown in 4 times of above-mentioned formulas of amount (V) is formed the tetraazatetradecane porphyrin skeleton After make the step of metallic atom coordination in this phthalocyanine frame. In the following formula, R3And R4Expression solvophilic group is namely with the middle R of above-mentioned formula (I)～(IV)1And R2Identical group maybe can become the parent The group of solvent group. The group that can become the solvophilic group comprises R1、R
2The protection attitude, for example in the building-up process of porphyrin compound, for preventing R1And R2Middle at least one party's complete reaction is protected R with blocking group1And R2。
Describe the synthetic method of porphyrin compound shown in the above-mentioned formula (X) below in detail.This compound can be synthetic by route for example shown in Figure 2.At first, under the condition that acetone, Propanal dimethyl acetal and tosic acid exist, 3,5-cyclohexadiene-1, the 2-glycol reacts, and obtains hydroxyl shielded compound 2 ' (i ').Diels-alder reaction takes place in compound 2 and dicyano acetone under the condition that toluene exists, get dicyano compound 3 ' (ii ').Replace under the environment gained compound 3 ' be dissolved in the propyl carbinol equal solvent with two propyl carbinol magnesium at nitrogen, by reacting tetraploidization formation tetraazatetradecane porphyrin skeleton, simultaneously, metallic element coordination in the tetraazatetradecane porphyrin skeleton gets compound 4 ' (iii ').Then, compound 4 ' carry out hydroxyl is broken away from protective reaction and get compound 5 ' (iv ') that above-mentioned formula (X) relates to.The solubleness of 25 ℃ of following compounds 5 ' in water is about 50 quality %.
Then, shown in step (v '), compound 5 ' generation retro Di, dehydroxylation compound 6 ', 25 ℃ of following compounds 6 ' water insoluble (solubleness is zero).
[compound] with oiliness group
The compound that aqueous solvent is had good solubility more than has been described, but the technology that the present invention relates to is not limited thereto, make the compound generation retro Di that in the oiliness organic solvent, has good solubility, can reduce its solubleness in oil-based solvent.This compounds comprises compound with structure shown in the following formula (XI) etc.By the hydroxyl in the above-claimed cpd group is become solvatable groups such as alkyl, or when synthetic, initial substance is processed, can be synthesized this compounds simply.
[application examples of new compound of the present invention]
The following describes the application of above-mentioned all cpds in multiple use.
[ink]
Owing to can control the solubleness of above-mentioned all cpds in solvent, so ink is used in ink and can be carried out high quality printing.Particularly, for example: the material that can become pigment type colorant by the dye-type tinting material.More particularly, exist with dissolved state in ink, the generation retro Di is reduced in the solubleness in the solvent on recording medium, the tinting material on the recording medium can be separated rapidly with solvent thus.In addition,, make the material of (comprising photostabilization, the gasproof) structure that has excellent durability, may obtain the advantage of dye ink and paint ink two aspects by the compound (tinting material) that retro Di is formed according to technology of the present invention.Contained material as fine coloring agent does not have particular restriction in the ink composition that the present invention relates to, but it is firm generally especially preferably to gather state, solvability, dispersed low tinting material, and its effect is remarkable.For example: polycycle tinting material, various chelating tinting material, nitro tinting material, nitroso-group tinting material and nigrosines etc. such as preferred azo colouring agent, quinones tinting material, quinoline bifurcation ketone pigment.The most compound molecule interphase interactions of above-mentioned tinting material are big, solvability, dispersed low.
For compound (tinting material) being made the good material of weather resistance (stability), as previously mentioned, must make the structure that is not subject to extraneous main aging action (light, gas) influence by intermolecular interaction.Therefore, it is very important to control intermolecular interaction.
[ink for ink-jet print]
As above-mentioned formula (IX) or (X), as tinting material, can obtain the aqueous jet ink by the water-soluble cpds that will the present invention relates to.
The solvent of water-base ink comprises the mixture of water or water and water-miscible organic solvent.When making the mixture of water and water-miscible organic solvent, the content of water-miscible organic solvent is not had particular restriction, but be 3～50 quality % with respect to the preferable range of all-mass ink.In addition, with respect to the ink of all-mass, the content preferable range of water is 50～95 quality % in the ink.
Particularly, water-miscible organic solvent comprises C such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, Pentyl alcohol
1-5Alkyl alcohol, amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, ketone such as acetone, diacetone alcohol or ketols, ethers such as tetrahydrofuran (THF), dioxane, ethylene oxide or propylene oxide copolymers such as glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, polyoxyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, 1, ammediol, triglycol and 1,2, C such as 6-hexanetriol
2-6The aklylene glycol class, glycerine, low alkyl group ethers such as ethylene glycol one first (second) ether, glycol ether one first (second) ether and triglycol one first (second) ether, how pure lower dialkyl ethers such as triglycol diformazan (second) ether and Tetraglycol 99 diformazan (second) ether, alkanol amines such as monoethanolamine, diethanolamine and trolamine, tetramethylene sulfone, N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone and 3-dimethyl-2-imidazolone etc.As mentioned above, water-miscible organic solvent can be used alone or as a mixture.In addition, for water-base ink of the present invention (solvent is the ink of aqueous solvent) is made the ink with required physical parameter, other additive can be added as required in mentioned component, for example: viscosity modifier, defoamer, sanitas, mould inhibitor, tensio-active agent and oxidation inhibitor etc.
[other ink example]
Above-mentioned ink more than has been described with the situation of the compound that the present invention relates to, but in the ink that the present invention relates to, has reduced the deliquescent compound of solvent in ink pigment not necessarily by retro Di as tinting material.For example: can be with at least a as in the ink composition of the compound that the present invention relates to.For example: add in the ink with polymkeric substance as water-soluble binder change deliquescent compound by retro Di, make this polymkeric substance in ink, be dissolved state, when giving recording medium, become non-water soluble substance then, can obtain the good record thing of water tolerance thus by retro Di.
[ink jet recording method]
The water-base ink that contains the tetraazatetradecane porphyrin compound shown in porphyrin compound shown in the above-mentioned formula (IX) or the formula (X) can be applicable to ink-vapor recording.Particularly, for example: this ink is poured into commercially available ONDEMAND type ink-jet printer (BJ-F900 (trade(brand)name) for example, Canon Inc.'s system) behind the print cartridge, this print cartridge is contained on the printer, after this ink is given to recording medium, cause retro Di, to the ink external energy on the recording medium.As previously mentioned, light, heat etc. can be used as the energy that adds herein.After ink added on the recording medium, the ink on the recording medium, recording medium were the materials that glassware for drinking water is had excellent permeability, for example: when recording medium is common paper etc., ink fully is penetrated in the recording medium.For example: when being common paper (Canon system PB paper), owing to permeate well, ink and energy give the time difference preferably in one second.Therefore, in the ink-jet recording device used herein, it is almost synchronous that the energy of giving ink on time and the recording medium for the ink that makes recording medium adds the time, perhaps give behind the ink external energy in the time that can lack as far as possible, can or energy be set near record-header dirty near the record-header and add instrument.
[ink-jet recording device]
Bring out the recording unit of instrument below with primary heater unit, as retro Di of the present invention with Fig. 3 explanation.
Fig. 3 is the profile oblique drawing of printer, and this printer is equipped with removably print cartridge C of the record-header that can exchange (not having diagram) and relative this record-header.Print cartridge C is a kind of form of holding the ink accommodation section of ink of the present invention.Record-header and print cartridge C can freely load and unload carriage 3.Carriage 3 along the axis of guide 11 on slip direction, mesh, also the part with the rotating band 52 that moves by main-scanning engine (do not have diagram) links to each other, record-header and print cartridge can be along axis of guide scanning directions thus.From scanning in posting field inboard and the zone, front side of record-header, black case, the direction approximately parallel with the axis of guide has year roller 16 that prolongs existence.Year roller 16 controlled loops and the subscan engine (all not having diagram) that have the primary heater unit preheating concurrently drive, add on thermal recording media P and the recording medium new compound of the present invention contained in the ink, when bringing out retro Di, transport recording medium P.The recording medium P that is transported leads heating with infrared heating device 500 from the lettering back side at lettering pressing plate position, makes recording medium P and new compound of the present invention reach temperature required, and retro Di takes place rapidly.Infrared heating device 500 is by halogen heating unit 501 for example, stop netted lettering pressing plate 502 that recording medium enters and can efficiently heat, form at the red control loop (do not have and illustrate) of reflector (not having diagram), temperature sensor (thermistor) (not having diagram) and the controlled temperature transmitter of outside line optically focused that makes of recording medium one side.In addition, illustrated that the Infrared Heating that produces with halogen heater in the above-mentioned ink-jet recording device is as heater means, but the retro Di characteristic that new compound according to the present invention has, also the semiconductor laser that can use with warm wind type of heating or optics cracking etc. other bring out means.
[recording unit]
The recording unit that the present invention relates to has the essential record-header of ink-jet recording device, print cartridge (ink accommodation section), carriage 3 and paper transferrer, also has to bring out the necessary external energy applicator of new compound generation retro Di of the present invention (heating unit, illumination apparatus, electromagnetic wave irradiation device etc.).Said apparatus suitably selects equipment to carry out programme controlled controller and ink answering system device etc.
[print cartridge]
The print cartridge that the present invention relates to can suitably be selected the used print cartridge of common ink-jet recording for use, provide the device of ink comprising the head that can give record-header top, can provide the device of ink and with the incorporate device of record-header etc. to head with pipe.
[recording medium]
Recording medium for example in the used recording medium such as ink-vapor recording, can contain the new compound that the invention described above relates to.This recording medium is used for ink-vapor recording can obtains high-quality ink-vapor recording thing.The example that the new compound that the present invention relates to is included in recording medium as: the compound that the present invention relates to is coated on the recording medium as water-soluble binder.Behind use ink-mist recording on this recording medium, the water-soluble group that dissolves of this compound breaks away from by retro Di, can make recording medium surface hydrophobization thus.Can adjust the degree that retro Di carries out this moment by the energy of giving on the controlling recording medium, therefore also can adjust the degree of hydrophobization.The well secured property of the water-base ink that can satisfy on the recording medium thus to be given and the high level of low-permeability two aspects.
In this form, becoming the recording medium that is recorded object is the material of suitably selecting from the recording medium that is applicable to the ink jet recording method that utilizes water-base ink, no particular restriction, and for example: information such as film are passed on paper, fiber and leather etc.Information is passed on the preferred surface treated paper of paper, particularly, sets up in the preferred above-mentioned base material and stores layer.Ink stores layer, for example by with cationic polymers dipping or be coated on the above-mentioned base material, or cellular silica, alumina sol or special ceramics are coated on above-mentioned substrate surface with hydrophilic polymers such as polyvinyl alcohol design.In addition, common paper also can be used as recording medium.
[additive etc.]
Also can add additive etc. in ink, liquid composition or the recording medium.The concrete example of additive etc. does not have particular restriction, comprises oxidation inhibitor, salicylic acid, the benzotriazole category uv-absorbing agent of hindered amine, hindered phenol etc.Above-mentioned additive is generally non-water soluble substance, in the time of in being included in ink for ink-jet print, ink-jet recording device recording medium, generally imports water-soluble substituting group (hydroxyl, carboxyl, sulfonic group etc.) in additive.But this moment, moisture effects such as high humidity can cause additive migration phenomenons such as (outflow), and estimating can the reduction effect.If for anti-phenomenon here increases molecular weight, then the solvent borne of additive reduces, and may can not get the effect of initial expectation.In this case, by using the structure that group breaks away from, structure changes of dissolving of the present invention, thereby the control solvent borne can stop the migration of additive thus.In order to take into account solvability and transport property two aspects, preferred control break away from substituting group and the compound that forms from precursor on residual substituent size, polarity and position.
[environment resume method for detecting]
As previously mentioned, heating means are as making one of means of the compound generation retro Di that the present invention relates to, and this character also can be used as the hot resume method for detecting of this compound.That is: change compound structure by retro Di, particularly make up pi-conjugated system, retro Di front and back color is changed.Utilize this colour-change,, can know whether to have added to reach the above heat of specified temperature for example to article.For example as previously mentioned, the compound with porphyrin skeleton or tetraazatetradecane porphyrin skeleton that the present invention relates to is heated to the temperature of bringing out retro Di variable color when above.This temperature is different with designed compound, for example: the variable color under the hot resume more than 120 ℃ of above-mentioned new compound.Therefore, the compound that the present invention relates to is sticked on the article, observe this compound, thereby can know hot resume this price by whether variable color of retro Di.
[process for purification of compound]
The technology that utilization the present invention relates to can purified compound.For example: in various organic function materials, it is believed that useful, the related compound of πDian Zi expansion compound, for example in the tetraazatetradecane porphyrin compounds (phthalocyanine etc.), great majority are insoluble in solvent owing to molecule is overlapping, are difficult to remove intermolecular impurity and refining.But, the technology that utilization the present invention relates to is at the phthalocyanine synthesis phase, for example: be connected with hydrophilic radical, two cyclohexadiene skeletons that steric barrier is big by importing, guarantee that it has high resolution to aqueous solvent, this stage by filtering or ordinary method such as extraction is made with extra care, remove impurity after, retro Di takes place rapidly, and ethene is broken away from, expansion πDian Zi system, obtain required compound, phthalocyanine compound for example, and obtain highly purified phthalocyanine compound easily.
[pattern formation method]
The compound generation retro Di that the present invention relates to can be made the compound film with organic semiconductor characteristic.In general, known anthracene, tetracene, Polythiophene, porphyrin and tetraazatetradecane porphyrin class (phthalocyanine etc.) compound have the organic semiconductor characteristic, these compounds have the two dimensional structure of big pi-conjugated system, so majority is insoluble in solvent, generally can not be outside evaporation during the system film.Evaporation system film is owing to adopt intermittent type, and many aspects are subjected to the restriction of film forming condition, are difficult to carry out big area homogeneous system film, also are unfavorable for saving cost.
But, utilize the technology that the present invention relates to can make above-mentioned anthracene, tetracene, Polythiophene, porphyrin and tetraazatetradecane porphyrin class (phthalocyanine etc.) compound have solvent soluble, these solution can be made film by teeming practice etc.By retro Di ethene is broken away from behind the system film, expand pi-conjugated system, thereby can obtain from the organic semiconductor film of required compound formation.The system embrane method comprises teeming practices such as dip-coating, and these compounds of having given anthracene, tetracene, Polythiophene, porphyrin and the tetraazatetradecane porphyrin class (phthalocyanine etc.) etc. of solvent soluble also can be printed with silk screen printing or ink-jetting style.With these system embrane methods energy big area, low-cost system film.Further, if adopt the ink-jetting style printing, give ink to desired location very high degree of precision that can be on recording medium, retro Di takes place on this substrate make it be insoluble to solvent, can on recording medium, form the organic semi-conductor patterns of high precision thus.In addition, these compounds are beginning to be imparted to the solubleness that can be reduced in after base material (recording medium) is gone up in the solvent, therefore can make the behavior of solvent behavior on the recording medium and organic semiconductor material (referring to anthracene, tetracene, Polythiophene, porphyrin and tetraazatetradecane porphyrin class (phthalocyanine etc.) compound herein) independent.In a word, though at solvent under the situation of diffusion out of order on the base material, this organic semiconductor material that also can suppress to be insoluble to solvent is followed the diffusion of solvent and is spread.This point also helps the high precision int of pattern.
[embodiment]
The following describes based on embodiments of the invention, clear and definite effect of the present invention, but the invention is not restricted to these embodiment.
Use following abbreviation:
THF: tetrahydrofuran (THF)
DBU:1,8-diaza-bicyclo-[5,4,0]-11 carbon-7-alkene
[embodiment 1 (synthesizing of porphyrins)
By the synthetic porphyrins of the present invention as tinting material of the route of putting down in writing among Fig. 1, this compound has can be by the hydroxyl of retro Di disengaging.
At first prepare 3,5-cyclohexadiene-1,20% ethyl acetate solution (25ml) of 2-glycol (compound 1) is as raw material, behind the concentrating under reduced pressure solvent, toward wherein adding acetone (30ml), 2,2-Propanal dimethyl acetal (69ml) and micro-tosic acid stirred 4 hours under the room temperature.The aqueous sodium hydroxide solution (30ml) of adding 10% and saturated aqueous common salt (30ml) stir; stopped reaction; with ether (3 * 30ml) extractions; (3 * 30ml) clean organic layer with saturated aqueous common salt; use anhydrous sodium sulfate drying then; concentrating under reduced pressure gets 8.33g compound 2, the i.e. shielded compound of compound 1 hydroxyl.
In compound 2 (158mg, 1.04mmol) and 2-nitro-1-(benzenesulfonyl) ethene (230mg, 1.08mmol) reaction vessel of packing into, add toluene (2.00ml), 90 ℃ were stirred 3 hours down.After reaction finished, the concentrating under reduced pressure reaction soln separated with column chromatography (20～30 volume %, ethyl acetate/hexane), and concentrated Rf is that 0.24 (20 volume %, ethyl acetate/hexane) and Rf are the component of 0.18 (20 volume %, ethyl acetate/hexane).With above-mentioned substance difference recrystallization, get compound 3a124mg (0.339mmol, 3.26 quality %) and compound 3b62mg (0.17mmol, 16.3 quality %).
mp?151.9-152.6℃
1H NMR (solvent: CDCl
3Unit: δ ppm 7.87 (m, 2H), 7.71 (m, 1H), 7.59 (m, 2H), 6.16 (m, 2H), 4.81 (dd, J=5.6,2.4Hz, 1H), 4.33 (dd, J=6.8,2.9Hz, 1H), 4.19 (dd, J=6.8,2.9Hz, 1H), 4.04 (dd, J=5.6,1.5Hz, 1H), 3.70 (m, 1H), 3.48 (m, 1H) 1.28 (s, 3H), 1.22 (s, 3H)
IR(KBr)/cm
-1?2981w、1552s、1313s、1151s、1056s、727.0m、601.7m。
With compound 3a and 365mg (1mmol) compound 3b (2,2-dimethyl-8-nitro-9-benzenesulfonyl-3 α, 4; 7,7 α-tetrahydrochysene-4,7-ethanol-1; the 3-benzo) carries out nitrogen in the adding reaction vessel and replace, be dissolved in the anhydrous tetrahydro furan (5.00ml), reaction vessel is immersed in the ice bath.(0.110ml, 1.00mmol) (0.370ml 2.50mmol) divides and to drip for 5 times, removes ice bath, stirs 17 hours under the room temperature distilled DBU from potassium hydroxide in the back to add anhydrous isocyanide ethyl acetate.After reaction finishes, the hydrochloric acid (10.0ml) of adding 2%, (3 * 20.0ml) extractions are cleaned organic layer with saturated aqueous common salt, use anhydrous sodium sulfate drying then with ethyl acetate, concentrating under reduced pressure, separate with silica gel column chromatography (5 volume %, ethyl acetate/chloroform), concentrated Rf is 0.24 (20 volume %, ethyl acetate/hexane) and Rf be the component of 0.41 (5 volume %, ethyl acetate/chloroform).Get 283mg (97.8mmol, 97.8 quality %) compound 4 behind the recrystallization.
mp?114.9-146.3℃
1H NMR (solvent: CDCl
3, unit: δ ppm) 8.58 (Br, 1H), 6.68 (d, J=2.4Hz, 1H), 6.50 (m, 2H), 4.56 (m, 1H) 4.34 (m, 2H), 4.32 (q, J=7.oHz, 2H), 4.o6 (m, 1H), 1.42 (s, 3H), 1.38 (t, J=7.oHz, 3H), 1.3o (s, 3H)
IR(KBr)/cm
-1?3345s、2892w、1681s、1297m、1141s、1039s。
(289mg 1.00mmol) carries out nitrogen in the adding reaction vessel and replaces, and is dissolved in the anhydrous tetrahydro furan (5.00ml), and reaction vessel is immersed in the ice bath with compound 4.(114mg 3.00mmol), removes ice bath, stirs 1 hour under the room temperature to add lithium aluminum hydride.After reduction finishes, add saturated aqueous common salt (20.0ml), with diatomite elimination insolubles, (3 * 100ml) extractions are cleaned organic layer with saturated aqueous common salt, use anhydrous sodium sulfate drying then with chloroform.Add tosic acid (80.0mg) in the solution, stirred one day.(223mg, 0.907mmol) the back restir is one day to add chloranil again.After reaction finishes, use 1% sodium thiosulfate solution (50.0ml) and the clean reaction soln of saturated aqueous common salt (50.0ml) respectively, again with behind the anhydrous sodium sulfate drying, concentrating under reduced pressure, refining with column chromatography, get compound 5 (yield is 39.8 weight %) behind the recrystallization.
In reaction vessel, compound 5 and neutralized verdigris are dissolved in chloroform (30ml)-methyl alcohol (3ml), stirred 3 hours under the room temperature.After reaction finished, water (100ml * 2) and saturated aqueous common salt (40ml) were cleaned respectively, again with behind the anhydrous sodium sulfate drying, and concentrating under reduced pressure, recrystallization from chloroform-methanol gets red-violet colour crystalline compounds 6.
Gained compound 5 carries out deprotection reaction by hydrolysis under sour existence condition, get water-soluble purpose compound 7.
[embodiment 2 (making of ink for ink-jet print and pattern recording), reference example]
After with ultra-filtration membrane the compound 7 of gained among the embodiment 1 being carried out desalting treatment, prepare ink for ink-jet print (water-base ink) by following composition with as a reference example phthalocyanine dye (C.I. sun blue-199).
1) through the compound 7 of desalting treatment or C.I. sun blue-199 5.0 part
2) glycerine is 5.0 parts
3) urea is 5.0 parts
4) ethylene glycol is 5.0 parts
5) water is 80.0 parts
Amount to 100.0 parts
Be called the ink-jet printer of BJ-F87 0 in recording medium (trade(brand)name: PR-101 with this ink and Canon Co., Ltd's system commodity; Canon Co., Ltd's system) goes up seal one length and width and be 1cm red-purple four directions color lump.The color lump of embodiment 2 makes compound 7 that retro Di take place 12 ℃ of following thermal treatments one minute, and the color lump heating becomes cyan.So carry out light fastness, gasproof fastness, color fastness to water and the moisture-proof fastness of embodiment 2 and reference example color lump.
[light fastness]
Under following test conditions, carry out fast light exposure test with the xenon lamp light fastness tester.This test is to consider indoor pattern fastness test of passing the sunlight of window.
Test conditions:
Intensity of illumination: 70K lx test period: 520 hours
Humiture in the Thoughs: 24 ℃ of 60%RH
Spectral filter: soda-lime (outside), borosilicate (inside)
Estimate light fastness with following method:
A: the remaining rate of concentration is greater than 90%
B: the remaining rate of concentration is 89～80%
C: the remaining rate of concentration is less than 79%
[gasproof fastness]
Under following test conditions (ANSI/ISA-S71.04-1985), carry out the gas exposure test with the gaseous corrosion trier.This test is the pattern fastness test of considering indoor all gases influence.
Test conditions:
Expose gaseous constituent: H2S:50ppb, SO2:300ppb, NO2:1250ppb, Cl2:10ppb, O3:1200ppb
Test period: 72 hours, the interior humiture of Thoughs: 24 ℃ of 60%RH
Estimate the gasproof fastness with following method:
A: the remaining rate of concentration is greater than 90%
B: the remaining rate of concentration is 89～80%
C: the remaining rate of concentration is less than 79%
[color fastness to water]
After gained write down thing flood 5 minutes in tap water, take out dry, the change in concentration before and after the determination test.
A: the remaining rate of concentration is less than 1%
B: the remaining rate of concentration is 2～4%
C: the remaining rate of concentration is greater than 5%
[moisture-proof fastness]
Gained is write down thing in the constant temperature and humidity cabinet of 30 ℃ of 80%RH, placed one hour, take out drying, the change in concentration before and after the determination test.
A: the remaining rate of concentration is less than 1%
B: the remaining rate of concentration is 2～4%
C: the remaining rate of concentration is greater than 5%
More than the result of the ink (sun blue-199) of result before and after compound 7 heating change and reference example sums up as shown in table 1 in the test.
Table 1
As mentioned above, the recording method with the present invention relates to can make ink become the non-solvent dissolution system by the dissolution with solvents system on recording medium.By dissolution characteristics is changed (reduction), cause the aggegation of tinting material own, can obtain good pattern fastness.On the other hand, for ink, there is no need in ink, to add macromolecule dispersing agent etc. as existing paint ink.It is the effect that the present invention can realize existing dye ink and paint ink both sides.
3.1. compound 2 ' synthetic
At first prepare 3,5-cyclohexadiene-1,20% ethyl acetate solution (25ml) of 2-glycol (compound 1 ') is as raw material, behind the solvent concentrating under reduced pressure, toward wherein adding acetone (30ml), 2,2-Propanal dimethyl acetal (69ml) and micro-tosic acid stirred 4 hours under the room temperature.The aqueous sodium hydroxide solution (30ml) of adding 10% and saturated aqueous common salt (30ml) stir; stopped reaction; with ether (3 * 30ml) extractions; (3 * 30ml) clean organic layer with saturated aqueous common salt; use anhydrous sodium sulfate drying then; concentrating under reduced pressure, 8.33g compound 2 ', i.e. the shielded compound of compound 1 ' hydroxyl.
3.2. compound 3 ' synthetic
Compound 2 ' (158mg) and dicyan acetylene (230nmg) are packed in the reaction vessel, add toluene (2.00ml), 90 ℃ were stirred 3 hours down.After reaction finished, the concentrating under reduced pressure reaction soln separated with column chromatography (20～30 volume %, ethyl acetate/hexane), and concentrated Rf is that 0.24 (20 volume %, ethyl acetate/hexane) and Rf are the component of 0.18 (20 volume %, ethyl acetate/hexane).With above-mentioned substance difference recrystallization, get 184mg compound 3.
mp：151.9-152.6℃
1H NMR (solvent: CDCl
3Unit: δ ppm7.87 (m, 2H), 7.71 (m, 1H), 7.59 (m, 2H), 6.16 (m, 2H), 4.81 (dd, J=5.6,2.4Hz, 1H), 4.33 (dd, J=6.8,2.9Hz, 1H), 4.19 (dd, J=6.8,2.9Hz, 1H), 4.04 (dd, J=5.6,1.5Hz, 1H), 3.70 (m, 1H), 3.48 (m, 1H) 1.28 (s, 3H), 1.22 (s, 3H)
IR(KBr)/cm
-1?2981w、1552s、1313s、1151s、1056s、727.0m、601.7m
3.3. compound 4 ' synthetic
Compound 3 (365mg) packed into carry out nitrogen in the reaction vessel and replace, be dissolved in anhydrous tetrahydro furan (5.00ml), reaction vessel is immersed in the ice bath.The butanol solution that adds propyl carbinol magnesium, 150 ℃ of following heated and stirred, metal complex is carried out in four times of cyclisation.Reaction finishes, and (3 * 20.0ml) extract with ethyl acetate in the back.Clean organic layer with saturated aqueous common salt, use anhydrous sodium sulfate drying then, concentrating under reduced pressure, separate with silica gel column chromatography (5 volume %, ethyl acetate/chloroform), concentrated Rf is 0.41 (20 volume %, ethyl acetate/hexane) and Rf be the component of 0.41 (5 volume %, ethyl acetate/chloroform).Behind the recrystallization 283mg compound 4 '.
mp?114.9-146.3℃
1H NMR (solvent: CDCl
3, unit: δ ppm) 8.58 (Br, 1H), 6.68 (d, J=2.4Hz, 1H), 6.50 (m, 2H), 4.56 (m, 1H) 4.34 (m, 2H), 4.32 (q, J=7.0Hz, 2H), 4.06 (m, 1H), 1.42 (s, 3H), 1.38 (t, J=7.0Hz, 3H), 1.3o (s, 3H)
IR(KBr)/cm
-1?3345s、2892w、1681s、1297m、1141s、1039s。
Replace carrying out nitrogen in compound 4 ' (289mg) the adding reaction vessels, be dissolved in THF (5.00ml).Add 1N hydrochloric acid (114mg), stirred l hour under the room temperature.After reaction finishes; use the sodium thiosulfate solution (50.0ml) of saturated aqueous common salt (50.0ml) and 1% to clean reaction soln (the original text statement is unclear) respectively; behind anhydrous sodium sulfate drying; concentrating under reduced pressure; refining with column chromatography, the shielded water soluble metal phthalocyanine compound 5 of the hydroxyl behind the recrystallization ' (yield is 39.8 weight %).
Ink of the present invention has good solvability, can carry out the high speed solid-liquid separation after being endowed recording medium, and prior art is difficult to take into account this two aspect, and the present invention can satisfy this two specific character simultaneously with high level.
The present invention can change the characteristic of compound, for example makes the dissolution with solvents system become not dissolution system of solvent after forming pattern, can significantly improve image fastness.
Claims (8)
1. the pattern formation method of an organic semiconductor film, it is characterized by, utilize solution that printing will contain bicyclic compound at least to be imparted to desirable position on the base material, part in the two ring skeletons is broken away from from described bicyclic compound, expand pi-conjugated system, described bicyclic compound is transformed into organic semiconductor material, and retro Di takes place in selected position on this base material thus, thereby desirable position forms organic semiconductor film on base material.
2. the pattern formation method of organic semiconductor film as claimed in claim 1 is characterized by, and described printing is the printing that utilizes ink-jetting style to carry out.
3. the pattern formation method of organic semiconductor film as claimed in claim 1 is characterized by, and describedly is printed as silk screen printing.
4. the pattern formation method of an organic semiconductor film, it is characterized by, to have following formula at least, (I) or likes, the bicyclic compound of structure (II) is imparted on the base material, utilize retro Di to make described bicyclic compound change organic semiconductor material into, thereby formation organic semiconductor film, described retro Di is that the part of two ring skeletons is broken away from from described bicyclic compound, expand pi-conjugated system, described bicyclic compound is transformed into the organic semi-conductor reaction
In formula (I) and the formula (II), R
1And R
2Expression contains at least a polar group or the alkyl in Sauerstoffatom, nitrogen-atoms and the sulphur atom respectively, and M is zinc, copper, magnesium, aluminium.
5. the pattern formation method of organic semiconductor film as claimed in claim 4 is characterized by, and described bicyclic compound has the structure shown in the following formula (III),
6. the pattern formation method of an organic semiconductor film, it is characterized by, this method has following steps at least: by making bicyclic compound generation retro Di, form the step of the organic semiconductor film of the compound formation of being represented by following formula (IV) or formula V on base material
7. the pattern formation method of an organic semiconductor film, it is characterized by, this method has following steps at least: utilize retro Di, form by anthracene, tetracene on base material, have the compound of porphyrin skeleton and have the step of any one organic semiconductor film that constitutes in the compound of tetraazatetradecane porphyrin skeleton.
8. the pattern formation method of an organic semiconductor film, it is characterized by, at least the solution that contains bicyclic compound is imparted on the base material, by heating and rayed, the part of two ring skeletons is broken away from from described bicyclic compound, expand pi-conjugated system, described bicyclic compound is transformed into organic semiconductor material, on this base material retro Di taking place, thereby forms organic semiconductor film thus on base material.
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