CN85107391A - Photosensitive composition - Google Patents

Abstract

The present invention has introduced a kind of photosensitive composition, and it is made up of electron-donating quality organic compound and photosensitizer.Wherein, photosensitizer can be from the aromatic series halogen, the period of element Table VI _AThe aromatic series  salt of family's element or period of element Table V _AChoose in the aromatic series  salt of family's element.If contain compound and these two kinds of materials or wherein a kind of of alkaline fine powder of oxyethylene group in the composition in addition, and the compound that contains alcoholic hydroxyl, then the said composition effect is better.This photosensitive composition can generate many kinds of colors, and good heat-resisting, moisture-proof and retention are arranged.

Description

Photosensitive composition

The invention relates to a kind of photosensitive composition, said composition develops the color under the irradiation of light.

Up to now, people have known the photosensitive composition that many kinds can develop the color under the irradiation of light.It is the reversible photosensitive composition of photochromism that a kind of composition is arranged, and the color that it manifests under rayed does not change because of light-struck stopping; Another kind of composition is the reversible photosensitive composition of photochromism, and the color that it manifests under rayed fades away along with stopping of illumination.

Before the irreversible photosensitive composition of a kind of photochromism, known it formed by electron-donating quality organic compound and photosensitizer.Reporting used electron-donating quality organic compound is those compounds of being introduced in the following document: " pulp and paper industry magazine " (day) be Vol (KAMIPAGIKYOHSHI), P411(1976), " color material association magazine " (day) be Vol54 (SHIKIZAI), P.355(1981), KINOHSEISHIKISO NO KAGAKU PP.189-210(1981), (Japanese CMC Co., Ltd. publish), and United States Patent (USP) 4,028,118; Reporting used photosensitizer has: organohalogen compounds (United States Patent (USP) 3,042,515,3,040,516,3,042,517,3,042,518 and 3,042,519 and Japanese publication NO373/65), two nitrine quinones (Japanese publication NO30885/70) and diazo salt (Japanese publication NO521/74).

The reversible photosensitive composition of a kind of photochromism in back, reported the used inorganic photosensitive composition that has, it is silver halide to be dispersed in the glass make, also have the organic photo composition, as: azobenzene, N-salicylidene aniline, spiro-pyrans, bi triphenyl imidazoles, thionine (thionine), Wei Aolao be * * (Viologen), husband's machine moral * * (furgide) etc. to the greatest extent.

But, above-mentioned two kinds of photosensitive compositions have following a certain shortcoming at least, as: because the gas that produces during rayed and often produce bubble, has strong odour nuisance, versicolor quality is of poor quality, because the ageing-resistant performance that heat-resisting and moisture-proof poor stability causes is bad, and storage life is than weak point or the like.

In addition, the reversible photosensitive composition of photochromism also has following a certain shortcoming at least, as: when rayed stops, color disappearance poor performance; During repeated use, fast light voltinism can be bad; Material is difficult to obtain, material difficulty or the like.Therefore, also there is not gratifying multi-usage photochromism photosensitive composition to occur so far with commercial value.

This photosensitive composition must have following character: the photosensitivity that can develop the color rapidly under rayed, the color category that can manifest is many, become the color density height, do not have disgusting smell, do not have gas during rayed and produce, good thermotolerance and moisture-proof are arranged, long shelf-life, rich color, material obtains easily, and material system system is easy or the like.

Therefore, the purpose of this invention is to provide novel photosensitive composition, improving the shortcoming that general photochromism photosensitive composition is had, and can satisfy its necessary performance.Another object of the present invention provides novel photosensitive composition, and the photosensitizer of these compositions when illumination improves.A further object of the invention provides novel photosensitive composition, and these compositions have can satisfy the necessary performance of the reversible photosensitive composition of photochromism.

The present invention adopts the photosensitive composition of following type to realize above-mentioned purpose.

Photosensitive composition (1) is made up of electron-donating quality organic compound and photosensitizer, and photosensitizer can be chosen from the aromatic series salt of the aromatic series salt of aromatic series halogen, periodic table of elements V la family element or periodic table of elements V a family element.

Photosensitive composition (2) is made up of electron-donating quality organic compound, photosensitizer and the compound that contains alcoholic hydroxyl.Wherein photosensitizer can be chosen from the fragrant salt of the aromatic series salt of aromatic series halogen, periodic table of elements V la family element or periodic table of elements V a family element.

Photosensitive composition (3) is by electron-donating quality organic compound, photosensitizer and contain the compound of ethylene oxide group and these two kinds of materials of alkaline fine powder or wherein a kind of institute form.Wherein photosensitizer can be chosen from the aromatic series salt of the aromatic series salt of aromatic series halogen, periodic table of elements V la family element or periodic table of elements V a family element.

By being intended to improve all research of defective general photosensitizer performance in the practical application, inventor's of the present invention discovery, can realize its purpose with following method: choose the aromatic series salt of aromatic series halogen, periodic table of elements V la family element or the aromatic series salt of periodic table of elements V a family element and make photosensitizer, and be used with electron-donating quality organic compound.

The inventor finds: when the aromatic series salt of the aromatic series salt of aromatic series halogen, periodic table of elements V la family element or periodic table of elements V a family element and electron-donating quality organic compound combine, above-mentioned salt discharges quality components such as Br φ nstead acid, Lewis acid rapidly, thereby make the electron-donating quality organic compound quality immediately, even at this moment also can not produce bubble with rayed.The inventor finds further that also above-mentioned salt is a kind of extremely good photosensitizer.In photosensitizer, above-mentioned salt itself does not have disgusting smell, add that it has good thermotolerance and moisture resistance, thereby its ageing-resistant performance is good, long shelf-life.Therefore, the inventor thinks that the composition that above-mentioned photosensitizer combines with electron-donating quality organic compound is good novel photosensitive composition, the existing shortcoming of various photosensitive compositions before this photosensitive composition has been eliminated.This point is a most important characteristic of the present invention.

Secondly, contain the compound of alcoholic hydroxyl such as the photosensitive composition of above-mentioned photosensitive composition (1) coexistence formation and can improve colour sensitivity, and can not reduce the performance of photosensitive composition (1).This point is this present invention's a key character.

In addition, the compound and these two kinds of materials of alkaline fine powder or the wherein a kind of photosensitive composition that coexistence forms as photosensitive composition (1) that contain the ethylene oxide group, its colour former develops the color when having illumination, the performance that color disappeared when illumination stopped, i.e. so-called photochromic (photochromism) can not reduce the performance of photosensitive composition (1) simultaneously.This point also is a key character of the present invention.

The compound photosensitive composition that coexistence forms as a sense composition (3) that contains alcoholic hydroxyl can also improve colour sensitivity, and can not reduce the performance of photosensitive composition (3).In addition, its colour former develops the color when having illumination, the performance that color disappeared when illumination stopped, promptly so-called photic quality.This point is another key character of the present invention.

What list below is the novel photosensitive composition of several combinations: (1) electron-donating quality organic compound and photosensitizer.Wherein, photosensitizer is from the aromatic series halogen, chooses in the aromatic series salt of the aromatic series salt of periodic table of elements V la family element or periodic table of elements V a family element; (2) electron-donating quality organic compound, photosensitizer and the compound that contains alcoholic hydroxyl.Wherein, photosensitizer is chosen in the aromatic series salt of the aromatic series salt of periodic table of elements V la family element or periodic table of elements V a family element from the aromatic series halogen; (3) electron-donating quality organic compound, photosensitizer and compound and these two kinds of materials or wherein a kind of of alkaline fine powder of containing oxyethylene group.Photosensitizer in the composition is chosen in the aromatic series salt of the aromatic series salt of periodic table of elements V la family element or periodic table of elements V a family element from the aromatic series halogen.(4) electron-donating quality organic compound, photosensitizer contains compound and these the two kinds of materials of alkaline fine powder or the compound wherein a kind of and that contain alcoholic hydroxyl of ethylene oxide.Photosensitizer in the composition is chosen in the aromatic series salt of the aromatic series salt of periodic table of elements V la family element or periodic table of elements V a family element from the aromatic series halogen.Though the combinations thereof as photosensitive composition has good performance, show that the reason of the performance that these are good can only be described below roughly:

When illumination was mapped on the photosensitive composition, photosensitizer was quality components such as the acid of emitting Br φ nstead, Lewis acid, and the colour developing of sensitization electron-donating quality organic compound, and at this moment electron-donating quality organic compound is by these quality components colour developings.

We find: when compound that contains alcoholic hydroxyl and photosensitive composition coexistence, can demonstrate good performance, promptly electron-donating quality organic compound can be in light-struck moment colour developing.Perhaps, this is because the compound effects that photosensitizer contains alcoholic hydroxyl generates quality components such as Br φ nstead acid, Lewis acid rapidly, becomes and makes electron-donating quality organic compound supply with quality component electronics, and develop the color in moment.

In the photosensitive composition that the compound that contains oxyethylene group and these two kinds of materials of alkaline fine powder or wherein a kind of and photosensitive composition (1) or (2) coexistence form, quality component colour developings such as the Br φ nstead acid that electron-donating quality organic compound is discharged when the rayed by photosensitizer, Lewis acid.But if rayed stops, discharging quality components such as Br φ stead acid, Lewis acid from photosensitizer also stops, meanwhile contain the compound of oxyethylene group and these two kinds of materials of alkaline fine powder or wherein a kind of the beginning absorbs: quality components such as Br φ nstead acid, Lewis acid, so that electron-donating quality organic compound is by colour killing.That is to say, the electron-donating quality organic compound that has developed the color is accepted electronics, subsequently, contain compound and these two kinds of materials or wherein a kind of of alkaline fine powder of oxyethylene group, absorb quality components such as all Br φ nstead acid that from photosensitizer, discharged, Lewis acid.According to the present invention, comprise compound and these two kinds of materials or wherein a kind of of alkaline fine powder of containing oxyethylene group in the photosensitive composition, can infer electron-donating quality organic compound is along with whether electronics is supplied with and accepted to the existence of light, color is just appearing and subsiding thereupon also.Here it is, and this photosensitive composition has the reason of so-called photochromism.

Electron-donating quality organic compound used herein normally colourless or light colour developing, and have the quality component and: effect such as Br φ nstead acid, Lewis acid is the character that develops the color of power supply down.Employed electron-donating quality organic compound is with diphenyl-methane phthalide (triphenylmethanephthalides), fluorane (fluorans), phenothiazine (phenothiazines), indyl phenolphthalein (indolylphthalides), platinum amine (leucoauramines), rhodamine lactams (rhodamine lactams), rhodamine lactone (rhodamine lactones), dihydroindole (indolines), triphenyl methane, azepine phenolphthalein (azaphthalides), chomene indoles (chromenoindols), triazeness etc. are good, triphenyl methane phthalide wherein, fluorane, the indyl phthalide, platinum amine, the rhodamine lactams, triphenyl methane, azepine phthalide etc. are better.Employed electron-donating quality organic compound can be the potpourri of two or more compounds, and they can be compounds of the same race or not of the same race.Object lesson is as follows:

Crystal violet lactams (crystal violate lactone), malachite green lactone (malachite green lactone), rice Chi Shi hydrol (Micher ' s hydrol), 3-lignocaine-7-methyl fluorane, 3-lignocaine-7-(neighbour-chlorphenyl)-amino fluorane, 3-N-ethyl-N-is right-toluidino-7-methyl-N-phenyl amino fluorane, 3-pyrrolidinyl-6-methyl-7-anilino-fluorane, N-(2, the 3-dichlorophenyl) platinum amine, N-2,4,5-trichlorophenyl platinum amine, the N-benzoyl auramine, N-phenyl auramine, the rhodamine B lactams, the rhodamine B lactone, 2-(phenyl imine base ethanetetrayl)-3,3 '-the dimethyl indoline, the colourless serge blue of right-nitrobenzyl, the colourless serge blue of benzoyl, 3, the 7-22(dimethylamino)-10-benzoyl phenothiazine, 3,7-22 dimethylamino-10-(4 '-aminobenzoyl) phenothiazine, 3,7-22 dimethylamino-10-(4 '-pyrido benzoyl) phenothiazine), 3,7-22 dimethylamino-10-(4 '-22(4 ", 4 ' " dimethylamino phenyl) the methylamino benzoyl) phenothiazine etc.

The used photosensitizer of the present invention is the compound of choosing from the aromatic series salt of the aromatic series salt of aromatic series halogen, periodic table of elements V la family element or periodic table of elements V a family element.This compound is colourless or the light colour developing, and can discharge under rayed as quality components such as Br φ nstead acid, Lewis acid, thereby makes the electron-donating quality organic compound colour developing.

Photosensitizer compounds is with aromatic series halogen (salt of the halogen-containing complex ion of aromatic series halogen ion and Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As); The salt of the aromatic series ion of periodic table of elements V la family element (O, S, Se and Fe) and the halogen-containing complex ion of Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As; The salt of the aromatic series ion of periodic table of elements V a family element (N, P., As, Sb and Bi) and the halogen-containing complex ion of Sb, Fe, Sn, Bi, Al, Ga, Zn, Ti, Zr, B, P and As, and the salt of aromatic series ion and perchloric acid is good.

The photosensitizer compounds of more being recommended is aromatic series salt compounded of iodine (salt of the halogen-containing complex ion of aromatic series metal iodide ions and Sb, B, P and As); The salt of the aromatic series ion of periodic table of elements V la family's element (S) and the halogen-containing complex ion of Sb, B, P and As; The salt of the aromatic series salt ion of periodic table of elements V a family element (N and P) and the halogen-containing complex ion of Sb, B, P and As, and the salt of aromatic series ion and perchloric acid.

The photosensitizer compounds of being recommended most is aromatic series iodide ion and BF ₄Salt; Aromatic series iodide ion and PF ₆Salt; Aromatic matte ion and BF ₄Salt, and aromatic matte ion and PF ₆Salt

Details about above-claimed cpd is introduced in following document to some extent:

J.Org.Chem Vol35（8），P2532（1970）

Macromolecules Vol 10（6），P1307（1977）

J.Org.Chem.Vol 43（15），P3055（1978）

J.Radiat Curing Vol 5（1），P2（1978）

J.Radiat Curing Vol 6，P22（1979）

J.Polym.Sci，Polym.Chem.Ed，Vol17，PP977，1047（1979）

J.Polym，Sci，Polym.Chem.Ed.，Vol22，P1789（1984）

Adv.Polymer Sci.，Vol62，P.l（1984）

" material technology " (day) ZAIRYOH GIJUTSU) Vol.2(10), P553(1984)

Provide the object lesson of photosensitizer below, but photosensitizer of the present invention is not limited in following compounds.

The aromatic series halogen:

The compound that contains alcoholic hydroxyl among the present invention is colourless or the solid or the liquid of light colour developing, and has when coexisting with electron-donating quality organic compound, improves the performance of illumination color speed.The used compound that contains alcoholic hydroxyl mainly contains the fatty alcohol of carbon number more than 6 or 6, and its boiling point is equal to or higher than 150 ℃; The polyvalent alcohol of carbon number more than 6 or 6, its boiling point are equal to or higher than 150 ℃; The aromatic alcohols of carbon number more than 7 or 7, its boiling point are equal to or higher than 150 ℃; And molecular weight is 10,000-300,000 macromolecular alcohol.

The alcoholic hydroxyl compound of being recommended that contains is the fatty alcohol of carbon number more than 9 or 9, and its boiling point is equal to or higher than 200 ℃; The aromatic alcohol of carbon number more than 7 or 7, its boiling point are equal to or higher than 200 ℃; The polyvalent alcohol of carbon number more than 6 or 6, its boiling point are equal to or higher than 200 ℃; And molecular weight is 10,000-300,000 macromolecular alcohol.The object lesson of this compound is: fatty alcohol, as: hexanol, octanol, nonyl alcohol, alcohol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, docosyl alcohol, melissyl alcohol, oleyl alcohol, cyclohexanol, cyclopentanol etc.; Aromatic alcohols is as phenmethylol, beta-phenyl ethanol, styron, triphenylcarbinol etc.; Polyvalent alcohol, as ethylene glycol, diglycol, the sweet ether of ethylene glycol, ethyleneglycol monophenylether, glycol monomethyl methyl phenyl ethers anisole, propylene glycol, propylene glycol monobutyl ether, propylene glycol mono acrylic ester, propylene glycol monophenyl ether, butylene glycol, hexanediol, 2-ethyl-1,3-hexanediol, glycerine, glycerine monolaurate, glycerine monopalmitate, glycerine single-hard ester acid ester, glycerine dilaurate, pentaerythrite, mannitol, sorbitan, sorbitan single lauryl alcohol ester, sorbitan list oleyl alcohol ester, the hard ester acid esters of sorbitan sesquialter etc.; And macromolecular alcohol, as: polyvinyl acetal, polyvinyl butyral, acetyl cellulose, hydroxy ethyl fiber, hydroxypropyl cellulose, cellaburate ester, cellulose acetate phthalate, methylcellulose, ethyl cellulose, polysiloxane-many methyl alcohol etc.

The compound that contains oxyethylene group that the present invention is used is colourless or the liquid or solid of light colour developing, can be miscible although wish to contain the compound of oxyethylene group with power supply pneumatolytic look organic compound and photosensitizer, can not be miscible also can use.This compound is to contain three or three above oxyethylene groups, and molecular weight is good more than or equal to 100 compound; To contain 6 or 6 above oxyethylene groups, molecular weight is better more than or equal to 190 compound.The object lesson of above-claimed cpd has: diglycol, diethylene glycol monoethyl ether, diethyl carbitol, diethylene glycol monobutyl ether, the diglycol monotertiary phenylate, the diglycol monotertiary methyl phenyl ethers anisole, triethylene glycol, the triethylene glycol monobutyl ether, the triethylene glycol monophenyl ether, the triethylene glycol dioctyl ether, tetraethylene glycol, tetraethylene glycol list ether, tetraethylene glycol monobutyl ether acetate ester, polyglycol, ethylene oxide-propylene oxide block copolymer, poly-alcoxyl ethane Span-20, the polyethylene oxide sorbitan monopalmitate, polyethylene oxide sorbitan single-hard ester acid ester, polyethylene oxide sorbitan three hard ester acid esters, the polyethylene oxide sorbitan monooleate, the polyethylene oxide sorbitan trioleate, polyethylene oxide bay ether, the polyethylene oxide cetyl ether, polyethylene oxide octadecyl ether, polyethylene oxide oil ether, the polyethylene oxide octylphenol ether, polyethylene oxide nonyl phenolic ether, polyethyleneglycol diacrylate.

The compound that contains alcoholic hydroxyl and oxyethylene group in same molecule has these two kinds of performances of colour killing of improving color speed and illumination colour developing.

Used alkaline fine powder is colourless or light colour developing among the present invention, and not miscible with electron-donating quality organic compound and photosensitizer, and its mean grain size is about 0.01 μ m-100 μ m, is good with 0.1 μ m-10 μ m, and PH is 8-13.The meaning of " not miscible with electron-donating quality organic compound or photosensitizer " the words is that at room temperature its solubleness is less than or equal to 1%.

Alkaline fine powder commonly used has: alkali-metal oxyhydroxide such as lithium, sodium, potassium, earth alkali metal and carbonate thereof such as magnesium, calcium, barium.Also just like: alkaline fine powder-shaped silica, alkalescence are taken off alkaline process fine powders such as covering soil, alkaline talcum powder, alkaline lead sulfate, basic lead carbonate and also can be used.

Electron-donating quality organic compound, the compound that contains hydroxyl formula hydroxyl, the compound that contains oxyethylene group and alkaline fine powder can need according to the document of introducing previously synthetic with commercially available industrial goods, photosensitizer then owing to be difficult to obtain (although also being commercially available sometimes).

The weight ratio of photosensitizer and electron-donating quality organic compound for 0.01-100 part than 1 part, be good with 0.1-10 part than 1 part, 0.5-10 part is better than 1 part.

The compound that contains oxyethylene group and the weight ratio of electron-donating quality organic compound for 0.012-100 part than 1 part, be good with 0.1-10 part than 1 part, 0.5-5 part is better than 1 part.

The weight ratio of alkalescence fine powder and the coloured organic compound of electron-donating quality be 0.01-100 than 1 part, be good with 0.1-100 part than 1 part, 0.1-10 part is better than 1 part.

The compound that contains alcoholic hydroxyl and the weight ratio of electron-donating quality organic compound for 0.01-200 part than 1 part, be good with 0.1-100 part than 1 part, 0.1-20 part is better than 1 part.

Photosensitive composition of the present invention can just use under the initial state at it, also can use under other state, as their coatings, Yin Shua Huo Pinch are combined on certain carrier material.At length say, photosensitive composition of the present invention can follow these steps to prepare the back and use: its base stock and necessary additional ingredients are placed suitable solvent, in in the temperature range of room temperature to 100 ℃, with stirrer, decollator etc. with its dissolving or dispersion, thereby obtain photosensitive composition solution; Solution is placed a suitable containers, with printing machine or be coated with write device etc. with the solution printing or be coated with and write on the carrier material, perhaps with the solution dip-coating on carrier material.Photosensitive composition of the present invention can also use through the following step configuration back: Pinch Xia the heating and melting closes with sensitization base stock and other necessary component, cools off then and puts room temperature.

Photosensitive composition of the present invention can add various interpolation components according to its different purposes.As adding bonding agent (as: natural resin, synthetic resin etc.) as required, improve the sensitizer of colour sensitivity, Photoresist (as: titanium dioxide, alumina powder etc.), thickening agent (as: silica powder etc.), PH correctives (as: acid, alkali etc.), tone correctives (as: dyestuff, pigment etc.), plastifier, various stabilizing agents etc.

Above-mentioned photosensitive composition (1), (2), (3) and (4) can obtain like this: with the dissolving of its component or decompose in suitable solvent, and add additive as required simultaneously, boil off solvent then.

The photosensitive composition that obtains with said method can be at 400nm or is more developed the color under short wavelength's the UV-irradiation, especially can more effectively develop the color under the UV-irradiation of 250-350nm wavelength.Sunlight, mercury lamp, black lamp, xenon lamp, ultraviolet laser etc. are suitable as light source.Said composition can make its spectral sensitization with suitable sensitizer, as following dyestuff: acridine orange (C.I.46005), acridine yellow (C.I.46025), phosphine R(C.I.46045), benzoflavine (C.I.46065), plucked instrument pottery flavine T(C.I.49005) etc.; Aromaticity polynuclear compounds (perylene, anthracene, coronene, pyrene, aphthacene etc.), and ketone compounds (thioxanthone, chloro thioxanthone), benzophenone, 9-Fluorenone, anthrone etc.), thus make photosensitive composition can 400nm or more long wavelength's visible light (sunlight, tungsten lamp light) irradiation develop the color down.Even after long preservation was more than 1 year, its performance did not have reduction yet).

As mentioned above, photosensitive composition of the present invention can overcome all shortcomings of general photosensitive composition, it can print, coating or dip-coating on paper, plastic film, metal forming, various fiber, glass, pottery etc., also it can be clipped in and mix between two carriers or with carrier materials such as plastics, waxes; In addition, it can also be made into the ink shape, as the ink or the pigment of photosensitivity.Therefore, photosensitive composition of the present invention can be widely used in various industrial materials, recording materials, display medium, ornament materials, daily necessities, clothes, writing material, toy etc.

To introduce the present invention with example below, but the present invention is not only limited to these example ranges." part " word in the routine example is meant parts by weight down.

Example 1

NBP-1(Yamamoto chemical company (Yamamoto Kagaku Co.) produces

The trade name of electron-donating quality colored compound) 0.25 part

Tetrafluoride boron triphenyl acyl methyl microcosmic salt

(light sensation agent) 0.5 part

(the Shinnittetsu Kagaku of chemical company of MS-300(Nippon Steel

Co.) styrene-methacrylic resin of Sheng Chaning) 1.5 parts

6 parts of toluene

10 parts of butanone

1.5 parts of methyl alcohol

After above-mentioned component stirring and dissolving, be applied on the fine quality paper, coating weight is every square metre of 4-5 gram solids, so just can make the variable color paper that closes photosensitive composition, when variable color paper under the black lamp exposure 30 seconds after, exposed portion will be become blue look by original white.

Low, the odorlessness of this variable color, heat-resisting, heatproof and shelf characteric are all fine.In addition, can not produce gas or air bubble during exposure.This low colour sensitivity energy and color density are all well and good.

Example 2

RLA(hodogaya chemical company (Hodogaya Kagaku CO.)

The trade name of the electron-donating quality organic compound of producing) 0.25 part

0.75 part of tetrafluoride boron diphenyl iodnium (photosensitizer)

15 parts of butanone

5 parts of toluene

After above component stirring and dissolving, dip-coating is on fine quality paper, and the dip-coating amount is every square metre of 1-2 gram solids, so just can make the variable color paper that contains photosensitive composition.When this variable color paper under the sun exposure 30 seconds after, variable color paper becomes redness by original white.

This variable color paper odorlessness, heat-resisting, moisture-proof, retention is also good.In addition, do not produce gas or air bubble during exposure, the colour sensitivity energy and the color density of this variable color paper are all well and good.

Example 3

S-205(Yamamoto (the Yamamoto of chemical industrial company

Kagaku Kohgyoh CO.) electron-donating quality of Sheng Chaning is organic

The trade name of compound) 5 part

Two-(4-(diphenyl sulphur) phenyl)

10 parts of sulfide-pairs-hexafluorophosphates (photosensitizer)

1 part of triphenyl phosphate

30 parts of toluene

50 parts of butanone

After above-mentioned component stirring and dissolving, this ink is put in the fibre-tip pen, so just obtain a kind of photosensitive lettering pen.With this pen on the paper or the writing of writing on the plastic film blur.After the paper of the word write or plastic film were placed 20 seconds of exposing sunlight under, writing became black.This shows that this ink can be used as secret ink.

Tasteless with the writing that this ink is write as, heat-resisting, moisture-proof, retention is good.In addition, during exposure, do not produce gas or air bubble, and the colour sensitivity of this writing and color density are all good.

Example 4

TH-107(hodogaya chemical (the Hodogaya of industrial group

Kagaku Kohgyoh CO.) electron-donating quality of Sheng Chaning is organic

The trade name of compound) 0.25 part

0.5 part of triphenyl sulphur hexafluorophosphate (photosensitizer)

S-Lec BM-5(system iron chemical industrial company

(Sekisui Kagaku CO.) produces closes alcoholic hydroxyl

The trade name of the butyral resin of compound) 1.5 part

13 parts of butanone

3 parts of toluene

4 parts of methyl alcohol

After above-mentioned all compound stirring and dissolving, it is coated on the mylar, coating weight is every square metre 4 gram solids.Like this, just, make the film that contains the sensitization combination ingredient.After this film exposed for 30 seconds in the sun, exposed portion became black.

This film odorlessness, heat-resisting, moisture-proof, storing performance is good.In addition, do not produce gas or air bubble when the exposure.The colour sensitivity energy and the color density of this film are good.

Example 5

NC-BK(hodogaya chemical (the Hodogaya of industrial group

Kagaku CO.) the electron-donating quality organic compound of Sheng Chaning

5 parts of the trade names of thing

Structure as shown in the formula 10 parts of compounds (photosensitizer)

S-Lec BX-L(system iron chemical industrial company

What (Sekisui Kagaku CO.) produced contains

14 parts of the trade names of the butyral resin of alcoholic hydroxyl compound

71 parts of butanone

Above-mentioned all components are stirred, after dissolving or the dispersion, be coated on mylar or the good quality paper, coating weight is every square metre of 2-4 gram solids, has so just made the diaphragm or the paper that have photosensitive composition.This diaphragm or paper were exposed for 20 seconds in the sun, and exposed portion becomes black.

This diaphragm odorlessness, and heat-resisting, heatproof, retention is good.Do not produce gas or air bubble when exposing in addition, the photosensitive composition diaphragm has good colour sensitivity and color density.

Example 6

The Pergascript Red I-6B(vapour Ba Jiaji (Chiba of company

Geigy A.G.Co.) electron-donating quality of Sheng Chaning organises

The trade name of compound) 5 part

Two (4-(diphenyl sulphur) phenyl) thioether-two-hexafluoro

8 parts of arsenates

Ethyl cellulose, N-4(U.S. Hercules company produces

The trade name of the celluosic resin that contains the alcoholic hydroxyl compound) 5 parts

40 parts of butanone

The diaphragm that has photosensitive composition with the method preparation identical with example 1.Diaphragm was exposed for 20 seconds under daylight, and its exposed portion becomes redness.

This diaphragm odorlessness, and heat-resisting, moisture-proof, retention is good.In addition, do not produce gas or air bubble when exposure, the diaphragm of photosensitive composition has good colour sensitivity and color density like this.

Example 7

OR-55(hillside plot industrial chemistry (the Yamada Kohgyoh of company

Kagaku Co.) the electron-donating quality organic compound of Sheng Chaning

The trade name of thing) 5 part

Two (4-(diphenyl sulphur) phenyl) thioether-two-

8 parts of hexafluoro antimonates (photosensitizer)

1 part of beta-phenyl ethanol (compound that contains alcoholic hydroxyl)

(the Shin-of chemical industrial company of MS-300(Nippon Steel

Nittetsu Kagaku Co.) produces

Styrene-methacrylic acid copolymer resin

Trade name) 6 part

50 parts of butanone

20 parts of toluene

The diaphragm for preparing photosensitive composition by the method for example 1.When diaphragm exposed for 20 seconds under daylight, its exposed portion becomes orange.

This diaphragm odorlessness, and have good heat-resisting, moisture-proof, and retention.In addition, do not produce gas or air bubble in the light light time, the photosensitive composition diaphragm has good colour sensitivity and color density.

Example 8

The OR-55(hillside plot industrial chemistry (Yamada of company

Kohgyoh Kagaku Co.) power supply of Sheng Chaning

The trade name of quality organic compound) 0.25 part

0.5 part of triphenyl sulphur hexafluorophosphate (photosensitizer)

S-Lec BX-L(system iron chemical company

(Sekisui Kagaku Co.) produces

The commodity that contain the butyral resin of alcoholic hydroxyl compound

Title) 1.5 part

15 parts of butanone

3 parts of methyl alcohol

After all above-mentioned institute part dissolvings under agitation, be coated on the mylar, coating weight is every square metre of 4-5 gram solids, just makes the mylar of band photosensitive composition.Coated with adhesive then is made for label at the back side of film.This label is bonded on the container, above writing appliance, the toy etc., exposes under daylight after 20 seconds, label promptly becomes orange.

This label odorlessness, and have good heat-resisting, moisture-proof and retention.In addition, do not produce gas or air bubble during exposure.Contain this film of photosensitive composition, have good colour sensitivity and color density.

Example 9

The NBP-1(Yamamoto chemosynthesis worker (Yamarnoto of department

Kagaku Gohsei Co.) electron-donating quality of Sheng Chaning has

The trade name of organic compounds) 5 part

Structure as shown in the formula 10 parts of compounds (photosensitizer)

S-Lec BM-S(system iron chemical industrial company

(Sekisui Kagaku Co.) produces contains pure formula

The butyral resin trade name of formula hydroxyl compound) 6 part

30 parts of butanone

20 parts of toluene

Diaphragm with the method preparation band photosensitive composition identical with example 1.Diaphragm exposed under daylight after 20 seconds, and its exposed portion becomes blue look.

This diaphragm odorlessness, and have good heat-resisting, moisture-proof and retention.In addition, do not produce gas or air bubble when exposure, the film of this band photosensitive composition has good colour sensitivity and color density.

Example 10

Pergascript Rcd I-68(vapour Ba Jiaji

A.G company (Chiba Geigy A.G CO.)

The electron-donating quality organic compound trade name of producing) 5 part

8 parts of the compounds that structure is following (photosensitizer)

Ethyl cellulose, N-4(U.S. Ltercules

The cellulose tree that contains the alcoholic hydroxyl compound that company produces

The fat trade name) 5 part

40 parts of butanone

Diaphragm with the method preparation band photosensitive composition identical with example 1.Diaphragm is after 20 seconds of exposing under the daylight, and its exposed portion becomes redness.

This diaphragm odorlessness, and have good heat-resisting, moisture-proof and retention.In addition, do not produce gas or air bubble when exposure, the photosensitive composition film has good colour sensitivity and color density.

Example 11

The OR-55(hillside plot industrial chemistry (Yamada of company

Kohgyoh Kagaku Co.) power supply of Sheng Chaning

The trade name of quality organic compound) 5 part

8 parts of the compounds that structure is following (photosensitizer)

Chemical company of M-300(Nippon Steel

（Shinnittetsu Kagaku Co.）

The styrene of producing-methacrylic acid copolymer tree

The trade name of fat) 6 part

50 parts of butanone

20 parts of toluene

Be with the diaphragm of photosensitive composition by example 1 identical method preparation.Diaphragm exposed under daylight after 20 seconds, and its exposed portion becomes orange.

This diaphragm odorlessness, and have good heat-resisting, moisture-proof and retention.In addition, this diaphragm does not produce gas or air bubble when exposure.Have good colour sensitivity energy and color density.

Example 12

New day Cao chemical industrial company of PSD-G(

(Shinnisso Kako Co.) gives birth to

The commodity of the electron-donating quality organic compound that produces

Title) 0.25 part

0.5 part of triphenyl sulphur hexafluorophosphate (photosensitizer)

1 part of precipitated calcium carbonate fine powder (alkaline fine powder)

Chemical company of MS-300(Nippon Steel

（Shinnittetsu Kagaku

Co.) the phenyl ethylene-methacrylic acid copolymer of Sheng Chaning

The trade name of resin) 1.5 part

8 parts of toluene

12 parts of butanone

3 parts of methyl alcohol

After above-mentioned all components are under agitation dissolved or disperseing, coat on the polyester film base, coating weight is every square metre of 4-5 gram solids.Just make the white diaphragm of photochromic properties.Coat bonding agent at the diaphragm back side, just make label.This label is bonded at writing appliance, above the toy etc., exposes more than 20 seconds under daylight, and label becomes green.The label of light of will exposing to the sun after illumination stops at room temperature to be placed 24 hours, and label reverts to original white.

This label has good heat-resisting, heatproof and retention.

Example 13

NBP-1(Yamamoto chemical company

（Yamamoto Kagaku Co.）

The electron-donating quality organic compound of producing

Trade name) 0.25 part

Triphenyl acyl methyl phosphorus tetrafluoroborate

(photosensitizer) 0.5 part

1 part of acid sodium carbonate fine powder (alkaline fine powder)

7 parts of toluene

10 parts of butanone

3 parts of methyl alcohol

After above-mentioned all components are under agitation dissolved or disperseing, coat on the good quality paper, coating weight is every square metre of 5-8 gram solids, follow to the blank sheet of paper that photochromic properties is arranged, after 30 seconds of exposing under the black lamp, its exposed portion just becomes blue look, after illumination stops with paper, the paper of light of will exposing to the sun was at room temperature placed 24 hours, just recovered original white.Even after colour developing and the repetition 20 times of fading, its photochromic performance does not descend substantially yet.

This variable color paper has good heat-resisting, heatproof and retention.

Example 14

R-DCF(hodogaya chemical company

（Hodogaya Kagaku Co.）

0.25 part of the trade name of the electron-donating quality organic compound of producing

0.5 part of triphenyl benzoyl methyl tetrafluoroborate (photosensitizer)

1.5 parts of precipitated calcium carbonate fine powders (alkaline fine powder)

S-Lec BM-5(system iron chemistry

(the Sikisui kagaku of industrial group

Co.) butyral that contains the alcoholic hydroxyl compound of Sheng Chaning

The resin trade name) 1.5 part

15 parts of butanone

5 parts of toluene

5 parts of methyl alcohol

After above-mentioned all components are under agitation dissolved or disperseing, be coated on the polyester film base, coating weight is every square metre of 5g solids, obtains the white diaphragm of relevant photosensitive colour-changing performance.Diaphragm exposed for 30 seconds under daylight, and exposed portion becomes redness.After illumination stopped, after the diaphragm of the light that will expose to the sun was at room temperature placed 24 hours, diaphragm just reverted to original white.Even after colour developing and the repetition 20 times of fading, the also basic no change of its performance.

This diaphragm has good heat-resisting, moisture-proof and retention.

Example 15

Red-40P(Yamamoto chemical company

（Yamamoto kagaku Co.）

The electron-donating quality organic compound of producing

0.25 part of trade name

Diphenyl-4-thiophene oxy phenyl sulphur four

0.5 part of borofluoride (photosensitizer)

2.5 parts of lime carbonate fine powders

S-Lec BM-5(system iron chemistry

(the Sekisui kagaku of industrial group

That Co.) produces contains the alcoholic hydroxyl compound

The butyral resin trade name) 2 part

15 parts of butanone

5 parts of toluene

5 parts of methyl alcohol

After above-mentioned all components are under agitation dissolved or disperseing, be coated on the polyester film base, coating weight is every square metre of 5-6 gram solids, obtains the white diaphragm of photochromic properties.Diaphragm is after 30 seconds of exposing under the chemical light, and its exposed portion becomes redness.After illumination stopped, the diaphragm of the light that exposed to the sun was at room temperature placed 24 hours, and diaphragm reverts to original white.Even after colour developing and the repetition 20 times of fading, the basic no change of its photosensitive property.

This diaphragm has good heat-resisting, heatproof and retention.

Example 16

OR-55(Yamamoto chemical company

（Yamamoto Kagaku Co.）

The electron-donating quality organic compound of producing

Trade name) 0.25 part

0.5 part of triphenyl sulphur tetrafluoroborate (photosensitizer)

1.5 parts of magnesium carbonate fine powders (alkaline fine powder)

0.25 part of triphenyl phosphate

S-Lec BM-5(system iron chemistry

(the Sekisui Kagaku of industrial group

That Co.) produces contains the alcoholic hydroxyl compound

2 parts of butyral resin trade names

2 parts of butanone

2 parts of toluene

2 parts of methyl alcohol

After above-mentioned all components are under agitation dissolved or disperseing, be imprinted on the fine quality paper, then obtain the blank sheet of paper of photochromic properties with the method for serigraphy.Paper was shone under daylight after 30 seconds, and just variable color is orange at the printing position.After illumination stopped, the paper of the light that will expose to the sun was after room temperature is placed 24 hours, and paper just reverts to original white.Even the colour developing and the repetition 20 times of fading, its performance also remains unchanged substantially.

This variable color paper has good heat-resisting, moisture-proof and retention.

Example 17

New day Cao's chemical industry of PSD-170(

（Shinnissco Kako Co.）

The merchant of the electron-donating quality organic compound of producing

The product title) 0.25 part

0.5 part of diphenyl iodine tetrafluoroborate (photosensitizer)

2.5 parts of precipitated calcium carbonate fine powders (alkaline fine powder)

S-Lec BX-L system iron chemical industry

Company (Sekisui Kagaku Co.)

The butyral tree that contains the alcoholic hydroxyl compound that produces

The fat trade name) 2 part

20 parts of butanone

4 parts of toluene

5 parts of methyl alcohol

After above all compounds are under agitation dissolved or disperseing, be printed on the fine quality paper, obtain having the blank sheet of paper of photochromic properties with toppan printing.After it was placed under the sunlight 30 seconds of exposure, the printing position became black.After illumination stops, this paper was placed on room temperature following 24 hours.This paper reverts to original white again.Through developing the color and fading after 20 times, its performance remains unchanged substantially.

This variable color paper heat-resisting, heatproof and retention are all fine.

Example 18

NBP-1(Yamamoto chemical industrial company

（Yamamoto Kagaku Co.）

The electron-donating quality organic compound of producing

Trade name) 0.25 part

Triphenyl acyl methyl phosphorus tetrafluoroborate

(photosensitizer) 0.5 part

Newpol 50HB-2000

(Sanyo changes into the (Sanyo of company

Kasei Kagaku Co.) produces

Contain the poly-(oxidation of ethylene oxide based compound

The oxidation of ethylene propylene) commodity of glycol monoether

Title) 0.25 part

7 parts of toluene

10 parts of butanone

3 parts of methyl alcohol

After above all components are under agitation dissolved or being uniformly dispersed, be coated on the fine quality paper, coating weight is every square metre of 2-3 gram solids.Make blank sheet of paper with photochromic properties.When this paper under the black lamp exposure 30 seconds after, paper becomes blue look.Stop illumination, this paper is at room temperature deposited 24 hours after, paper reverts to original white again.Carry out after 20 times through developing the color and fading, its photochromic performance remains unchanged substantially.

That this variable color paper has is heat-resisting, heatproof and the good feature of storage.

Example 19

New day Cao's chemical industry of PSD-HR(

(the Shinnisso Kako of company

Co.) the electron-donating quality organic compound of Sheng Chaning

The trade name of thing) 0.25 part

0.75 part of triphenyl sulphur hexafluorophosphate (photosensitizer)

Long king-the Atlas of Tween 80(

Company (Kao-Atlas Co.) produces

The polyoxyethylene sorb that contains oxyethylene group

The trade name of sugar alcohol acid anhydride monoleate) 0.5 part

Ethyl cellulose, the N-4(U.S.

Hercules company produces contains alcoholic hydroxyl

The cellulose ester trade name of base) 1.5 part

10 parts of butanone

With above-mentioned all compounds stir dissolve down or be uniformly dispersed after, be applied on the polyester film base, coating weight is that every square half 5-8 restrains solids, makes the white polyester diaphragm with photochromic properties.Place this diaphragm under the sunshine or chemical light down after 30 seconds of exposure, the part of having exposed becomes redness.After illumination stops, this diaphragm was placed under room temperature 24 hours, diaphragm reverts to original white again.The colour developing and the process of fading repeat after 20 times, and its photochromic performance is constant substantially.

This variable color diaphragm heat-resisting, moisture resistance properties and shelf characteric are all fine.

Example 20

NG-100(Imperial Chemical Industries

(Teikoku kagaku Co.) gives birth to

The commodity of the electron-donating quality organic compound that produces

Title) 0.25 part

0.5 part of triphenyl sulphur tetrafluoroborate (photosensitizer)

PEG#600(Nof Corp.

（Ni-Ppon Yushi Co.）

The mean molecular weight of producing is 600, contains oxygen

The trade name of the polyglycol of change vinyl) 0.5 part

12.5 parts of methyl isobutyl ketones

12.5 parts of toluene

After above compound under agitation dissolved or being uniformly dispersed, this composition is poured in the handwriting, as the used ink of fibre-tip pen.

When writing on paper or on the plastic base, stay almost invisible latent image with this pen.

When solar irradiation was mapped on this latent image after 15 seconds, latent image becomes blue look, stops illumination, this latent image is at room temperature placed 24 hours after, it reverts to original white again.Although colour developing and the process of fading are carried out the basic no change of its photochromic performance 10 times.

Example 21

Red-40p(Yamamoto chemical industrial company

（Yamamoto Kagaku Co.）

The merchant of the electron-donating quality organic compound of producing

The product title) 0.25 part

Triphenyl-4-thiophene oxygen phenyl sulphur four

0.5 part of borofluoride (photosensitizer)

Emulgen 903(flower king-A

Special Lars (Kao-Atlas Co.)

The polyoxygenated that contains the oxyethylene group compound of producing

The trade name of nonylphenol ethylene ether) 0.5 part

S-Lec BM-5(system iron chemistry worker

Industry (the Sekisui Kagaku of company

That Co.) produces contains the alcoholic hydroxyl compound

The butyral resin trade name) 2 parts

15 parts of butanone

5 parts of toluene

5 parts of methyl alcohol

After above-mentioned all compounds are under agitation dissolved or being uniformly dispersed, cover with paint, lacquer, colour wash, etc. on polyester film base, covering with paint, lacquer, colour wash, etc. consumption is every square metre of 5-6 gram solids.Make white polyester diaphragm with photochromic properties.This variable color diaphragm is after 30 seconds of exposing under the chemical light, and exposed portion becomes redness.Stop illumination, after placing 24 hours under the room temperature, diaphragm reverts to original white with the variable color diaphragm.Though repeat colour developing and the process 20 times of fading, the basic no change of its photochromic performance.

Example 22

OR-55(hillside plot chemical industrial company

（Yamada Kagaku Co.）

The electron-donating quality organic compound of producing

Trade name) 0.25 part

0.5 part of triphenyl sulphur hexafluorophosphate (photosensitizer)

Uniox C-2300(Japan grease

Company (Nippon Yushi Co.)

The poly-second that contains the alcoholic hydroxyl compound of producing

The trade name of glycol castor-oil plant grease) 0.5 part

S-Lec BM-5(makes ironization

Learn (the Sekisui Kagaku of industrial group

That Co.) produces contains alcoholic hydroxyl chemical combination

The butyral resin trade name of thing) 2 part

8 parts of butanone

2 parts of toluene

2 parts of methyl alcohol

After dissolving under the above compound stirring condition or being uniformly dispersed, composition is printed on the good quality paper by method for printing screen.Thereby make the variable color blank sheet of paper with photochromic properties, it is exposed after 30 seconds in the sun, the position of printing then becomes orange.Stop solar radiation, be placed on room temperature after following 24 hours, revert to original white again.Although repeat colour developing and colour killing process 20, the photochromic performance of this variable color paper remains unchanged substantially.

Example 23

The new day Cao Huaxue worker of PSD-170(

Industry (the Shinnisso KaKo C of company

Co.) electron-donating quality of Sheng Chaning organises

The trade name of compound) 0.25 part

0.25 part of diphenyl iodine tetrafluoroborate (photosensitizer)

PEG#600(Nof Corp.

(Nippon Yushi Co.) produces

Mean molecular weight be 600, contain oxidation second

The commodity of the polyglycol of alkenyl compound

Title) 0.5 part

S-Lec BX-L(makes iron

(the Sekisui of chemical industrial company

That Kagaku Co.) produces contains the alcoholic hydroxyl compound

The butyral resin merchant of formula hydroxyl compound

The product title) 2 part

20 parts of butanone

4 parts of toluene

5 parts of methyl alcohol

After dissolving under above all compound stirring conditions or disperseing, by letterpress this composition is printed onto on the good quality paper, thereby makes variable color paper with photochromic properties.This variable color paper exposes after 30 seconds in the sun, and the position of printing becomes black.Stop irradiation of sunlight, after it was deposited at room temperature 24 hours, it had recovered original white again.Even repeat colour developing and the process 20 times of fading, its photochromic performance still remains unchanged substantially.

This variable color paper has good heat-resisting, heat resistance and shelf characteric.

Example 24

OR-55(hillside plot chemical industrial company

(Yamada Kagaku Co.) produces

The electron-donating quality organic compound trade name) 1 part

Two (4-(diphenyl sulphur) phenyl) sulphur

5 parts in ether-two-tetrafluoroborate (photosensitizer)

PEG#1000(Sanyo changes into company

(Sanyo Kasai Co.) produces,

Be that mean molecular weight is 1000, contain oxygen

The polyglycol trade name of change vinyl compound) 4 part

MSK-PO(Maruo Calcium company

The trade name of the alkaline fine powder lime carbonate of producing) 10 part

S-Lec BX-L(system iron chemical industrial company

(Sekisui Kagaku Co.) produces

The butyral resin that contains the alcoholic hydroxyl compound

Trade name) 5 part

25 parts of butanone

After above all organic compounds are dissolved under stirring condition or being uniformly dispersed, be coated on the good quality paper, consumption is: every square metre of 5-8 gram solids, thus make variable color blank sheet of paper with photochromic properties.After this variable color blank sheet of paper exposed for 15 seconds in the sun, the position of the light that exposed to the sun became orange.Stop irradiation of sunlight, place room temperature after following 24 hours on variable color paper, paper reverts to original white again.Although colour developing and the process of fading have repeated the basic no change of photochromic performance of this paper 20 times.

This variable color paper heat-resisting, moisture resistance properties and retention are all fine.

Example 25

ATP(hillside plot (the Yamada of chemical industrial company

Kagaku Co.) electron-donating quality of Sheng Chaning

The trade name of organic compound) 1 part

Two (4-(diphenyl sulphur) phenyl) thioether

4 parts of-two-hexafluoro arsenates (photosensitizer)

Amiet 302（Kao Sekken

The commodity of the polyoxyethylene alkyl amine that company produces

Title) 0.2 part

PEC#600(Sanyo changes into company

(Sanyo Kasei Co.) produces,

Be that mean molecular weight is 600, contain oxygen

Change the merchant of the polyglycol of vinyl compound

The product title) 5 part

25 parts of butanone

5 parts of methyl alcohol

Above all compound are stirred, after dissolving or being uniformly dispersed, pour into the ink of making fibre-tip pen in the handwriting.

When writing on paper or on the plastic base, can obtain visible hardly latent image with this fibre-tip pen.After 15 seconds, the latent image image becomes green with solar light irradiation latent image position.Stop solar light irradiation, it is deposited in room temperature after following 24 hours, latent image image disappears, and reverts to original colourless.Even colour developing and the process of fading have repeated the basic no change of its photochromic performance 20 times.

Example 26

OR-55(hillside plot chemical industrial company

(Yamada Kagaku Co.) produces

The trade name of electron-donating quality organic compound) 1 part

(photosensitive by the compound that following structural formula is represented

Agent) 5 part

PEG#1000(Sanyo changes into company

(Sanyo Kasei Co.) produces,

Mean molecular weight is 1000, contains oxidation second

The trade name of the polyglycol of alkenyl compound) 4 part

MSK-PO（Maruo Calium

The commodity of the alkaline calcium carbonate powder that company produces

Title) 10 part

S-Lel BX-L(system iron chemistry

(the Sekisui Kagaku of industrial group

That Co.) produces contains the alcoholic hydroxyl compound

The butyral resin trade name) 5 part

25 parts of butanone

Above all compound are stirred, after dissolving or being uniformly dispersed, coat on the polyester film base, coating weight is every square metre of 5-8 gram solids, so just makes the white polyester diaphragm of photochromic properties.This variable color diaphragm is exposed after 15 seconds in the sun, and the exposure position becomes orange.Stop solar radiation, after the variable color diaphragm was at room temperature placed 24 hours, the variable color diaphragm reverted to original white again.Even colour developing and the process of fading have repeated 20 times, its photochromic performance remains unchanged substantially.

This variable color diaphragm heat-resisting, moisture-proof and shelf characteric are all fine.

Example 27

NBP-1(hillside plot chemical industrial company

（Yamamoto Kagaku Gohsei

Co.) electron-donating quality of Sheng Chaning organises

The trade name of compound) 1 part

4 parts of the compounds that structure is following (photosensitizer)

Rheodoll Tw-0120（Kao

Sekken company produces, and is to contain oxidation second

The polyoxyethylene sorbitol acid anhydride of alkenyl compound

The trade name of monoleate) 1 part

MSK-PO（Maruo Calcium

The commodity of the alkaline calcium carbonate powder that company produces

Title) 10 part

Ethyl cellulose, the N-4, (U.S.

Hercules company produces contains alcoholic hydroxyl

The trade name of the fibre resin of compound) 6 part

30 parts of butanone

Make the variable color diaphragm of photochromic properties by the method for example 26.After this variable color diaphragm exposed for 15 seconds in the sun, the position of exposing became blue look.Stop illumination, be placed on room temperature after following 24 hours, the variable color diaphragm recovers original white again.Although the colour developing and the process of fading are carried out 20 times repeatedly, its photochromic performance remains unchanged substantially.

Example 28

NC-BK(hodogaya chemical industrial group

(Hodogaya Kagaku Co.) gives birth to

The commodity of the electron-donating quality organic compound that produces

1 part of title

As 5 parts of the compounds (photosensitizer) of following structure

(Sanyo Kasei Co.) produces,

Be that mean molecular weight is 600, contain oxidation

3 parts of the polyglycol trade names of vinyl compound

MSK-PO（Maruo Calcium

The commodity of the alkaline calcium carbonate powder that company produces

9 parts of titles

1 part of triphenyl phosphate

Ethyl cellulose, the N-4(U.S.

Hercules company produces contains pure formula hydroxyl

The celluosic resin trade name of based compound) 6 part

35 parts of butanone

Make the variable color diaphragm of photochromic properties by the method for example 27.The variable color diaphragm exposes after 15 seconds in the sun, and the exposure position becomes black.Stop illumination, be placed on room temperature after following 12 hours, the variable color diaphragm reverts to original white again.Although develop the color repeatedly with the process 20 times of fading, the basic no change of its photochromic performance.

This variable color diaphragm has good heat-resisting, moisture-proof and retention.

Example 29

ATP(hillside plot (the Ya-of chemical industrial company

Mada Kagaku Co.) confession of Sheng Chaning

The trade name of electronics quality organic compound) 1 part

4 parts of compounds (photosensitizer) with following structural

Amit 302(Kao Sekken company

The poly-second that contains the ethylene oxide based compound of producing

The glycol trade name) 0.2 part

PEG#600(Sanyo changes into company

(Sanyo Kasei Co.) produces

Mean molecular weight is 600, contains oxyethylene group

The polyglycol trade name of based compound) 5 part

25 parts of butanone

5 parts of methyl alcohol

Above all compound are stirred, after dissolving or being uniformly dispersed, pour among the handwriting of fibre-tip pen, make the ink of fibre-tip pen.

When writing on paper or on the plastic base, obtain a kind of visible hardly latent image with this pen.

When solar radiation at the latent image position after 15 seconds, the latent image pattern becomes green.Stop solar radiation, be placed on room temperature after following 12 hours, the latent image pattern disappears, and becomes original colourless state.Although repeat the process that develops the color and fade 20 times, its photochromic performance is constant substantially.

Example 30

NC-BK(hodogaya chemical industrial group

（Hodagaya Kagaku Co.）

The merchant of the electron-donating quality organic compound of producing

1 part of product title

As 4 parts of the compounds (photosensitizer) of following structural formula

MSK-PO（Maruo Calcium

The commodity of the alkaline calcium carbonate powder that company produces

Title) 10 part

Chemical industrial company of MS-300(Nippon Steel

（Shinnittetsu Kagaku Co.）

Styrene-methacrylic acid copolymer resins of producing

Trade name) 5 parts

MIBK(ethyl isobutyl ketone) 50 part

10 parts of butanone

Above-mentioned all compound are stirred, after dissolving or being uniformly dispersed, coat on polyester film base or the fine quality paper, consumption is: every square metre of 5-8 gram solids, this lotus has just been made the variable color of photochromic properties blank sheet of paper.This variable color paper exposes after 15 seconds in the sun, and the exposure position becomes black.Stop irradiation, be placed on room temperature after following 12 hours, variable color diaphragm or paper revert to original white again.Although repeat colour developing and the process 20 times of fading, the basic no change of its photochromic performance.

This variable color diaphragm or paper have good heat-resisting, moisture-proof and shelf characteric.

Example 31

NBP-1(Yamamoto chemical industrial company

（Yamamoto Kagaku Co.）

The commodity of the electron-donating quality organic compound of producing

Title) 0.25 part

Triphenyl acyl methylphosphine tetrafluoroborate

(photosensitizer) 0.5 part

Newpol 50HB-2000

(Sanyo changes into (the Sanyo Kasei of company

Co.) produce the polyoxy that contains the oxyalkylene group thing

Change the oxidation of ethylene propylene) ethylene glycol mono-ether

Trade name) 0.25 part

0.2 part of oleyl alcohol (compound) with alcoholic hydroxyl

7 parts of toluene

10 parts of butanone

3 parts of methyl alcohol

Above-mentioned all compound are stirred, and after dissolving or being uniformly dispersed, dip-coating is on polyester film base, and the dip-coating amount is: every square metre of 3-5 gram solids.Make the white diaphragm of the variable color of photochromic properties.The variable color diaphragm exposed under black lamp after 30 seconds, and diaphragm becomes blue look.Stop the irradiation of light, place room temperature after following 24 hours on the variable color diaphragm, diaphragm reverts to original white again.Even develop the color repeatedly with the process 20 times of fading, its photochromic performance does not change substantially.

This variable color diaphragm has good heat-resisting, moisture-proof and retention.

Example 32

S-205(hillside plot chemical industrial company

(Yamada Kagaku Co.) gives birth to

The merchant of the electron-donating quality organic compound that produces

The product title) 0.5 part

1 part in the potpourri that structure is following (photosensitizer)

PEG#1500(Sanyo changes into public affairs

Department (Sanyo Kasei Co.) gives birth to

Producing, is that mean molecular weight is 1540,

The poly-second two that contains the ethylene oxide based compound

The alcohol trade name) 1.5 part

MSK-PO（Marao Calcium

Company produces, alkaline calcium carbonate powder

Trade name) 3.5 part

Amisol SME(grinds essence in the river

(the Kawaken Fine of refinement company

Chemical Co.) wax of Sheng Chaning

Trade name) 10 part

Above-mentioned all compounds are arrived 100-120 ℃ with attitor with its dispersed-heated, pour into then in the test tube that diameter is 9mm, at room temperature place.Just make a kind of colourless variable color wax crayon.

With this variable color wax crayon letter that draws on notebook, pattern etc. all are invisible.

When solar radiation after these in last 30 seconds, these monograms etc. all become black.Stop solar radiation, it is at room temperature placed 24 hours after, letter, pattern etc. revert to original colourless state again.Although colour developing and the process of fading repeat the basic no change of its photochromic performance 20 times.

Example 33

Make colourless variable color wax crayon by the method for example 32, just replace S-205 with Pergascript Red I-6B in the prescription.

With the letter that this variable color wax crayon is drawn on notebook, pattern etc., all be invisible.

When solar radiation to notebook after 30 seconds, letter, pattern etc. all become redness.Stop the irradiation of sunlight, notebook is positioned over room temperature after following 24 hours, letter, pattern etc. move back into original colourless.Though develop the color repeatedly with the process 10 times of fading, its photochromic performance remains unchanged substantially.

Example 34

Method by example 32 prepares colourless variable color wax crayon.Just replace S-205 with Green 24P in the prescription.

With the letter of this crayon drawing, pattern etc. all are invisible.

When solar radiation to the notebook after 30 seconds, letter, patterns etc. become green.After stopping solar radiation, notebook was at room temperature placed 24 hours, letter, pattern etc. revert to original colourless state again.Although colour developing and the process of fading are carried out 20 times, its photochromic performance remains unchanged substantially.

Example 35

Replace S-205 with NBP-1 in the prescription, the method for use-case 32 prepares wax crayon.

Even if with this wax crayon on notebook, write letter, picture etc., also cannot see person's handwriting.

After the notebook that crayon drawing is crossed shone for 30 seconds in the sun, letter, picture etc. became blue look.After illumination stops, notebook at room temperature placed 24 hours after, it reverts to original colourless again.After even colour developing and colour killing repeat 20 times, the also basic no change of its photochromic performance.

Example 36

Replace S-205 with OR-55, prepare wax crayon by the method for example 32.

Figure that writes letter on notebook, draws with this wax crayon etc. is invisible.

After notebook was placed under the sunlight 30 seconds of irradiation, letter and figure etc. became orange.After illumination stops, this notebook was placed 24 hours in room temperature, it just reverts to original colourless.After even colour developing and colour killing repeat 20 times, the also essentially no variation of its coloured light performance.

Example 37

NBP-1(Yamamoto chemosynthesis company produces

The trade name of electron-donating quality organic compound) 0.25 part

0.5 part of triphenyl sulphur hexafluorophosphate (photosensitizer)

MIRT 52(flower king-Atlas public affairs

The polyoxy that contains the ethylene oxide based compound that department produces

The trade name of the hard ester acid esters of change ethene) 0.5 part

Nectarine is red ^#312(east chemical company produces

The trade name of red) 0.05 part

Chemical company of MS-300(Nippon Steel produces

Styrene-methacrylic acid copolymer resin

Trade name) 1.5 part

8 parts of toluene

12 parts of butanone

3 parts of methyl alcohol

After all components are under agitation dissolved or disperseing, be coated on the polyester film base, coating weight is every square metre of 4-5 gram solids, just makes the red diaphragm of photochromic properties, at the back side of diaphragm coated with adhesive, just makes label.Label is bonded at writing material, and above the toy etc., after 20 seconds of exposing in the sun, this label promptly becomes purple.After illumination stopped, after room temperature was placed 24 hours, it reverted to original redness again with this label.Even after colour developing and colour killing repeated 20 times, its coloured light performance did not reduce basically yet.

This variable color label has good heat-resisting, heatproof and retention.

Example 38

Perqascript Red I-6B(vapour

The electron-donating quality that Ba Jiaji company produces is organic

The trade name of compound) 1 part

Two (4-(diphenyl sulphur) phenyl) sulphur

5 parts in ether-two-tetrafluoroborate (photosensitizer)

MS-1(Maruo Calcium public affairs

The commodity of the alkaline calcium carbonate powder that department produces

Name) 12 part

S-Lec BX-L(makes iron

Chemical industrial company produces contains alcoholic hydroxyl

The trade name of the butyral resin of compound) 5 part

Oil yellow ^#109(east chemical company gives birth to

The trade name of the yellow dye that produces) 0.2 part

25 parts of butanone

By the method preparation of example 37, just can be made into the pornographic movie diaphragm of photochromic properties.Diaphragm exposes after 15 seconds in the sun, and its exposed portion just becomes green.After illumination stops, this diaphragm at room temperature placed 24 hours after, diaphragm reverts to original yellow again.Even after colour developing and colour killing repeated 20 times, its photochromic performance did not reduce basically yet.

This variable color diaphragm has good heat-resisting, moisture-proof and anti-retention.

Example 39

Red-40P(Yamamoto chemical company produces

The trade name of electron-donating quality organic compound) 0.25 part

0.5 part of triphenyl sulphur perchlorate (photosensitizer)

S-Lec BM-S(system iron chemistry

Industrial group produces contains the alcoholic hydroxyl compound

The trade name of butyral resin) 1.5 part

Oil yellow ^#107(east chemical company produces

The trade name of yellow dye) 0.05 part

9 parts of toluene

25 parts of butanone

After above component under agitation dissolved or disperseing, be printed on the good quality paper, just make the yellow diaphragm of photochromic properties with toppan printing.This diaphragm exposes after 30 seconds in the sun, and the printing position just becomes green.After illumination stops, this diaphragm at room temperature placed 24 hours after, it just reverts to original yellow.Even after colour developing and colour killing repeated 20 times, its photochromic performance did not descend basically.

This diaphragm has good heat-resisting, moisture-proof and retention.In addition, do not produce gas or air bubble when exposure, this diaphragm also has good colour sensitivity and color density.

Example 40

NC-Y-2-1(hodogaya chemical company

Hodogaya Kagaku Co.) produces

The trade name of electron-donating quality organic compound) 0.25 part

0.5 part of triphenyl sulphur tetrafluoroborate (photosensitizer)

0.25 part of triphenyl phosphate

S-Lec BM-S(system iron chemical industrial company

The butyral of producing that contains the alcoholic hydroxyl compound

The trade name of resin)

0.5 part of alkalescence finely powdered silica

Nectarine is red ^#312(east chemical company gives birth to

The trade name of the red that produces) 0.1 part

7 parts of butanone

2 parts of toluene

2 parts of methyl alcohol

After above-mentioned component under agitation dissolved or disperseing, be printed on the good quality paper, just make the red diaphragm of photochromic properties with method for printing screen.Diaphragm exposed for 30 seconds with high-pressure sodium lamp, and its printing position just becomes green.After rayed stops, this diaphragm was placed 24 hours in room temperature, it just reverts to original redness.Even colour developing and colour killing repeat 20 times, its photochromic performance does not still reduce basically.

This diaphragm has good heat-resisting, moisture-proof and retention.In addition, do not produce gas or air bubble when exposure, this diaphragm also has good colour sensitivity and color density.

In sum, photosensitive composition of the present invention has multiple color and luster product, and has good heat-resisting, moisture-proof and retention, this composition scope that is widely used.

As detailed understanding the present invention, and behind the instantiation with reference to it, the people who is proficient in this technology obviously can carry out variations and modifications in its main idea and scope.

Claims (21)

1, photosensitive composition, it comprises electron-donating quality organic compound and photosensitizer.Photosensitizer is chosen in the aromatic series salt of the aromatic series salt of periodic table of elements Vla family element or periodic table of elements V a family element from the aromatic series halogen.

2,, wherein, also be added with the compound that contains alcoholic hydroxyl according to the photosensitive composition described in the claim 1.

3,, wherein, also be added with compound and these two kinds of materials or wherein a kind of of alkaline fine powder of containing oxyethylene group according to the photosensitive composition described in the claim 1.

4,, wherein, also be added with the compound that contains alcoholic hydroxyl according to the photosensitive composition described in the claim 3.

5, according to the photosensitive composition described in the claim 1, wherein, the electron-donating quality organic compound that can Gong choose has triphenyl methane phthalide, fluorane, phenothiazine, indyl phthalide, platinum amine, rhodamine lactams, rhodamine lactone, dihydroindole, triphenyl methane, azepine phthalide, chomene indoles, triazenes.

6, according to the photosensitive composition described in the claim 1, wherein, the electron-donating quality organic compound that can Gong choose has triphenyl phthalide, fluorane, indyl phthalide, platinum amine, rhodamine lactams, triphenyl methane, azepine phthalide.

7, according to the photosensitive composition described in the claim 1, wherein, photosensitizer can be chosen from following compounds: aromatic series halogen (salt of the halogen-containing complex ion of aromatic series halogen ion Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As); The salt of the aromatic series ion of periodic table of elements V la family element (O, S, Se and Te) and the halogen-containing complex ion of Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As; The salt of the aromatic series ion of periodic table of elements V a family element (N, P, As, Sb and Bi) and the halogen-containing complex ion of Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, B, P and As, and the salt of aromatic series ion and perchloric acid.

8, according to the photosensitive composition described in the claim 1, wherein, photosensitizer can be chosen from following compounds: aromatic series salt compounded of iodine (salt of the halogen-containing complex ion of aromatic series iodide ion and Sb, B, P and As); The salt of the aromatic series ion of periodic table of elements V la family's element (S) and the halogen-containing complex ion of Sb, B, P and As; The salt of the aromatic series ion of periodic table of elements V a family element (N and P) and the halogen-containing complex ion of Sb, B, P and As, and the salt of aromatic series ion and perchloric acid.

9, according to the photosensitive composition described in the claim 1, wherein, photosensitizer can be chosen from following compounds: aromatic series iodide ion and FB ₄Salt, and aromatic series sulphion and PF ₆Salt.

10, according to the photosensitive composition described in the claim 2, wherein, the compound that contains alcoholic hydroxyl can be chosen from following compounds: boiling point is equal to or higher than 150 ℃, the fatty alcohol of carbon atom more than six or six; Boiling point is equal to or higher than 150 ℃, the polyvalent alcohol of carbon number more than six or six; Boiling point is equal to or higher than 150 ℃, the aromatic alcohols of carbon atom more than seven or seven; And molecular weight is 10,000-300,000 macromolecular alcohol.

11, according to the photosensitive composition described in the claim 2, wherein, the compound that contains alcoholic hydroxyl can be chosen from following compounds: boiling point is equal to or higher than 200 ℃, the carbon atom individual or fatty alcohol more than nine in the nine periods; Boiling point is equal to or higher than 200 ℃, the aromatic alcohol of carbon number more than seven or seven; Boiling point is equal to or higher than 200 ℃, the polyvalent alcohol of carbon number more than six or six; And molecular weight is 10,000-300,000 macromolecular alcohol.

12, according to the photosensitive composition described in the claim 3, wherein, contain the compound of oxyethylene group, be molecular weight more than or equal to 100, contain the compound of three or three above oxyethylene groups in the molecule.

13, according to the photosensitive composition described in the claim 3, wherein, contain the compound of oxyethylene group, be molecular weight more than or equal to 190, contain the compound of six or six above oxyethylene groups in the molecule.

14, according to the photosensitive composition described in the claim 3, wherein, alkaline fine powder can be chosen from following material: the oxyhydroxide of alkaline metal (lithium, sodium, potassium etc.); Earth alkali metal (magnesium, calcium, barium etc.) and carbonate thereof; Alkalescence finely powdered silica, alkalescence are taken off and are covered soil, alkaline talcum powder, alkaline lead sulfate, basic lead carbonate.

15, according to the photosensitive composition described in the claim 4, wherein, the compound that contains alcoholic hydroxyl can be chosen from following compounds: boiling point is equal to or higher than 150 ℃, the fatty alcohol of carbon number more than six or six; Boiling point is equal to or higher than 150 ℃, the polyvalent alcohol of carbon number more than six or six; Boiling point is greater than or equal to 150 ℃, the aromatic alcohol of carbon number more than seven or seven; And molecular weight is 10,000-300,000 macromolecular alcohol.

16, according to the photosensitive composition described in the claim 4, wherein, the compound that contains alcoholic hydroxyl can be chosen from following compounds: boiling point is equal to or higher than 200 ℃, the carbon atom individual or fatty alcohol more than nine in the nine periods; Boiling point is equal to or higher than 200 ℃, the aromatic alcohol of carbon number more than seven or seven; Boiling point is equal to or higher than 200 ℃, the polyvalent alcohol of carbon number more than six or six, and molecular weight is 10,000-300,000 macromolecular alcohol.

17, according to the photosensitive composition described in the claim 1, wherein, light sensation agent and electron-donating quality organic compound and weight ratio for 0.01-100 part than 1 part.

18, according to the photosensitive composition described in the claim 3, wherein, the compound that contains oxyethylene group and the weight ratio of electron-donating quality organic compound for 0.01-100 part than 1 part.

19, according to the photosensitive composition described in the claim 3, wherein, the weight ratio of alkaline fine powder and electron-donating quality organic compound for 0.01-100 part than 1 part.

20, according to the photosensitive composition described in the claim 2, wherein, the compound that contains alcoholic hydroxyl and the weight ratio of photosensitizer for 0.01-200 part than 1 part.

21, according to the photosensitive composition described in the claim 4, wherein, the compound that contains alcoholic hydroxyl and the weight ratio of photosensitizer for 0.01-200 part than 1 part.