CN1107884C - Squaric acid dye/iodate composite and its use - Google Patents
Squaric acid dye/iodate composite and its use Download PDFInfo
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- CN1107884C CN1107884C CN99107347A CN99107347A CN1107884C CN 1107884 C CN1107884 C CN 1107884C CN 99107347 A CN99107347 A CN 99107347A CN 99107347 A CN99107347 A CN 99107347A CN 1107884 C CN1107884 C CN 1107884C
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Abstract
The present invention relates to a squaric acid dye/iodate composite and a function thereof, the squaric acid dye/iodate composite is used as a visual light/near infrared light photosensitive polymerization composition initiator, and the present invention belongs to the field of macromolecular chemistry and sensitization polymer materials. The composite is prepared from a squaric acid dye and iodate via electrostatic interaction and dipolar interaction in a solvent, and the weight of the iodate is 1 to 10 times of that of the squaric acid dye. The squaric acid dye/iodate composite can be used as a visual light/near infrared light polymerization initiator of allyl monomers or a visual light/near infrared light photocuring initiator of a photocuring coating material, a photoetching material, a photoimaging material, a hologram recording material, an optical material and a three-dimensional model material.
Description
The invention belongs to high polymer chemistry and field of light-sensitive high molecular materials, particularly relate to visible light/near infrared light photosensitive polymerization composite initiator-squaraine dye/iodonium salt compound and uses thereof.
Squaraine dye is a class important function dyestuff, and its absorbing light scope can cover whole visible lights and near infrared range.It has the electronic structure characteristic of electron donor-electron accepter in the molecule-electron donor (D-A-D), thereby has good photoelectric functional character, in xerox, photo-voltaic cell, be used widely in aspect such as optical recording and nonlinear optics, the report of this respect is referring to " image science magazine " nineteen ninety 34 volumes, 2 phase 31-37 page or leaf (K.Y.Law, Squraine Chemistry:Solution Electrochemistry and Its Usein Assessing the Relative Photosensitivity of Squaraines in Bilayer XerographicDevice Journal of Imagine Science 34,2,31-37,1990), " chemistry summary " 1993 93 volume 449-464 pages or leaves (Kock-Yee Law, Organic Photoconductive Materials:Recent Trends andDevelopments, Chemistry Reviews, 93,449-464,1993) and " physical chemistry magazine " 1994 98 volume 11563-11569 page or leaf (Gary W.Scott, Kim Tran, Squaraine Photophysics inPolymer Films, J.Phys.Chem.98,11563-11569,1994) article.Yet squaraine dye directly but is difficult to realize as initiator of polyreaction.
The objective of the invention is to overcome squaraine dye and in vinyl monomer, be difficult to initiated polymerization, the photosensitive composite initiator-squaraine dye of a kind of visible light/near infrared light/salt compounded of iodine compound is provided; Another object of the present invention provides this type of composite initiator as the photopolymerisable initiating agent of vinyl monomer visible light/near infrared light or as the initiating agent of light solidifying coating material, photoetching material, photoimaging material, hologram recording material, optical material and three-dimensional modeling material visible-light/near infrared light photocuring.
Visible light of the present invention/near infrared light photoinitiator-squaraine dye/salt compounded of iodine complex solution, its compound is to be 1～10 times of squaraine dye weight by squaraine dye (SQ) and salt compounded of iodine (On) with the weight of salt compounded of iodine, forms in solvent by electrostatic interaction and dipolar interaction.The squaraine dye and the salt compounded of iodine structure that are suitable for forming this compound are as follows:
(1) squaraine dye (SQ) structure is suc as formula shown in (I):
Wherein, Ar is following group:
Or
R wherein
1Be H, alkyl or aryl etc.; R
2Be H, halogen, alkyl, alkoxy, alkylamino or aryl; R
3Be H or alkyl etc.
(2) salt compounded of iodine (On) structure is suc as formula shown in (II):
Wherein:
Or
R
4: H, OH, Cl or alkyl X
-: Cl
-, BF
4 -, AsF
6 -, PF
6 -, SbF
6 -, ClO
4 -Or TsO
-
The preparation method of visible light of the present invention/near infrared light photoinitiator-squaraine dye/salt compounded of iodine complex solution carries out as follows:
Under the lucifuge condition, squaraine dye and salt compounded of iodine are joined in benzene, toluene, chloroform or the acetone and other organic solvent, wherein the salt compounded of iodine consumption is 1～10 times of squaraine dye weight, under 20-50 ℃ of temperature, be stirred to dissolving fully, promptly obtain as visible light/near infrared light photoinitiator-squaraine dye/salt compounded of iodine complex solution.
Wherein, described squaraine dye is synthetic as follows:
Generally carry out the condensation reaction preparation by 1 mole of side's acid and 2 moles of corresponding nucleophilicity aromatic compounds, product is 1,3 pair of replacement side acid derivative, i.e. squaraine dye.According to the type difference of square acid and derivant thereof, synthetic route is divided two kinds of acid system and ester methods, and the present invention adopts acid system, and concrete steps are as follows:
In reaction vessel, acid of adding side and corresponding nucleophilicity aromatic compound, its molar ratio is 1: 2.Add the doubly normal butyl alcohol of the sour weight in side and 5-30 organic solvents such as the benzene of the sour weight in side or toluene doubly of 10-50 then, doubly the pyrroles or the quinoline of the sour weight in side are made catalyzer can to add 1-3 if necessary, reflux 5-20 hour, reaction finishes, cooling, filter, obtain squaraine dye after crude product is purified.
Wherein said side's acid is:
Described corresponding nucleophilicity aromatic compound is:
Described salt compounded of iodine is by document: " the polymer science magazine. polymer chemistry " synthetic methods of 395 pages of 1998 years 27 volumes carry out [Crevillo J.V, Lee J, J.Polym.Sci.Polym.Chem.Ed1998,27,395].
Visible light of the present invention/near infrared light photoinitiator is squaraine dye/salt compounded of iodine compound, can be used as the photopolymerisable initiating agent of vinyl monomer visible light/near infrared light or as the initiating agent of visible light/near infrared light photocurings such as photo-curing material such as light solidifying coating material, photoetching material, photoimaging material, hologram recording material, optical material and three-dimensional modeling material, its consumption, preparation and using method during as the photopolymerisable initiating agent of vinyl monomer visible light/near infrared light with as the initiating agent of photo-curing material visible light/near infrared light photocuring is as follows:
Each component and content thereof were (percent by weight) when A. squaraine dye/salt compounded of iodine compound was as vinyl monomer visible light/near infrared light Photoepolymerizationinitiater initiater:
Vinyl monomer 29.9%-70%
Organic solvent 29.9%-70%
Squaraine dye/salt compounded of iodine compound 0.001%-0.1%
Reaction concrete operations step is as follows:
In reactor, the adding percent by weight is that organic solvent and the percent by weight of 14%-30% is the vinyl monomer of 29.9%-70%, lead to nitrogen 20-30 minute then to remove oxygen, under the lucifuge condition, (wherein squaraine dye/salt compounded of iodine compound accounts for the 0.001%-0.1% of overall reaction liquid weight to add percent by weight and be squaraine dye/salt compounded of iodine complex solution of 15.901%-40.1%, organic solvent accounts for the 15.9%-40% of overall reaction liquid weight), use light source irradiation under the room temperature, react and stopped illumination in 0.5-5 hour, polymkeric substance is separated out, promptly get crude product, handle, can obtain the polymkeric substance of refining vinyl monomer if carry out reprecipitation.
Each component and content thereof were (percent by weight) when B. squaraine dye/salt compounded of iodine compound was as visible light/near infrared light photo-curing material initiating agent:
Light reactive resin 40%～75%
Multi-functional acrylate's crosslinking chemical 10%～30%
Simple function group acrylate reactive diluent 5%～15%
Squaraine dye/salt compounded of iodine compound 1%～11%
Organic solvent 5%～10%
Reaction concrete operations step is as follows:
In the container of mixing plant is housed, add percent by weight and be 40%～75% light reactive resin and percent by weight and be multi-functional acrylate's crosslinking chemical of 10%～30%, under 40 ℃～50 ℃ temperature, stir and make it to mix, the B1 component.
In another container, (wherein squaraine dye/salt compounded of iodine compound accounts for the 1%-11% of overall reaction liquid weight to add percent by weight and be squaraine dye/salt compounded of iodine complex solution that 5%～15% reactive diluent and percent by weight be 6%-21%, organic solvent accounts for the 5%-10% of overall reaction liquid weight), stir, dissolve the B2 component.
Following B2 component of condition is added in the B1 component under lucifuge, mixes, and uses light source irradiation 1-10 minute under the room temperature, can obtain the light solidifying coating material.
Wherein said vinyl monomer is esters of acrylic acid, acrylic amide, vinyl cyanide, styrene, vinyl acetate or vinyl pyrrole ketone etc.;
Described organic solvent is aromatic hydrocarbons such as benzene, toluene, halogenated hydrocarbon such as methenyl choloride, methylene chloride, ketone such as acetone, alcohols such as ethanol, gylcol ether, glycol ether acetates, propylene glycol ethers, propylene-glycol ether acetate class etc.;
Described light reactive resin is epoxy acrylate, polyesters acrylate, urethane acrylate or saturated polyester etc. not;
Described multi-functional acrylate's crosslinking chemical is a trimethylolpropane triacrylate, ethoxyquin (or third oxidation) trimethylolpropane triacrylate, pentaerythritol triacrylate, double pentaerythritol methacrylate, various alkane double methacrylates, glycols double methacrylate such as tripropylene glycol double methacrylate, ethylene glycol diacrylate, glycerine double methacrylate, a condensed ethandiol double methacrylate, tirethylene glycol double methacrylate, hexanediol double methacrylate etc.;
Described simple function group acrylate reactive diluent is ethers simple function group acrylate, alkyl simple function group acrylate, hydroxyalkyl acrylates or hydroxyalkyl methacrylates.Alkyl simple function group acrylate is acrylic acid tetrahydrofuran ester, isobornyl acrylate; Hydroxyalkyl acrylates is hydroxy-ethyl acrylate or hydroxypropyl acrylate; Hydroxyalkyl methacrylates is hydroxyethyl methylacrylate or hydroxy propyl methacrylate.
Described light source can adopt visible light source such as xenon lamp, incandescent lamp or iodine-tungsten lamp etc., also can adopt LASER Light Source such as argon laser or helium-neon laser semiconductor laser etc.
Squaraine dye of the present invention/salt compounded of iodine compound initiated polymerization mode can be with emulsion polymerization, micro-emulsion polymerization, the mode of solution polymerization and carrying out in the thickness system.
As visible light/near infrared light photoinitiator the time, the consumption of squaraine dye (SQ) and salt compounded of iodine (On) plays an important role, and squaraine dye has very high molar extinction coefficient (～10
5Mol
-1.L.cm
-1), consumption is too high, can polymerization rate is descended, and consumption is low excessively, makes reaction conversion ratio low because of the very fast consumption of dyestuff again because of the negative effect of resistance light generation, and the squaraine dye consumption is generally the 0.001-1% (percent by weight) of light reaction system total amount.Salt compounded of iodine is the component that produces initiating activity free radical fragment, its bond distance R and to ion (X
-) directly influence its solubleness, along with chain length R increases and to ion (X
-) increase of radius increase solubility property, its consumption is 1～10 times of squaraine dye.
The spectral response range of visible light of the present invention/near infrared light photoinitiator-squaraine dye/salt compounded of iodine compound, photochemical properties, living radical formation efficiency, the solubility property all structure with them are relevant with composition.Table 1 has been listed squaraine dye and has been worked as R
1Be Me, R
2Be H, R
3Maximum absorption wavelength during for Me.
Table 1 squaraine dye is worked as R
1Be Me, R
2Be H, R
3Maximum absorption wavelength during for Me
Wherein, in the table as substituent R
1Also can be H, alkyl, aryl etc.; R
2Also can be halogen, alkyl, alkoxy, alkylamino, aryl etc.; R
3Also can be H, alkyl etc.
In view of having intramolecular charge, squaraine dye shifts complex structure, it is that salt compounded of iodine is made activator that the present invention proposes to use a kind of suitable electron acceptor compound, form compound (SQ-On) by salt compounded of iodine and squaraine dye, their chemical property have following characteristics, be not subjected under the illumination effect very stable, and it is very active under the illumination effect, after being subjected to optical excitation, electron transfer reaction takes place, cause that salt compounded of iodine decomposes, produce active free radical fragment, thereby be easy to cause Raolical polymerizable, therefore the extinction scope of squaraine dye can cover whole visible lights and near infrared range in addition, and this squaraine dye/salt compounded of iodine compound extremely is suitable for visible light/near infrared light and causes photopolymerisable purposes.
Squaraine dye of the present invention/salt compounded of iodine compound (SQ-On), another characteristics of its chemical property are to have the structure that forms the bimolecular compound.This makes squaraine dye/salt compounded of iodine generation photoinduction electronic transfer process mainly be undertaken by intramolecular approach.For polymerization reaction system, general viscosity is higher, molecular diffusion is obstructed, and is unfavorable for the bimolecular sensitized reaction, but the compound system of forming by squaraine dye/salt compounded of iodine, owing to form compound, can overcome molecular diffusion effectively and be obstructed, guarantee that Photoinitiated reactions carries out smoothly, therefore have the rapid-action feature the restriction of reaction, make and be not vulnerable to the influence of introduced contaminants by free radical reaction of formation efficient height.The light initiation polymerization of very suitable thickness system.
Squaraine dye of the present invention/salt compounded of iodine compound (SQ-On), the another feature of its chemical property is to have photobleaching.Just squaraine dye can be oxidized to shadow in photochemical reaction process, thereby has solved squaraine dye because of molar extinction coefficient big (～10
5Mol
-1.L.cm
-1) and the resistance optical issue that causes make that Photoinitiated reactions is able to take place in than deep layer, thereby help improving the photopolymerization tempo.Therefore it extremely is suitable for the solid or the semi-solid photopolymerisable purposes of mobile difference.
Specifically set forth the present invention below in conjunction with embodiment:
Embodiment 1
1, two (right-N, the accelerine) squaraine dye-phenyl of 3-, the preparation of octyloxyphenyl hexafluoro-iodide antimonate salt composite solution:
The first step: 1, two (right-N, the accelerine) squaraine dyes of 3-synthetic:
Sour 5g in adding side (44mmol) and N in reaction vessel, accelerine 10.6g (88mmol), add normal butyl alcohol 200g and toluene 120g then, heating reflux reaction 6 hours produces blue sediment, reaction finishes, through supercooling, filtration, drying, obtain 1 after crude product is purified, 3-is two (right-N, accelerine) squaraine dye 4.5g, productive rate 31%.
Second step: phenyl, octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine synthetic:
1. octyloxy benzene is synthetic:
With 88% phenol solution 37.3g (0.5mol), tetrabutylammonium iodide 5.7g, potassium hydroxide 37.3g, bromooctane 29ml, water 83.3ml and toluene 83.3ml join in the reaction vessel, at logical N
2With reflux under the stirring condition 10 hours, cooling, branch vibration layer, with sodium hydrate aqueous solution and water washing organic layer, dry back is removed to desolvate and is promptly got colourless octyloxy benzene product liquid.
2. two acetic acid iodobenzenes is synthetic:
After acetic anhydride 305ml is heated to 40 ℃, drip 30%H
2O
270ml, 40 ℃ of isothermal reactions 4 hours add iodobenzene and reacted 4 hours again, remove and desolvate, and obtain white crystal product two acetic acid iodobenzenes after the cooling.
3. phenyl, octyloxyphenyl is synthetic to the pyrovinic acid salt compounded of iodine:
5.4g pyrovinic acid sulfuric monohydrate and 5g two acetic acid iodobenzenes are dissolved in the 30ml acetonitrile, stir rapidly, get white precipitate.With the above-mentioned white precipitate of 5g, 2.5g octyloxy benzene, the 2ml acetonitrile, the 1ml glacial acetic acid is stirred and heated to 40 ℃, reacts 2 hours, and cooling after adding entry under quick the stirring, can obtain white crystal product phenyl, and octyloxyphenyl is to the pyrovinic acid salt compounded of iodine.
4. phenyl, octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine synthetic:
7.5g phenyl, octyloxyphenyl be to the pyrovinic acid salt compounded of iodine, 4.6g sodium hexafluoroantimonate (NaSF
6), 20ml acetone, stirring reaction is 1 hour under the room temperature, the filtering reaction thing, the concentrated back of mother liquor is adding entry under stirring fast, get solid crude product, gets crystalline product phenyl, octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine behind the methanol-water recrystallization.
The 3rd step: 1, two (right-N, the accelerine) squaraine dye-phenyl of 3-, the preparation of octyloxyphenyl hexafluoro-iodide antimonate salt composite solution:
Under the condition of room temperature and stirring and lucifuge with 5g1, two (right-N, accelerine) squaraine dyes of 3-and 45g phenyl, octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine is dissolved in and obtains the desired complex solution of 100g in the 50g acetone.
Embodiment 2
1, two (N-isopropyl-2,3, the 3 tri-methyl indole quinolines) squaraine dye-phenyl of 3-, the preparation of octyloxyphenyl iodonium hexafluorophosphate father-in-law salt composite solution:
The first step: 1, two (N-isopropyl-2,3, the 3 tri-methyl indole quinolines) squaraine dyes of 3-synthetic:
Side sour 3g (25mmol) and N-isopropyl-2,3,3-tri-methyl indole quinoline salt compounded of iodine 16.5g (50mmol) normal butyl alcohol 200g and pyrroles 8g, after the heated and stirred dissolving, refluxed 7 hours, decompression steams solvent, add methanol aqueous solution (65%) recrystallization three times, get purpose product 7g, yield 58.2%.
Second step: phenyl, octyloxyphenyl hexafluorophosphoric acid salt compounded of iodine synthetic:
With phenyl among the embodiment 1, the synthetic method of octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine is basic identical, just 4. uses NaPF in the step the
6Replace NaSbF
6, all the other are just the same.
The 3rd step: 1, two (N-isopropyl-2,3, the 3 tri-methyl indole quinolines) squaraine dye-phenyl of 3-, the preparation of octyloxyphenyl iodonium hexafluorophosphate salt composite solution:
Under room temperature and lucifuge condition with 0.001g1, two (the N-isopropyls-2 of 3-, 3,3 tri-methyl indole quinolines) squaraine dye and 0.01g phenyl, octyloxyphenyl hexafluorophosphoric acid iodonium salt adds in the 100g methenyl choloride, can obtain 1 after the stirring and dissolving, two (the N-isopropyls-2 of 3-, 3,3 tri-methyl indole quinolines) squaraine dye-phenyl, octyloxyphenyl iodonium hexafluorophosphate salt composite solution.
Embodiment 3
1, two (N-methyl-2-methyl-benzothiazole) squaraine dye-phenyl of 3-, the preparation of octyloxyphenyl hexafluoro-iodide antimonate salt composite solution:
The first step: 1, two (N-methyl-2-methyl-benzothiazole) squaraine dyes of 3-synthetic:
Side sour 4g (35mmol) and N-methyl-2-methylbenzothiazole salt compounded of iodine 20.5g (70mmol), normal butyl alcohol 200g, benzene 100g and quinoline 10g, after the heated and stirred dissolving, loading onto fraction water device water-dividing refluxed 15 hours, having solid to separate out after the cooling, filter the back filter cake with ether drip washing three times, is that developping agent carries out the chromatographic column separation and obtains the purpose product with methenyl choloride.
Second step: phenyl, octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine synthetic:
With phenyl among the embodiment 1, the synthetic method of octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine is identical
The 3rd step: 1, two (N-methyl-2-methyl-benzothiazole) squaraine dye-phenyl of 3-, the preparation of octyloxyphenyl hexafluoro-iodide antimonate salt composite solution:
Under the condition of room temperature and stirring and lucifuge with 4g1, two (N-methyl-2-methyl-benzothiazole) squaraine dye and the 40g phenyl of 3-, octyloxyphenyl hexafluoro-antimonic acid salt compounded of iodine is dissolved in the 56g acetone and just can obtains 100g
1, two (N-methyl-2-methyl-benzothiazole) squaraine dye-phenyl of 3-, octyloxyphenyl hexafluoro-iodide antimonate salt composite solution.
Embodiment 4
As the visible photopolymerisable initiating agent of vinyl monomer:
Methyl methacrylate 8g (percent by weight is 40%)
Chloroform 2g (percent by weight is 10%)
Prepared among the embodiment 21, two (N-isopropyl-2,3,3 tri-methyl indole quinolines) squaraine dye and the phenyl of 3-, octyloxyphenyl iodonium hexafluorophosphate salt composite solution 10g (percent by weight is 50%)
Reaction concrete operations step is as follows:
In glass reactor, add 2g chloroform and 8g methyl methacrylate, logical N
2Removed oxygen in 20 minutes, under the lucifuge condition, add then prepared among the 10g embodiment 21, two (N-isopropyl-2,3,3 tri-methyl indole quinolines) squaraine dye and the phenyl of 3-, octyloxyphenyl iodonium hexafluorophosphate salt composite solution, after treating to dissolve fully, place illumination under the 1KW iodine-tungsten lamp under the room temperature, after 2 hours, the reactant methanol extraction can obtain white polymerizate polymethylmethacrylate.
Embodiment 5
Initiating agent when solidifying as the light solidifying coating material visible-light:
In the glass container of stirrer is housed, add 60g (percent by weight is 60%) epoxy acrylate CN124 and 20g (percent by weight is 20%) trimethylolpropane triacrylate (TMPTA), under 40 ℃, mix, get the B1 component.
Under the lucifuge condition, in another container, add prepared among 10g (percent by weight is 10%) hydroxy-ethyl acrylate and 10g (10%) embodiment 11,3-is two (right-N, accelerine) squaraine dye and phenyl, octyloxyphenyl hexafluoro-iodide antimonate salt composite solution, stir, dissolve the B2 component.
Under the lucifuge condition, the B2 component is added in the B1 component, mix.The solution for preparing is applied on the substrate, and drying and volatilizing is fallen solvent, places under the 1KW xenon lamp illumination 1 minute, the photocuring film.
Embodiment 6
Urethane acrylate 65g (percent by weight is 65%)
Pentaerythritol triacrylate 10g (percent by weight is 10%)
Isobornyl acrylate 15g (percent by weight is 15%)
Prepared among the embodiment 31, two (N-methyl-2-methyl-benzothiazole) squaraine dye and the phenyl of 3-, octyloxyphenyl hexafluoro-iodide antimonate salt composite solution 10g (percent by weight is 10%)
Press embodiment 5 method preparations, coating and illumination, get the high photocuring film of cross-linking density.
Claims (11)
1. the purposes of squaraine dye/salt compounded of iodine compound, it is characterized in that: the initiating agent when squaraine dye/salt compounded of iodine compound can be as the photopolymerisable initiating agent of vinyl monomer visible light/near infrared light or as photo-curing material visible light/near infrared light photocuring, the squaraine dye consumption is the 0.001-1wt% of light reaction system total amount; Wherein compound is to be 1～10 times of squaraine dye weight by squaraine dye and salt compounded of iodine with the weight of salt compounded of iodine, forms by electrostatic interaction and dipolar interaction in solvent.
2. the purposes of squaraine dye as claimed in claim 1/salt compounded of iodine compound is characterized in that described squaraine dye structure is suc as formula shown in (I):
Wherein, Ar is following group:
Or
R wherein
1Be H, alkyl or aryl; R
2Be H, halogen, alkyl, alkoxy, alkylamino or aryl; R
3Be H or alkyl.
3. the purposes of squaraine dye as claimed in claim 1/salt compounded of iodine compound is characterized in that described salt compounded of iodine structure is suc as formula shown in (II):
Wherein:
Or
R
4: H, OH, Cl or alkyl X
-: Cl
-, BF
4 -, AsF
6 -, pF
6 -, SbF
6 -, ClO
4 -Or TsO
-
4. the purposes of squaraine dye as claimed in claim 1/salt compounded of iodine compound, when it is characterized in that described squaraine dye/salt compounded of iodine compound as vinyl monomer visible light/near infrared light Photoepolymerizationinitiater initiater, each component and content thereof are:
Vinyl monomer 29.9wt%-70wt%
Organic solvent 29.9wt%-70wt%
Squaraine dye-salt compounded of iodine compound 0.001wt%-0.1wt%
5. the purposes of squaraine dye as claimed in claim 1/salt compounded of iodine compound, when it is characterized in that described squaraine dye/salt compounded of iodine compound as the initiating agent of visible light/near infrared light photo-curing material, each component and content thereof are:
Light reactive resin 40wt%～75wt%
Multi-functional acrylate's crosslinking chemical 10wt%～30wt%
Simple function group acrylate reactive diluent 5wt%～15wt%
Squaraine dye-salt compounded of iodine 1wt%～11wt%
Organic solvent 5wt%～10wt%
6. the purposes of squaraine dye as claimed in claim 4/salt compounded of iodine compound is characterized in that described vinyl monomer is esters of acrylic acid, acrylic amide, vinyl cyanide, styrene, vinyl acetate or vinyl pyrrole ketone.
7. the purposes of squaraine dye as claimed in claim 5/salt compounded of iodine compound is characterized in that described light reactive resin is epoxy acrylate, polyesters acrylate, urethane acrylate or saturated polyester not.
8. the purposes of squaraine dye as claimed in claim 5/salt compounded of iodine compound is characterized in that described multi-functional acrylate's crosslinking chemical is trimethylolpropane triacrylate, ethoxyquin or the third oxidation trimethylolpropane triacrylate, pentaerythritol triacrylate, double pentaerythritol methacrylate, alkane double methacrylate or glycols double methacrylate.
9. the purposes of squaraine dye as claimed in claim 8/salt compounded of iodine compound is characterized in that described glycols double methacrylate is tripropylene glycol double methacrylate, ethylene glycol diacrylate, glycerine double methacrylate, a condensed ethandiol double methacrylate, tirethylene glycol double methacrylate, hexanediol double methacrylate.
10. the purposes of squaraine dye as claimed in claim 5/salt compounded of iodine compound is characterized in that described simple function group acrylate reactive diluent is ethers simple function group acrylate, alkyl simple function group acrylate, hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
11. the purposes of squaraine dye as claimed in claim 10/salt compounded of iodine compound is characterized in that described alkyl simple function group acrylate is acrylic acid tetrahydrofuran ester, isobornyl acrylate; Hydroxyalkyl acrylates is hydroxy-ethyl acrylate or hydroxypropyl acrylate; Hydroxyalkyl methacrylates is hydroxyethyl methylacrylate or hydroxy propyl methacrylate.
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|---|---|---|---|
| CN99107347A CN1107884C (en) | 1999-05-19 | 1999-05-19 | Squaric acid dye/iodate composite and its use |
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|---|---|---|---|
| CN99107347A CN1107884C (en) | 1999-05-19 | 1999-05-19 | Squaric acid dye/iodate composite and its use |
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