CN1415679A - Visible light solidified compsn. - Google Patents
Visible light solidified compsn. Download PDFInfo
- Publication number
- CN1415679A CN1415679A CN 01134384 CN01134384A CN1415679A CN 1415679 A CN1415679 A CN 1415679A CN 01134384 CN01134384 CN 01134384 CN 01134384 A CN01134384 A CN 01134384A CN 1415679 A CN1415679 A CN 1415679A
- Authority
- CN
- China
- Prior art keywords
- methyl
- composition
- acrylate
- phenyl
- ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
A visible light solidified composition (paint or ink) contains at least one prepolymer containing unsaturated enyl (30-75 wt.%), at least one monomer containing unsaturated enyl (20-65 wt.%), at least one free group type optical trigger and/or cotrigger (1-10 wt.%) and assistant (0-20 wt.%).
Description
Invention field
The present invention relates to a kind of the irradiation by visible light source and cause that solidified contains the composition of free radical photo-initiation, said composition can be widely used in furniture application and the big area indoor and outdoor coating project.
Background of invention
Ultraviolet light polymerization polymerization technique in the past is applied in various fields, is used on woodenware, paper, metal and the plastics as the printing Lacquer finish, plays and decorates and provide protection; In electronic information field, be used for optical fiber, CD, electronic circuit board manufacturing etc.But ultraviolet ray has two aspect disadvantages: the one, and short-wave ray has injury to human body, needs fine shielding during use.Especially the effect of 200-315nm band ultraviolet is fast, and contact can make skin rubefaction, inflammation, cornea is burnt accidentally.Temporary blindness takes place sometimes.The 2nd, the ozone that ultraviolet ray produces air can cause headache, fatigue, and eyes and lung are had pungency, and long-term operator at this environment is had certain harm.These problems have limited the ultraviolet light polymerization polymerization technique to a certain extent in the more application and the development greatly of wide spectrum.And visible light solidified composition does not produce ozone because of not containing short wave ultraviolet in its light source, and skin is not had the effect of burning, and is safe in utilization easy to operate; Movable light source is coated with in big area more and loads onto application, more can have people's active place to use; Visible wavelength is long, and penetration power is strong, solidifies more favourable to bottom.
So people are attempting research and development can be by the composition of visible-light curing always.For example, US6106999 discloses a kind of visible-light curing resin combination, wherein adopts organoboron compound as light trigger, adopts Ar or YAG laser vibration light as light source; JP10-17604A discloses a kind of visible light photosensitive resin composition, wherein adopts titanium compound and coumarin compound as light trigger; US6110987 discloses photocurable composition, has wherein adopted season boron salt and free radical uv photopolymerization initiator; US5368990A discloses a kind of photocurable composition, wherein contains the diaryl iodine compound as polymerization starter.These visible lights cause positively charged ion as light trigger solidified example, and its initiator is very expensive, is difficult to promote the use of; In addition, CN1215421A discloses a kind of visible light polymerizable composition, and it contains the combination of polythiol and acylphosphine oxide class initiator, but the said composition shelf lives have only about a week, use very inconvenient.
Therefore, the visible light solidified composition that needs advantages such as security, the penetrance of advantage such as, good stability low in conjunction with ultraviolet light polymerization initiator price of a kind of while, quick solidifying and visible light is good.
The present invention satisfies above-mentioned requirements by providing a kind of as visible light solidified composition described in detail below.
Summary of the invention
The invention provides a kind of using visible light light source irradiation and cause that solidified contains the composition of light trigger, can replace existing ultraviolet light polymerization product, can extensively be used in the big area indoor and outdoor coating project in addition.
The invention provides a kind of like this visible light curable compositions, it comprises:
(1) at least a prepolymer that contains alkene class unsaturated group of 30-75% by weight;
(2) at least a monomer that contains alkene class unsaturated group of 20-65% by weight;
(3) at least a radical photoinitiator of 1-10% or radical photoinitiator and aided initiating by weight;
(4) auxiliary agent of 0-20% by weight.
In preferred embodiments, adopt the combination of radical photoinitiator and aided initiating in the component (3).
Detailed Description Of The Invention
Specifically, the invention provides a kind of visible light curable compositions, it comprises:
(1) at least a prepolymer that contains alkene class unsaturated group of 30-75% by weight;
(2) at least a monomer that contains alkene class unsaturated group of 20-65% by weight;
(3) at least a radical photoinitiator of 1-10% or radical photoinitiator and aided initiating by weight;
(4) auxiliary agent of 0-20% by weight.
Prepolymer that contains alkene class unsaturated group in can the composition by visible-light curing of the present invention and monomer are can polymerization under free radical causes and solidified material.Suitable this class prepolymer and the monomer that uses is well-known in the art.
The example of component (1) prepolymer comprises urethane (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate and polyethers (methyl) acrylate.
The example of urethane (methyl) acrylate comprises the reaction product that the reaction by (methyl) acrylate of hydroxyl and polyvalent alcohol and organic multiple isocyanate makes.The example of polyvalent alcohol comprises ethylene glycol, propylene glycol, butyleneglycol etc.The example of organic multiple isocyanate comprises tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.The example of (methyl) acrylate of hydroxyl comprises (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate and (methyl) vinylformic acid-2-hydroxypropyl ester.
Polyester (methyl) acrylic ester prepolymer comprises polyester polyol and (methyl) acrylic acid dehydrating condensation product.The example of polyester polyol comprises the reaction product of polyvalent alcohol and diprotic acid, for example ethylene glycol, polyoxyethylene glycol, hexanaphthene dimethyl alcohol, 3-methyl isophthalic acid of polyvalent alcohol wherein, 5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexylene glycol and TriMethylolPropane(TMP) or its oxyalkylene adduct, diprotic acid is hexanodioic acid, succsinic acid, phthalic acid, hexahydro-phthalic acid and terephthalic acid for example, or its acid anhydrides.
The epoxy acrylate class is for example adduct of (methyl) vinylformic acid reaction of Resins, epoxy and unsaturated carboxylic acid, comprises for example (methyl) acrylate of diglycidyl ether of epoxy (methyl) acrylate of epoxy (methyl) acrylate, phenol or cresol-novolac epoxy resin of bisphenol A type epoxy resin and polyethers.
The example of polyethers (methyl) acrylate comprises polyalkylene glycol two (methyl) acrylate, for example polyoxyethylene glycol two (methyl) acrylate and polypropylene glycol two (methyl) acrylate, and oxyalkylene modified product.
Component (2) monomer comprises styrenic, (methyl) acrylate, vinyl ether etc. and composition thereof.
The example of styrenic and derivative thereof comprises vinylbenzene, alpha-methyl styrene etc.(methyl) acrylate comprises (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate and (methyl) vinylformic acid-2-hydroxypropyl ester; (methyl) alkyl acrylate, for example (methyl) butyl acrylate, (methyl) isobutyl acrylate and (methyl) acrylic acid-2-ethyl polyhexamethylene; Alicyclic alkyl (methyl) acrylate, for example (methyl) cyclohexyl acrylate; Aryl (methyl) acrylate that replaces, for example (methyl) vinylformic acid benzyl ester; (methyl) vinylformic acid alcoxyl base ester, for example (methyl) vinylformic acid-2-methoxy ethyl ester and (methyl) vinylformic acid-2-ethoxyethyl group ester; (methyl) vinylformic acid iso-borneol thiazolinyl ester; With (methyl) acrylate that contains alkoxysilyl.Oxyalkylene adds the acrylate of phenol, for example (methyl) vinylformic acid phenoxy group ethyl ester, and the product of halogen nucleophilic substitution; The list of glycol (methyl) acrylate, for example list (methyl) acrylate of list (methyl) acrylate of list (methyl) acrylate of the list of ethylene glycol (methyl) acrylate, methoxyl group ethylene glycol, Tetraglycol 99 and triglycol; The example that contains the useful monomers of two or more ethylenic unsaturated groups comprises alkylene glycol two (methyl) acrylate, for example ethylene glycol bisthioglycolate (methyl) acrylate and propylene glycol two (methyl) acrylate; Low-molecular-weight polyalkylene glycol two (methyl) acrylate, for example glycol ether two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, dipropylene glycol two (methyl) acrylate and tripropylene glycol two (methyl) acrylate, with and the product of oxyalkylene modification; Polyvalent alcohol many (methyl) acrylate, for example trimethylolpropane tris (methyl) acrylate, tetramethylolmethane two or three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, TriMethylolPropane(TMP) four (methyl) acrylate, Dipentaerythritol five or six (methyl) acrylate, 1,6 hexanediol diacrylate with and the product of oxyalkylene modification; With two or three (methyl) acrylate with the modification of isocyanuric acid oxyalkylene.
The example of vinyl ether comprises hexanaphthene dimethyl alcohol divinyl ether, hydroxyethyl vinyl ether and triethylene glycol divinyl ether.
Other monomeric example comprises N-vinyl pyrrolidone, N-caprolactam, acryloyl morpholine, N-vinyl formamide and N-vinyl acetamide.
Composition of the present invention can add the compound that an ethylenic unsaturated group is arranged as required, to regulate the binding property and the snappiness of cured film.The example of the compound that these are useful comprises (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate and (methyl) vinylformic acid-2-hydroxypropyl ester; (methyl) acrylate of the ethylene oxide adduct of phenol, for example (methyl) vinylformic acid benzene oxygen ethyl ester; The list of glycol (methyl) acrylate, for example glycol monomethyl (methyl) acrylate, methoxyl group glycol monomethyl (methyl) acrylate, triglycol list (methyl) acrylate, Tetraglycol 99 list (methyl) acrylate; And N-vinyl compound, for example N-vinyl pyrrolidone and N-caprolactam.
Preferred polyvalent alcohol many (methyl) acrylate that uses is as two functionality 1,6 hexanediol diacrylates and three-functionality-degree Viscoat 295.1,6 hexanediol diacrylate is a kind of linear chain structure, gives the good snappiness of filming.Contain 3 two keys in the Viscoat 295, can improve the curing speed of filming.
Free radical photo-initiation in the component (3) is photochemical reaction can take place produce a free radical or a hydrionic compounds accepting illumination.Thereby the free radical that radical photoinitiator produced can cause the Raolical polymerizable of system and solidify.The light trigger of different structure has different absorption spectrums and free radical activity, and the light trigger of selecting comparatively to mate with the light source light spectrum energy distribution will improve curing speed greatly.When the formula for a product of definite purposes of design and using method, from used light source, set time require, film properties requires, and and many-side screening light trigger such as economy and different light trigger makes up may produce synergism.Some initiator is a light aging resisting, and some then xanthochromia and scent of can take place, and for example the tackiness agent of white ink, food product pack and printing-ink etc. must be avoided to tight product that special requirement are arranged for these.
The example of light trigger comprises bitter almond oil camphor and alkyl oxide thereof, for example bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor ethyl ether and bitter almond oil camphor isopropyl ether; Acetophenones, methyl phenyl ketone for example, 2,2-dimethoxy-2-phenyl methyl phenyl ketone (BDK), 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1, the 1-dichloroacetophenone, the 1-hydroxy acetophenone, 1-hydroxycyclohexylphenylketone (184), 2-hydroxy-2-methyl-1-phenyl third-1-ketone (1173), 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone (1116), 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl third-1-ketone (2959), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-propane-1-ketone (907) and 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone (369); Anthraquinone, for example 2-tertiary butyl anthraquinone, 1-chloroanthraquinone and 2-amyl anthraquinone; Thioxanthone, for example 2,4-dimethyl thioxanthone (DMTX), 2,4-diethyl thioxanthone (DETX), 2 (or 4)-isopropyl thioxanthones (ITX), 2-clopenthixal ketone (CTX) and 2,4-di-isopropyl thioxanthone; Ketal, for example methyl phenyl ketone dimethyl ketal and benzil dimethyl ketal; Benzophenones, for example benzophenone and 4-benzoyl-4 '-dimethyl diphenyl sulfide (DMS); And xanthone; Acyl group is seen oxygen compound as 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (TPO), two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide (819), two (2, the 6-dimethylbenzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide (BAPO), 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide (TPO-L).
For transparent varnish system, the addition of above-mentioned a kind of light trigger or multiple mixture is preferably based on 5 parts of 100 parts of visible light solidified compositions or littler, more preferably 2-3 part or littler.
For coloured system, the addition of light trigger is preferably based on 1-10 parts of 100 parts of compositions, more preferably 2-8 part or littler.
These light triggers can be used in combination with the aided initiating of amine, dimethylaminobenzoic acid ester class etc.Dimethylaminobenzoic acid ester class, for example ethyl-right-(dimethylamino) benzoic ether (EDAB), octyl group-right-(dimethylamino) benzoic ether (ODAB); Alkyl hydroxyethyl amine, for example: trolamine, tri-isopropanolamine, methyldiethanolamine; The acrylic ester monomer of amine modification or prepolymer.Good promoter action is arranged is well-known to aided initiating to carrying the Hydrogen initiator, and it has the oxygen inhibition of overcoming effect to radical polymerization simultaneously.
The addition of aided initiating is preferably based in the 0.1-10 of 100 parts of Photocurable compositions part or littler, more preferably 0.5-5 part.
Except that above-mentioned necessary component (1)-(3), can also comprise auxiliary agent composition (4).
For example, pigment is to make the necessary composition of printing ink, all pigment that are fit to manufacturing printing ink may be used among the present invention, and the color except that white, black, red, yellow and blue these primitive colour can directly be selected suitable pigment for use or reach the color requirement by the allotment primitive colour.When selected pigment granularity does not reach when requiring, can further reduce granularity by grinding plant and make it to reach service requirements.
Select pigment will consider its disadvantageous effect to curing speed, shelf stability also is a serious problem.
Suitable black pigment can be selected carbon black for use; The example of white pigment is a titanium dioxide; Blue pigments can be a phthalocyanine blue; Yellow ultramarine can be a diarylide yellow; Red pigment can be naphthol red, lithol red etc.The preferred 2-20% of the consumption of each pigment, more preferably 3-15%.
Sometimes also can add filler, for example: barium sulfate, silicon-dioxide, talcum powder, clay and lime carbonate, the performance that can effectively reduce the printing ink cost or give other.
Another kind of special filler is the nano material that can improve toughness and wear resistance, can be very effective in the occasion that particular requirement is arranged, though can increase the cost of product.
According to applied product difference, auxiliary agent also can be the additive of other type.For example, in order further to improve product stability and cured film weather resistance, can add one or more stoppers and weather resistance improving agent.The example of stopper has quinhydrones, Hydroquinone monomethylether, thiodiphenylamine and N-nitrophenyl oxyamine aluminium salt, and their addition should be based on the 10ppm-2% of said composition.The weather resistance improving agent comprises UV light absorber, photostabilizer and antioxidant.The preferred 0.01-5% of their addition.
Press usual method and use guaranteeing additives such as the effective film coalescence aid of product performance, thickening material, flow agent and defoamer.
Composition of the present invention can solidify with ultraviolet light source and visible light source, more preferably uses visible light source, because its safety and reliability and of many uses.If composition of the present invention is used for outdoor coating, then they also can solidify by solar ray.
The present invention preferably uses the visible light source of spectral range 350-750nm.They comprise sunlight, luminescent lamp, metal halide lamp, xenon lamp etc.Preferred metal halide lamp, the especially dysprosium lamp of using, its spectrum is at 350-650nm, and more effective spectral range is 380-480nm.
The present composition can be in packaging vessel stably stored more than six months.
The present composition can or be printed on the base material with the perception method coating of common institute.
Embodiment
Following embodiment and reference examples can illustrate further characteristics of the present invention, but are not subjected to the restriction of these examples.
Involved testing method sees the following form 1 in the embodiments of the invention
Table 1
| Test event | Reference standard |
| Snappiness | ????GB1731 |
| Gloss | ????GB1743 |
| Hardness | ????GB1730 |
Embodiment uses the 400W dysprosium lamp as light source, and test piece and filament are apart from 20cm, but the present invention is not limited thereto.
Reference examples uses the 500W ultraviolet lamp as light source, and test piece and filament are apart from 20cm.
Abbreviation among the embodiment has following connotation:
TPO-L:2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide (TPO-L)
TPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide (TPO)
1173:2-hydroxy-2-methyl-1-phenyl third-1-ketone (1173)
ITX:2 (or 4)-isopropyl thioxanthone (ITX)
907:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-propane-1-ketone (907)
184:1-hydroxycyclohexylphenylketone (184)
BDK:2,2-dimethoxy-2-phenyl methyl phenyl ketone (BDK)
CN972: acrylic-amino ester, the product of SARTOMER
CN120: epoxy acrylate, the product of SARTOMER
CN292: polyester acrylate, the product of SARTOMER
Embodiment 1
60 parts of bisphenol A epoxy acrylates
Viscoat 295 (TMPTA) 25
Hexanediyl ester (HDDA) 12.5
TPO-L????????????????????????????2.5
Trolamine 0.85
Set time 20s
Reference examples 1
The prescription sample of embodiment 1 is at UV lamp 20s set time.
Embodiment 2
Bisphenol A epoxy acrylate 60
Viscoat 295 (TMPTA) 25
Hexanediyl ester (HDDA) 12.5
TPO??????????????????????????????0.63
1173?????????????????????????????1.90
Trolamine 0.85
Set time 20s
Reference examples 2
The prescription sample of embodiment 2 is at UV lamp 10s set time.
Embodiment 3
CN972(SARTOMER)??????????????????9.6
CN120(SARTOMER)??????????????????29
CN292(SARTOMER)??????????????????19
Viscoat 295 (TMPTA) 29
Hexanediyl ester (HDDA) 9.6
ITX??????????????????????????????2.9
Trolamine 0.96
Set time 30s
Reference examples 3
The prescription sample of embodiment 3 is at UV lamp 30s set time.
Embodiment 4
CN120(SARTOMER)??????????????????48
CN292(SARTOMER)??????????????????19
Viscoat 295 (TMPTA) 29
BDK??????????????????????????????2.9
(dimethylamino)-ethyl benzoate 0.96
Set time 60s
Snappiness 15mm
60 ° of gloss 131
Hardness 0.67
Reference examples 4
The prescription sample of embodiment 4 is at UV lamp 20s set time
Snappiness 15mm
60 ° of gloss 132
Hardness 0.69
Embodiment 5
48 parts of CN120 (SARTOMER)
CN292(SARTOMER)?????????????????19
Viscoat 295 (TMPTA) 29
907?????????????????????????????2.9
ITX?????????????????????????????0.48
Trolamine 0.96
Set time 20s
Snappiness 15mm
60 ° of gloss 131
Hardness 0.67
Reference examples 5
The prescription sample of embodiment 5 is at UV lamp 10s set time
Snappiness 15mm
60 ° of gloss 132
Hardness 0.72
Embodiment 6
48 parts of CN120 (SARTOMER)
CN292(SARTOMER)?????????????????19
Viscoat 295 (TMPTA) 29
TiO2????????????????????????????5
TPO?????????????????????????????4
ITX?????????????????????????????0.48
907?????????????????????????????0.8
Trolamine 0.96
Set time 20s
Reference examples 6
The prescription sample of embodiment 6 is at UV lamp 20s set time.
Embodiment 7-12
Prepolymer and monomer be 8g altogether, adds initiator in the trolamine 0.1g mixture, be coated on the corresponding test panel, and after the curing, the curing membrane performance test result.
Table 2: the light trigger of each embodiment and content and test result
Annotate: 1) 1000 is the mixture of 80% (weight) 1173 and 20%184;
| Embodiment | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Light trigger | ???ITX | ???BDK | ????1173 | ????184 | ????1000 1) | ????4265 2) |
| Amount (g) | ???0.2 | ???0.3 | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| Set time | ???20s | ???40s | ????40s | ????40s | ????40s | ????40s |
| 60 ° of gloss | ???135 | ???131 | ????131 | ????135 | ????125 | ????/ |
| Snappiness | ???1mm | ???1mm | ????1mm | ????1mm | ????1mm | ????/ |
| Hardness | ???0.20 | ???0.24 | ????0.21 | ????0.23 | ????0.21 | ????/ |
2) 4265 is the mixture of 50% (weight) 1173 and 50%TPO.
Content disclosed according to the present invention, other embodiment of the present invention is conspicuous to those of ordinary skills.The specification sheets of this paper and embodiment only are intended as exemplary, and actual range of the present invention and essence will be indicated by claims of the present invention.
Claims (12)
1, a kind of visible light solidified composition, it comprises:
(1) at least a prepolymer that contains alkene class unsaturated group of 30-75% by weight;
(2) at least a monomer that contains alkene class unsaturated group of 20-65% by weight;
(3) at least a radical photoinitiator of 1-10% or radical photoinitiator and aided initiating by weight;
(4) auxiliary agent of 0-20% by weight.
2, according to the composition of claim 1, wherein, described prepolymer is selected from: urethane (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate and polyethers (methyl) acrylate.
3, according to the composition of claim 1, wherein, described monomer is selected from: styrenic, (methyl) acrylate, vinyl ether.
4, according to arbitrary composition of claim 1 to 3, wherein, described radical photoinitiator is selected from:
The substituted benzoyl phosphinoxides; A-hydroxy phenyl ketone; A-aminophenyl ketone; Replace thioxanthones; Or benzil class and derivative thereof; Benzophenone and composition thereof.
5, according to the composition of claim 4, wherein, described free radical photo-initiation is selected from: 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2, the 6-dimethylbenzoyl)-2,4,4-tri-methyl-amyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide; 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 1-hydroxycyclohexylphenylketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl third-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone; 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thia anthrone; Bitter almond oil camphor and ether thereof, benzil, benzoin dimethylether; Perhaps benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide; And the mixture of above-claimed cpd.
6, according to arbitrary composition of claim 1 to 3, wherein, it contains 0.1 to 10% aided initiating.
7, according to the composition of claim 6, wherein, aided initiating is selected from: the acrylic ester monomer or the prepolymer of dimethylaminobenzoic acid ester class, alkyl hydroxyethyl amine and amine modification.
8, according to the composition of claim 7, wherein, aided initiating is selected from: ethyl-right-(dimethylamino) benzoic ether, octyl group-right-(dimethylamino) benzoic ether, trolamine, tri-isopropanolamine or methyldiethanolamine and composition thereof.
9, according to the composition of claim 5, wherein, it contains 0.1 to 10% aided initiating.
10, the composition of claim 1 to 9 solidified under 350-750nm visible-range spectrographic light source irradiation is used.
11, according to the application of claim 10, wherein, the emmission spectrum of visible light source mainly concentrates in the 350-650nm scope.
12, according to the application of claim 11, wherein, what visible light source adopted is dysprosium lamp.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01134384 CN1415679A (en) | 2001-11-02 | 2001-11-02 | Visible light solidified compsn. |
| PCT/CN2002/000777 WO2003037936A1 (en) | 2001-11-02 | 2002-11-01 | Visible-light curable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01134384 CN1415679A (en) | 2001-11-02 | 2001-11-02 | Visible light solidified compsn. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1415679A true CN1415679A (en) | 2003-05-07 |
Family
ID=4672459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01134384 Pending CN1415679A (en) | 2001-11-02 | 2001-11-02 | Visible light solidified compsn. |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1415679A (en) |
| WO (1) | WO2003037936A1 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100549116C (en) * | 2003-08-08 | 2009-10-14 | 帝国化学工业公司 | Autoxidisable architectural coating compositions |
| CN101948643A (en) * | 2010-09-29 | 2011-01-19 | 安徽光谷新材料科技有限公司 | UV photocuring ink material for printing window lens of digital product |
| CN101979449A (en) * | 2010-11-30 | 2011-02-23 | 中国乐凯胶片集团公司 | Ultraviolet curing coating for white board |
| CN101993654A (en) * | 2010-12-17 | 2011-03-30 | 江苏海田技术有限公司 | Ultraviolet (UV) high elasticity primer |
| CN102061125A (en) * | 2010-12-17 | 2011-05-18 | 江苏海田技术有限公司 | UV (Ultra-Violet)-high elastic putty |
| CN102220070A (en) * | 2011-05-10 | 2011-10-19 | 上海富臣化工有限公司 | Ultraviolet solidified yellowing resistant and glossy woodenware paint and application technology thereof |
| CN102432995A (en) * | 2011-09-09 | 2012-05-02 | 上海金汇通创意设计发展股份有限公司 | Crosslinking plasticized resin liquid and production method of glue-free type paper-print composite film |
| CN102969116A (en) * | 2012-07-20 | 2013-03-13 | 横店集团东磁股份有限公司 | UV (ultraviolet) solidified bonding magnet and preparation method thereof |
| CN101319015B (en) * | 2006-12-28 | 2013-10-16 | 信越化学工业株式会社 | Photoradical curable resin composition and method for preparing the composition |
| CN103627311A (en) * | 2012-08-21 | 2014-03-12 | 上海大桥化工有限公司 | Vacuum plating UV-curable priming paint |
| CN103666073A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | Novel ultraviolet-curable silk-screen pearlescent ink and preparation method thereof |
| CN103666079A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | Ultraviolet curing printing ink for silk-screen printing and preparation method thereof |
| CN103666078A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | Ultraviolet light curing ink for ink jet printer and preparation method of ultraviolet light curing ink |
| CN103666075A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | UV (ultraviolet) curing ink with excellent curing performance and preparation method of UV curing ink |
| CN107868581A (en) * | 2017-11-26 | 2018-04-03 | 山西大学 | A kind of quick-drying ultraviolet light solidification back cover coating and preparation method thereof |
| CN109181383A (en) * | 2018-09-06 | 2019-01-11 | 左晓玲 | A kind of visible-light curing water paint and preparation method thereof |
| CN109679436A (en) * | 2018-12-24 | 2019-04-26 | 清远市美佳乐环保新材股份有限公司 | A kind of antifouling leather finishing agent and preparation method thereof |
| CN110527334A (en) * | 2019-09-11 | 2019-12-03 | 南京工程学院 | A kind of vacuum visible light room temperature curing composite membrane and preparation method based on carbon quantum dot |
| CN111471347A (en) * | 2020-05-15 | 2020-07-31 | 深圳市国瓷永丰源瓷业有限公司 | Screen printing medium composition, printing transfer paper and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7349990B2 (en) * | 2018-08-02 | 2023-09-25 | 林テレンプ株式会社 | Retardation film and its manufacturing method |
| EP3686252A1 (en) * | 2019-01-24 | 2020-07-29 | Agfa-Gevaert Nv | Radiation curable inkjet ink for manufacturing printed circuit boards |
| CN113405880A (en) * | 2021-05-21 | 2021-09-17 | 刘济忠 | Pathological specimen sealing liquid and preparation and sealing methods thereof |
| CN113547817A (en) * | 2021-07-30 | 2021-10-26 | 深圳市宏宇辉科技有限公司 | Anti-drape acrylic and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001069535A (en) * | 1999-08-30 | 2001-03-16 | Oki Comtec Ltd | Connection pin insertion/ejection mechanism |
-
2001
- 2001-11-02 CN CN 01134384 patent/CN1415679A/en active Pending
-
2002
- 2002-11-01 WO PCT/CN2002/000777 patent/WO2003037936A1/en not_active Application Discontinuation
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100549116C (en) * | 2003-08-08 | 2009-10-14 | 帝国化学工业公司 | Autoxidisable architectural coating compositions |
| CN101319015B (en) * | 2006-12-28 | 2013-10-16 | 信越化学工业株式会社 | Photoradical curable resin composition and method for preparing the composition |
| CN101948643A (en) * | 2010-09-29 | 2011-01-19 | 安徽光谷新材料科技有限公司 | UV photocuring ink material for printing window lens of digital product |
| CN101979449A (en) * | 2010-11-30 | 2011-02-23 | 中国乐凯胶片集团公司 | Ultraviolet curing coating for white board |
| CN101979449B (en) * | 2010-11-30 | 2013-04-24 | 中国乐凯胶片集团公司 | Ultraviolet curing coating for white board |
| CN101993654A (en) * | 2010-12-17 | 2011-03-30 | 江苏海田技术有限公司 | Ultraviolet (UV) high elasticity primer |
| CN102061125A (en) * | 2010-12-17 | 2011-05-18 | 江苏海田技术有限公司 | UV (Ultra-Violet)-high elastic putty |
| CN102061125B (en) * | 2010-12-17 | 2013-02-06 | 江苏海田技术有限公司 | UV (Ultra-Violet)-high elastic putty |
| CN102220070A (en) * | 2011-05-10 | 2011-10-19 | 上海富臣化工有限公司 | Ultraviolet solidified yellowing resistant and glossy woodenware paint and application technology thereof |
| CN102432995A (en) * | 2011-09-09 | 2012-05-02 | 上海金汇通创意设计发展股份有限公司 | Crosslinking plasticized resin liquid and production method of glue-free type paper-print composite film |
| CN102432995B (en) * | 2011-09-09 | 2013-08-07 | 上海金汇通创意设计发展股份有限公司 | Crosslinking plasticized resin liquid and production method of glue-free type paper-print composite film |
| CN102969116A (en) * | 2012-07-20 | 2013-03-13 | 横店集团东磁股份有限公司 | UV (ultraviolet) solidified bonding magnet and preparation method thereof |
| CN103627311A (en) * | 2012-08-21 | 2014-03-12 | 上海大桥化工有限公司 | Vacuum plating UV-curable priming paint |
| CN103666079B (en) * | 2013-11-29 | 2016-08-17 | 安徽吉思特智能装备有限公司 | A kind of silk screen printing UV curable ink and preparation method thereof |
| CN103666079A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | Ultraviolet curing printing ink for silk-screen printing and preparation method thereof |
| CN103666078A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | Ultraviolet light curing ink for ink jet printer and preparation method of ultraviolet light curing ink |
| CN103666075A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | UV (ultraviolet) curing ink with excellent curing performance and preparation method of UV curing ink |
| CN103666078B (en) * | 2013-11-29 | 2016-04-27 | 当涂县科辉商贸有限公司 | A kind of inkjet printer UV curable ink and preparation method thereof |
| CN103666073B (en) * | 2013-11-29 | 2016-04-27 | 当涂县科辉商贸有限公司 | A kind of Novel ultraviolet-curable silk-screen pearlescent ink and preparation method thereof |
| CN103666073A (en) * | 2013-11-29 | 2014-03-26 | 当涂县科辉商贸有限公司 | Novel ultraviolet-curable silk-screen pearlescent ink and preparation method thereof |
| CN107868581A (en) * | 2017-11-26 | 2018-04-03 | 山西大学 | A kind of quick-drying ultraviolet light solidification back cover coating and preparation method thereof |
| CN109181383A (en) * | 2018-09-06 | 2019-01-11 | 左晓玲 | A kind of visible-light curing water paint and preparation method thereof |
| CN109679436A (en) * | 2018-12-24 | 2019-04-26 | 清远市美佳乐环保新材股份有限公司 | A kind of antifouling leather finishing agent and preparation method thereof |
| CN110527334A (en) * | 2019-09-11 | 2019-12-03 | 南京工程学院 | A kind of vacuum visible light room temperature curing composite membrane and preparation method based on carbon quantum dot |
| CN110527334B (en) * | 2019-09-11 | 2022-03-25 | 南京工程学院 | Vacuum visible light room temperature curing composite film based on carbon quantum dots and preparation method |
| CN111471347A (en) * | 2020-05-15 | 2020-07-31 | 深圳市国瓷永丰源瓷业有限公司 | Screen printing medium composition, printing transfer paper and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003037936A1 (en) | 2003-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1415679A (en) | Visible light solidified compsn. | |
| CN1247712C (en) | Visible light cured metal paint | |
| CN1170904C (en) | Energy-curable composition for making pressure sensitive adhesive | |
| CN1526740A (en) | Photoinitiator composition capable of initiating via visible light and its use | |
| DE2534012C3 (en) | Process for the production of binders | |
| EP3263656B1 (en) | White ink composition for photocurable inkjet printing | |
| CN1247711C (en) | Visible light cured plastic paint | |
| CN1247713C (en) | Visible light cured woodenware paint | |
| CN1599735A (en) | Multi-functional thioxanthone photoinitiators | |
| EP1914279A2 (en) | Photo curable ink composition set, and recording method and recordings employing ink compositon set | |
| CN1959530A (en) | Ultraviolet light solidified coating in use for post processing of imaging material | |
| CN1964997A (en) | Radiation-curable high gloss overprint varnish compositions | |
| RU2705339C2 (en) | Composition of uv-curable coating having improved resistance to sunlight | |
| KR20120041728A (en) | Michael addition reaction product and active energy ray-curable composition | |
| CN1726264A (en) | Energy curable, water washable printing inks suitable for waterless lithographic printing | |
| JP2003508546A (en) | Water-compatible energy-curable composition containing maleimide derivative | |
| EP3604458B1 (en) | Photocurable ink composition and image formation method | |
| CN1422288A (en) | Composition | |
| CN1659194A (en) | Polyamphoteric superabsorbent copolymers | |
| JP6742502B2 (en) | Photocurable ink composition and image forming method | |
| CN1305911C (en) | A new class of amine coinitiators in photoinitiated polymerizations | |
| JP2001172554A (en) | Active energy ray curable metal coating composition containing maleimide derivative | |
| NZ208675A (en) | Photopolymerisation using alpha-halogenated benzene derivatives as photoinitiators | |
| JP7277674B2 (en) | Active energy ray-curable composition and method for producing matte coating film | |
| JP6727397B2 (en) | Photocurable ink composition and image forming method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ASS | Succession or assignment of patent right |
Owner name: ZHUHAI DONGCHENG CHEMICAL CO., LTD. Free format text: FORMER OWNER: HUNAN YADA NEW MATERIAL TECHNOLOGY CO., LTD. Effective date: 20030228 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20030228 Applicant after: Yingli Science and Technology Development Co., Ltd., Beijing Co-applicant after: Zhuhai Dongcheng Chemical Co., Ltd. Applicant before: Yingli Science and Technology Development Co., Ltd., Beijing Co-applicant before: Hu'nan Yada New Material Science & Technology Co. Ltd. |
|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |