CN110389499A - A kind of Photocurable composition and its application - Google Patents
A kind of Photocurable composition and its application Download PDFInfo
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- CN110389499A CN110389499A CN201810722231.1A CN201810722231A CN110389499A CN 110389499 A CN110389499 A CN 110389499A CN 201810722231 A CN201810722231 A CN 201810722231A CN 110389499 A CN110389499 A CN 110389499A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Spectroscopy & Molecular Physics (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention discloses a kind of Photocurable composition and its application, which is selected from compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular compound of primary structure.Photocurable composition disclosed by the invention has preferably response to the light source in 200-500nm wave-length coverage, composition curing rate is very fast, the properties of cured film are more excellent, so that Photocurable composition of the invention can be in the further genralrlization application of the fields such as paint, coating, ink, moulding material.
Description
Technical field
The present invention relates to photocuring technology field, specially a kind of Photocurable composition and its in multiple solidification fields
Using.
Background technique
Photocuring is the emerging environmental protection industry (epi) gradually to attract attention in recent years, with solidification rate is very fast and production cost
Lower advantage.Photocuring system in the prior art generally mainly includes: light source and Photocurable composition, but the prior art
In most of photocuring systems there are absorbability of the Photocurable composition to light source is poor, generally require to consolidate for a long time
Change or need the problem of being heating and curing, this is easy, and the production cost increases and what production efficiency reduced asks to bringing in production
Topic.In view of above, developing a kind of Photocurable composition in 200-500nm wave-length coverage with excellent light-cured performance is this
Field technical staff's technical problems to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of Photocurable compositions, have to the light source in 200-500nm wave-length coverage
There is preferable response, curing rate is very fast, and the properties of cured article all have advantage.
Specifically, Photocurable composition of the invention is included the compound of structure shown in formula (I) and/or is changed with formula (I)
Close the macromolecular compound that object is primary structure:
(I), wherein R1、R2, X, Y be independently represented each other hydrogen, C1-C40's
Linear or branched alkyl group, C1-C40Alkoxy ,-O-CO-R3At least one of base, nitro, cyano, halogen, R3Represent C3-C20
Naphthenic base, C4-C20Alkyl-cycloalkyl or cycloalkyl-alkyl, C2-C40Contain ester group or C2-C40Base containing epoxy group
Group, and the acyclic-CH in above-mentioned group2Optionally replaced by-O- ,-CO- ,-NH- ,-S- or Isosorbide-5-Nitrae-phenylene.
Of the invention can be formula (I) compound by gathering by the macromolecular compound of primary structure of formula (I) compound
Close (including homopolymerization and copolymerization), esterification or ester exchange reaction and the macromolecular compound that is formed.
Illustratively, formula (I) compound can be one of compound shown in having structure, two or more
Combination:
Further, Photocurable composition of the invention can form first kind composition, which includes
Following component:
(A1) selected from the compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular of primary structure
Compound；In technical solution of the present invention, by percentage to the quality, the content of component (A1) in the composition is 0.001-
10%, preferably 0.01-8%.
(B1) first kind performed polymer；
In Photocurable composition of the invention, component (B1) can be (methyl) acrylic ester compound and/or alkene
Pyridyl ethers compound.Specifically it is chosen as (methyl) the esters of acrylic acid chemical combination recorded in the specification of patent 201610238231.5
At least one of object and alkenyl ether compound.
Illustratively, component (B1) can be selected from or include: phthalic acid list [2- (methyl) acryloyl-oxyethyl] ester,
ω-carboxy-polycaprolactone list (methyl) acrylate etc. has list (methyl) propylene of the polymer of carboxyl and hydroxyl in two ends
Acid esters；Hydroxyethyl (methyl) acrylate-maleic ester, hydroxypropyl (methyl) acrylate-maleic ester, two rings penta 2
The insatiable hungers such as alkene-maleate or the multifunctional (methyl) acrylate of (methyl) acryloyl group with 1 carboxyl and 2 or more
And polyacid；(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) glycidyl
Ester, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate,
(methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid,
(methyl) stearyl acrylate, (methyl) lauryl acrylate, (methyl) methoxyethyl acrylate, (methyl) acrylic acid diformazan
Base amino methyl, (methyl) acrylate, (methyl) acrylic-amino propyl ester, (methyl) acrylic acid dimethyl
Poly- (ethyoxyl) ethyl ester of amino propyl ester, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid, (methyl) acrylate, butoxy
Ethoxy ethyl ester, (methyl) ethylhexyl acrylate, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid tetrahydrofuran
Ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, ethylene glycol two (methyl) third
Olefin(e) acid ester, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) propylene
Acid esters, propylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) propylene
Acid esters, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six
(methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three
(methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three [(methyl) acryloyl ethyl] isocyanide ureas
The ester of the unsaturation monoacid and polyalcohol or polyphenol such as acid esters, polyester (methyl) acrylate oligomer；Vinyltoluene, second
Alkenyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4- vinylbenzenesulfonic acid, vinyl benzyl methyl ether, vinyl benzyl contracting
The unsaturation aromatic compound such as water glycerin ether；The beta-unsaturated ketones such as methyl vinyl ketone；The vinyl alcohols such as allyl alcohol, crotonyl alcohol；
The second such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether
Alkene ether；Unsaturated acyls imines such as maleimide, N-phenylmaleimide, N- N-cyclohexylmaleimide etc..This hair
In bright technical solution, by percentage to the quality, the content of component (B1) is 80-98%, preferably 80-97%.
(C1) radical photoinitiator；
Common radical photoinitiator can be selected such as in C1 of the invention: Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone,
α-amine alkyl phenones, acylphosphine oxide, benzophenone, benzoin class, benzil class, heterocycle arone class, oxime esters light draw
Send out agent etc..Based on considering for the composite factors such as cost, for example light-initiated efficiency of the effect being used cooperatively, curing rate, component (C1)
At least one of the radical photoinitiator preferably recorded in the specification of patent 201610238231.5.
Illustratively, C1 can be selected from or include: phenyl biphenyl ketone, 1- hydroxyl -1- 2-benzoyl-cyclohexane, benzil diformazan
Base ketal, 1- benzyl -1- dimethylamino -1- (4 '-morpholino benzoyl) propane, 2- morpholinyl -2- (4 '-methyl mercapto)
The chloro- 4- propoxythioxanthone of benzoyl propane, thioxanthones, 1-, isopropyl thioxanthone, diethyl thioxanthone, ethyl hydrazine, 4-
Benzoyl -4 '-methyldiphenyl sulfide, benzoin butyl ether, 2- hydroxy-2-methyl phenyl propyl- 1- ketone, 2- hydroxyl -2-
(4 '-isopropyl) benzoyl propane, 4- butylbenzoyl chloroform, 4- phenoxybenzoyl methylene chloride, benzene first
Bis- (9 '-acridinyl) heptane of acyl group methyl formate, 1,7-, 9- normal-butyl -3,6- bis- (2 '-morpholino isobutyryl) carbazoles, 2-
Bis- (the trichloromethyl)-s- triazines of methyl -4,6-, bis- (the trichloromethyl)-s- triazines of 2- phenyl -4,6-, 2- naphthalene -4,6- bis- (three
Chloromethyl)-s- triazine, 4,4- azodiisobutyronitrile, triphenylphosphine, camphorquinone, N-1414, N-1717, N-1919, NCI-831,
NCI-930 (ADEKA corporation), IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE
02 (BASF system), TR-PBG-304, TR-PBG-305, TR-PBG-314 (Tronly system) etc..In above-mentioned photocuring of the invention
In composition, by percentage to the quality, the content of component (C1) in the composition is 0.001-10%, preferably 0.1-10%.
Further, Photocurable composition of the invention can form the second class composition, which includes
Following component:
(A1) selected from the compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular of primary structure
Compound；In technical solution of the present invention, by percentage to the quality, the content of component (A1) in the composition is 0.001-
10%, preferably 0.01-8%.
(B2) the second class performed polymer；
Component (B2) is the performed polymer containing epoxy group and/or the performed polymer containing alkenyl ether groups, the performed polymer
It can be monomer, prepolymer and/or resin.The performed polymer containing epoxy group can be selected from or including patent
201610235083.1, the glycidyl ether type epoxy resin recorded in 201610238062.5 specifications, glycidol esters
Epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan epoxy resin, aliphatic category epoxy resin or oxa- ring fourth
At least one of alkyl compound.
Illustratively, component (B2) can be selected from or including having cyclic ether groups such as epoxy group, oxetane groups
With the compound of dioxolanes group；With the acrylic acid or vinyl compound of above-mentioned substituent group on its side chain；Carbonic acid
Ester compounds；Low molecular weight melamine compound；Vinyl carbazole；Styrene derivative；α-methylstyrene derivative；Vinyl
Alcohol ester includes the ester of vinyl alcohol and acryloyl group and methylacryloyl；And the list with cationic polymerizable vinyl bonds
Body etc..
Further, as epoxide, can be selected from or including alicyclic epoxide compound, as Celloxide2021,
Celloxide2021A, Celloxide2021P, Celloxide2081, Celloxide2000 and Celloxide3000
(Daicel Chemical)；(methyl) acrylate compounds with epoxy group, such as CyclomerA200 and Cyclomer
M100；Such as the methacrylate of the methylglycidyl of MGMA；Beta-methyl epichlorohydrin；Australene olefinic oxide；With 12-14
The alpha-olefin monoepoxide of a carbon atom；Alpha-olefin monoepoxide with 16-18 carbon atom；Such as Dimac S-300K
Epoxidized soybean oil；Such as the epoxidized linseed oil of DimacL-500；Such as more officials of Epolead GT301 and EpoleadGT401
Energy epoxide etc..Alicyclic epoxide compound (such as Cylacure, Dow Chemical) can also be selected from；Terminal hydroxy group is by ring
Hydrogenation that oxygen groups replace and alicyclic ring low molecular weight oxybenzene compound；Polyhydroxy fatty race alcohol/alicyclic alcohol,
As ethylene glycol, glycerol, neopentyl alcohol, hexylene glycol and trimethyl alcohol propane glycidol ether；It polymerize with ethylene oxide base
One end of object has the compound of glycidyl ether；The contracting of hexahydro-phthalic acid or the aromatic polyvalent polyol carboxylic acid of hydrogenation
Water glyceride etc..
The aliphatic that can be selected from or alicyclic oxetane compound include two [1- ethyl (3- oxetanyls)]
Methyl ether, 3- ethyl -3- (2- ethyl hexyl yloxymethyl) oxetanes, [(1- ethyl -3- oxetanyl) methoxyl group]
Butylcyclohexane, bis- [(1- ethyl -3- oxetanyl) methoxyl group] hexamethylenes contain oxa- containing wherein at least introducing one
The compound of the alicyclic group of cyclobutane group, such as bis- [(1- ethyl -3- oxetanyl) methoxyl group] norbornanes；?
The ether compound containing aliphatic polyol such as ethylene glycol, propylene glycol and neopentyl alcohol, the alcohol of the azetidine containing dioxygen can be used
Such as 3- ethyl -3- hydroxymethyl oxetane and the aliphatic polyol dehydrogenative condensation.In addition, what be can be selected from contains aromatic series
The specific example of the oxetane compound of skeleton include bis- [(1- ethyl -3- oxetanyl) methoxyl group] benzene of Isosorbide-5-Nitrae -,
1,3- bis- [(1- ethyl -3- oxetanyl) methoxyl group] benzene, 4,4 '-bis- [(3- ethyl -3- oxetanyl) methoxies
Base] at least one of biphenyl or phenol novolacs oxetanes；May include or selected from Tronly Tcm series of products,
Specifically: Tcm101, Tcm102-1, Tcm105, Tcm202, Tcm203EO, Tcm204, Tcm205EO, Tcm206EO,
At least one of Tcm207, Tcm207ME, Tcm208 or Tcm210.In the inventive solutions, with mass percent
Meter, the content of component (B2) are 80-99%, preferably 80-98%.
(C2) cationic photoinitiator；
In the inventive solutions, component (C2) can be aryl diazonium salts, salt compounded of iodine, sulfosalt, aryl cyclopentadienyl iron
The combination of one or more of salt.It is comprehensive based on cost, for example light-initiated efficiency of the effect being used cooperatively, curing rate etc.
Factor is considered, component (C2) preferably salt compounded of iodine and sulfosalt photoinitiator, especially 201610235083.1 explanation of patent
The compound of structure shown in the formula (II) recorded in book and/or (III) and its further preferably in the chemical structure enumerated
At least one, cationic photoinitiator can be Al [OC (CF3)3]4-、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、
(SbX6)-、(AsX6)-、(PX6)-, sulfonate ion, B (C6X5)4-Or [(Rf)bPF6 -b]-substitution the salt compounded of iodine, sulfosalt or
The compound that anion is formed in aryl cyclopentadienyl molysite, wherein X is F or Cl, RfIndicate that >=80% hydrogen atom is replaced by fluorine atoms
Alkyl, b indicates the integer of 1-5, and b RfGroup is identical or different.In technical solution of the present invention, with quality percentage
Than meter, the content of component (C2) in the composition is 0.001-10%, preferably 0.1-10%.
Further, Photocurable composition of the invention can form third class composition, which includes
Following component:
(A1) selected from the compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular of primary structure
Compound；
(B1) first kind performed polymer；
(C1) radical photoinitiator；
(B2) the second class performed polymer；
(C2) cationic photoinitiator.
(B1) in the third class composition may include or selected from Tronly Thm series of products, specifically:
Thm201, Thm202, Thm203, Thm204, Thm205, Thm206, Thm207, Thm301, Thm403, Thm401 or Thm404
At least one of；(B2) in third class composition may include or selected from Tronly Tcm series of products, specifically:
Tcm101、Tcm102-1、Tcm105、Tcm202、Tcm203EO、Tcm204、Tcm205EO、Tcm206EO、Tcm207、
At least one of Tcm207ME, Tcm208 or Tcm210.In technical solution of the present invention, by percentage to the quality, above-mentioned group
The content divided is successively are as follows: (A1) 0.001-10%, (B1) 28-70%, (C1) 0.001-10%, (B2) 25-70%, (C2)
0.001-10%.
In technical solution of the present invention, according to products application needs, above-mentioned first kind composition, the second class composition,
It can further include in three classes composition component (D1), (D1) is organic and/or inorganic assistant commonly used in the art,
Including but not limited to color material, levelling agent, curing accelerator, light heat acid agent, plasticizer, adhesion promoters, filler, defoaming
Agent, surface conditioner, antioxidant, ultraviolet absorbing agent, dispersing aid, anticoalescent, catalyst, thickener, sensitizer or
At least one of crosslinking agent etc..
Illustratively, as color material, pigment, dyestuff, natural pigment etc. can be enumerated, these color materials can be used alone, or will
It is two or more to be used in mixed way.As pigment, such as nitro compound can be used, contain nitrogen compound and its metal complex, quinoline
Compound, anthraquinone compounds, coumarin compound, phthalocyanine compound, isoindoline compounds, quinoline azone compound, anthanthrene
Naphtoquinone compounds, purple cyclic ketone compound, perylene compound, pyrrolo-pyrrole-dione compound, thioindigo compound, dioxazines
Close object, triphenylmethane compounds, quinophthalone compound；Graphite, ketjenblack EC, active carbon, carbon fiber, carbon nanotube, spiral shell
Revolve shape carbon fiber, carbon nanohorn, carbon aerogels, fullerene；Nigrosine, pigment black 7, titanium be black, chrome oxide green, cobalt green, cobalt blue, manganese
System, native indigo plant in general Shandong, ultramarine, zinc yellow, red iron oxide, synthesis iron oxide black, the carbon black obtained with oven process, channel process or pyrolysis method, second
Acetylene black, Ketjen black, lampblack or by after its chemical modification, average grain diameter >=8nm, oil absorption be 90ml/100g substance below, from
CO, CO in volatile ingredient at 950 DEG C2Whole oxygen amount of calculating are every 100m2The surface area of carbon black is the substance of 9mg or more,
Etc. organic or inorganic pigments.As dyestuff, can enumerate azo dyes, anthraquinone dye, indigoid dye, triarylmethane dye,
Xanthene dye, alizarin dyes, acridine dye, Stilbene dyestuff, thiazole dye, naphthol dye, quinoline dye, nitro dye, phthalocyanine dye
Material, cyanine dyes etc..
Illustratively, as can be used as antireflection agent, conductive agent, stabilizer, fire retardant, mechanical strength enhancer, special
The filler of the purposes such as wavelength absorption agent or oleophobic ink agent, can enumerate such as: nickel oxide, yttrium oxide, titanium oxide, zinc oxide, oxidation
The metal oxides such as calcium, silica, aluminium oxide；Layered clay mineral, calcium carbonate, magnesium carbonate, cobalt system, manganese systems, glass powder, cloud
Mother, talcum powder, kaolin, ferrocyanide, metal sulfate, sulfide, selenides, alumina silicate, calcium silicates, aluminium hydroxide,
Platinum, gold, silver, copper etc..
In technical solution of the present invention, the weight additive amount of the filler is component first kind composition, the second class group
0-0.4 times, preferably 0.001-0.4 times for closing the sum of object or third class composition additive amount.
Illustratively, it as the dispersing aid for making color material and/or filler dispersion, stabilization can be added, can enumerate such as:
Macromolecule dispersing agent, the tool that the BYK series of BYK-Chemie, the polyester with basic functionality, polyethers or polyurethane are constituted
Nitrogen-atoms is as basic functionality and the functional group with nitrogen-atoms is amine and/or its quaternary ammonium salt and amine value is 20-
The dispersing agent etc. of 95mgKOH/g.
In technical solution of the present invention, the weight additive amount of the color material or dispersing aid be component first kind composition,
0-0.1 times, preferably 0.005-0.06 times of the sum of second class composition or third class composition additive amount.
Photocurable composition provided by the invention can be used preparation method in the prior art and be prepared, and such as pacify in yellow
Under full lamp, being uniformly mixed after each component is weighed according to quantity can be obtained Photocurable composition of the invention, be kept in dark place.For
The sequence that reactant is added in mixer is B1, A1, (auxiliary agent) C1 by a kind of composition；It, will be anti-for the second class composition
The sequence for answering object to be added in mixer is B2, A1, (auxiliary agent) C2；For third class composition, reactant is added in mixer
Sequence be B1, A1, C1, B2, (auxiliary agent) C2；Wherein, any of the above-described component includes two small components or more, is needed pre-
It is first uniformly mixed to obtain pre-composition, then pre-composition is mixed with other components by step.Then, spinner, sized roller applicator, stick can be passed through
Device, die coating device, curtain coaters, various printings, impregnating known approaches are applied by Photocurable composition application provided by the invention
In in the support substrates such as soda-lime glass, quartz glass, semiconductor substrate, metal, paper, plastics；It can also be briefly applied to the branch such as film
It is transferred in other support substrates again after on support group body, so that there is no limit for its application method.
In addition, the light source as energy-ray used when solidifying composition of the invention, can enumerate such as: super-pressure
Mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, deuterium lamp, chemical lamp, in 365,385,
395, the ultraviolet ranges such as 405nm have the LED light of wavelength, fluorescent lamp, tungsten lamp, Nd-YAG3 times of wave laser, He-Cd laser, nitrogen
Laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excite Solid State Laser, i ray (365nm), h ray
(405nm), g ray (436nm) etc. have wavelength for 200nm or more and the active ray of 500nm or less wavelength etc., composition
The energy such as electron beam, alpha ray, β ray, gamma-rays, X-ray and neutral sub-line can also be used in solidification.In addition, as needed can also
To adjust irradiation by light splitting filter as long wavelength cutoff filter, short wavelength's cut-off filter, bandpass filter
Light, light exposure are preferably 1~500mJ/cm2。
Compared with prior art, the Photocurable composition disclosed by the invention containing structural formula I is to 200-500nm wavelength model
Enclosing interior light source has preferably response, and with host component type alternative, more, zero solvent adds, is solid Photocurable composition
The advantages that change process Diamond Search discharges, can apply paint, coating, ink and in terms of, items after solidification
Can show it is more excellent, have the stronger market competitiveness, be suitable for further large-scale promotion application.
Specific embodiment
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.Raw material used in embodiment unless otherwise stated, is versatile material in the art, can lead to
Commercial channel is crossed to buy.
Application as Photocurable composition of the invention in transition paint field can be enumerated: a kind of vacuum metal film plating use
Transition paint base composition, the formula in the first kind composition of technical solution of the present invention are as follows:
(A1) selected from the compound with structure shown in formula (I)；Wherein, X, Y are independently represented each other hydrogen, R1Represent first
In base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, n-hexyl, n-heptyl, 1-7 base amyl or n-octyl
It is a kind of when, R2Representative and R1Identical group；By percentage to the quality, the content of component (A1) in the composition is 0.001-
10%；
(B1) first kind performed polymer；
Component (B1) be selected from aliphatic urethane acrylate (B11, NORMIC RJ4235), epoxy acrylate (B12,
NORMIC E58), pure acrylate (B13, NORMIC HK-1018), polyester acrylate (B14, RYOJI RJ544) or three
At least one of hydroxymethyl-propane triacrylate (B15, DSM-AGI Agisyn 2811)；By percentage to the quality, component
(B1) content is 80-98%.
(C1) radical photoinitiator；
Component (C1) be selected from 2- hydroxy-2-methyl phenyl propyl- 1- ketone (C10, Ai Kemu chemical industry), TR-PBG-305 (C11),
At least one of 1- hydroxycyclohexyl phenyl ketone (C12), by percentage to the quality, the content of component (C1) in the composition
For 0.01-10%；
(D1) auxiliary agent；
Component (D1) is selected from levelling agent (in BYK371 (D101), efka 3778 (D102) or SP-934 (D103 is won sincere)
At least one), adhesion promoter (Castle 6300 (D111), Golsperse-8276 (D112), CD9051 (D113)
At least one of) and conductive agent (at least one of BYK-ES80 (D121), EA-562 (D122)), with mass percent
Meter, the weight content of each component in the composition is 0.005-0.06 times of the sum of (A1), (B1) and (C1) three's additive amount, tool
Body is as shown in table 1 below:
Table 1
Above-mentioned composition is the preparation method comprises the following steps: under yellow safety lamp, and the formula for first including by above-mentioned A1 is from top to bottom successively
Be dispersed with stirring after feeding intake uniformly, the formula that B1 includes is dispersed with stirring uniformly after from top to bottom successively feeding intake, the formula that C1 includes by
It is dispersed with stirring after successively feeding intake under above uniformly, the formula that D1 includes is dispersed with stirring uniformly after from top to bottom successively feeding intake；Again according to
It is secondary B1, A1, D1, C1 are successively fed intake after be dispersed with stirring uniformly, obtain vacuum metal film plating transition paint base composition, be protected from light guarantor
It deposits.
By the above-mentioned paint base composition prepared, using 15 μm of bar spreaders, once coating forms a film on substrate, then leads to
The UVLED crawler type light source for crossing wavelength 385nm is exposed (with light intensity 178mJ/cm2Exposure 3 times), it is put at room temperature after exposure
It sets and is tested for the property afterwards for 24 hours, the substrate is the test level tinplate and domestic 1060 ordinary aluminum plate for meeting GB2520.
The cured film of above-mentioned substrate surface is tested below, wherein adhesive force is tested referring to GB/T9286-1998；
Upper plating property uses vacuum coating equipment electric plating method, with flat appearance, light, does not fall off by baige method test coating as upper plating
Excellent, on the contrary then upper plating property is general；Salt fog resistance test is under the conditions of 25 DEG C, relative humidity 50% with 10% (mass concentration) chlorine
Change sodium distilled water solution to drip in above-mentioned cured film, observe afterwards for 24 hours, test result is used: zero (unchanged), ◎ (elephant skin), × it is (de-
Falling) three grades evaluates；Water boiling resistance is boiled in the distilled water for hang over the 2/3 area leaching of the substrate with cured film boiling
Boiling keeps 2h, observes coating conditions, and test result uses: zero (unchanged), ◎ (falling off on a small quantity), × (largely falling off) three etc.
Grade is evaluated；Hardness test (tests pencil using MTTSU-BISHI/UNI, not destroy painting referring to GB/T6739-2006 test
The highest pencil hardness of film is that result is evaluated)；Resistivity/M Ω .cm, is tested using resistivity tester.Tinplate and
The test result of domestic 1060 ordinary aluminum plate is respectively in the following table 2 .1 and 2.2:
Table 2.1
Table 2.2
As seen from the above table, when technical solution of the present invention is applied to vacuum metal film plating transition paint base composition, have
Host component type alternative is more, the addition of zero solvent, there is preferably response, solidification process Diamond Search to discharge ultraviolet source
The advantages that, the properties after solidification show more excellent.
Above-mentioned a kind of vacuum metal film plating transition paint base composition, in the third class composition of technical solution of the present invention
In preferably be formulated it is as follows:
(A1) selected from the compound with structure shown in formula (I)；
Wherein, X, Y are independently represented each other hydrogen, R1Represent methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
When one of n-pentyl, n-hexyl, n-heptyl, 1- ethylpentyl or n-octyl, R2Representative and R1Identical group；With quality
Percentages, the content of component (A1) in the composition are 0.001-10%；
(B1) first kind performed polymer；
Component (B1) is selected from aliphatic urethane acrylate (B11, NORMIC RJ4235；B16, RYOJI RJ429),
Epoxy acrylate (B12, NORMIC E58；B17, RYOJI RJ34714), pure acrylate (B13, NORMIC HK-1018；
B18, JAZO JZ-402), polyester acrylate (B14, RYOJI RJ544；B19, Dongtou perseverance found HL-2238) or trihydroxy methyl
At least one of propane triacrylate (B15, DSM-AGI Agisyn 2811)；By percentage to the quality, component (B1)
Content is 28-70%；
(C1) radical photoinitiator；
Component (C1) is selected from 2- hydroxy-2-methyl phenyl propyl- 1- ketone (C10, Ai Kemu chemical industry；It is C13, so outstanding that be full of), TR-
At least one of PBG-305 (C11), 1- hydroxycyclohexyl phenyl ketone (C12), by percentage to the quality, component (C1) In
Content in composition is 0.001-10%；
(B2) the second class performed polymer；
Component (B2) is selected from Celloxide2021 (B20), Celloxide3000 (B21) (is
DaicelChemical), structural formula isB22, structural formula beAt least one of B23 or Tronly Thm series of products, by percentage to the quality, group
Dividing the content of (B2) in the composition is 25-70%；
(C2) cationic photoinitiator；
Component (C2) is selected from structural formula(C20) or structural formula be(C21), at least one of PAG20001 (C22, Tronly system).With quality hundred
Divide than meter, the content of component (C2) in the composition is 0.001-10%.
(D1) auxiliary agent；
Component (D1) is selected from levelling agent (in BYK371 (D101), efka 3778 (D102) or SP-934 (D103 is won sincere)
At least one), adhesion promoter (Castle 6300 (D111), Golsperse-8276 (D112), CD9051 (D113)
At least one of) and conductive agent (BYK-ES80 (D121), EA-562 (D122), at least one in efka 6780 (D123)
Kind), by percentage to the quality, the weight content of each component in the composition is (A1), (B1), (C1), (B2) and (C2) five
0.005-0.06 times of the sum of additive amount, shown in table 3 specific as follows:
Table 3
The preparation method of composition of above-described embodiment 9-16 are as follows: under yellow safety lamp, first include by A1 in above-mentioned table 3
Formula is dispersed with stirring uniformly after from top to bottom successively feeding intake, and the formula that B1 includes is dispersed with stirring after from top to bottom successively feeding intake
Even, the formula that C1 includes is dispersed with stirring uniformly, after the formula that B2 includes from top to bottom successively feeds intake after from top to bottom successively feeding intake
It is dispersed with stirring uniformly, the formula that C2 includes is dispersed with stirring uniformly after from top to bottom successively feeding intake, and the formula that D1 includes is from top to bottom
It is dispersed with stirring after successively feeding intake uniformly；It is dispersed with stirring after successively B1, A1, B2, C2, D1, C1 successively feed intake again uniformly, obtains vacuum
Metal-coated membrane transition paint base composition, is kept in dark place.
By the above-mentioned paint base composition prepared, using 15 μm of bar spreaders, once coating forms a film on substrate, then leads to
The crawler type ultraviolet source for crossing wavelength 200-450nm is exposed (70201 models, with light intensity 120mJ/cm2Exposure 1 time),
Place after exposure and be tested for the property afterwards for 24 hours at room temperature, the substrate be meet GB2520 test level tinplate and
Domestic 1060 ordinary aluminum plate.
The embodiment in table 3 is tested using the test method of embodiment 1-8 below, tinplate and domestic 1060
The test result of ordinary aluminum plate is respectively in the following table 4 .1 and 4.2:
Table 4.1
Table 4.2
By the above test result it is found that using technical solution of the present invention resulting vacuum metal film plating transition priming paint group
Closing object has that upper plating property is excellent, salt fog resistance, water boiling resistance are good, and hardness and the more excellent advantage of adhesive force use the formula of A1
Combination may make composition photosensitive property of the invention more excellent, and energy needed for solidifying is lower, and curing rate is very fast, solidification effect
Fruit is preferable, solidification process VOC free, can meet later period vacuum plating requirement (metal film plated does not fall off, improves yields), have
Effect improves utilization efficiency of coatings, is suitable for further genralrlization application.
As Photocurable composition of the invention in the application of field of functional coatings, can enumerate: a kind of porcelain class substrate use is anti-
Shield type Photocurable composition is preferably formulated as follows in the second class composition of technical solution of the present invention:
(A1) selected from the compound with structure shown in formula (I)；Wherein, X, Y are independently represented each other hydrogen, R1Represent first
In base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, n-hexyl, n-heptyl, 1- ethylpentyl or n-octyl
It is a kind of when, R2Representative and R1Identical group；By percentage to the quality, the content of component (A1) in the composition is 0.001-
10%；
(B2) the second class performed polymer；Component (B2) be selected from Celloxide2021 (B20), Celloxide3000 (B21),
Celloxide2081 (B24) (being DaicelChemical), structural formula are
B22, structural formula beB23, structural formula beB25,
Structural formula isAt least one of B26 or Tronly TCM series of products, with matter
Percentages are measured, the content of component (B2) in the composition is 80-99%；
(C2) cationic photoinitiator；
Component (C2) is selected from structural formula(C20), structural formula be(C21), PAG20001 (C22, Tronly system) or structural formula beAt least one of (C23).By percentage to the quality, component (C2)
Content in the composition is 0.001-10%.
(D1) auxiliary agent；
Component (D1) is selected from levelling agent (in BYK371 (D101), efka 3778 (D102) or SP-934 (D103 is won sincere)
At least one)；Adhesion promoter (Castle 6300 (D111), Golsperse-8276 (D112), CD9051 (D113)
At least one of)；Filler (oxide powder and zinc (Lishui chemical industry D124), talcum powder (silver-colored plumage GY915 D125), magnesium silicate
At least one of (safe prosperous D126 processed)), by percentage to the quality, levelling agent, adhesion promoter are distinguished in the composition
Weight content is 0.005-0.06 times of the sum of (A1), (B2) and (C2) three's additive amount, the weight of filler in the composition
Content is 0.001-0.4 times of the sum of (A1), (B2) and (C2) three's additive amount, filler D127 shown in table 5 be D124,
The mixture that D125, D126 three in mass ratio 1.3: 1.4: 1 is formed, specific as follows:
Table 5
The preparation method of composition of above-described embodiment 17-24 are as follows: under yellow safety lamp, first include by A1 in above-mentioned table 5
Formula from top to bottom successively feed intake after be dispersed with stirring uniformly, the formula that B2 includes is dispersed with stirring after from top to bottom successively feeding intake
Even, the formula that C2 includes is dispersed with stirring uniformly, after the formula that D1 includes from top to bottom successively feeds intake after from top to bottom successively feeding intake
It is dispersed with stirring uniformly；It is dispersed with stirring after successively A1, B2, D1, C2 successively feed intake again uniformly, it is solid to obtain porcelain class substrate protection type light
Change composition, is kept in dark place.
By the above-mentioned composition prepared, using 20 μm of bar spreaders, once coating forms a film on substrate, then only respectively
It is exposed from by the UVLED crawler type light source of wavelength 365nm (with light intensity 178mJ/cm2Exposure 3 times) and wavelength 200-
The crawler type ultraviolet source of 450nm is exposed (70201 models, with light intensity 150mJ/cm2Exposure 1 time), in room after exposure
It is tested for the property after placing the porcelain substrate that must have protecting film for 24 hours under temperature, the substrate is 96 oxidations that armour rainbow flies electronics
Aluminium ceramics experimental plate, below tests embodiment 17-24, test method are as follows: (1) by the above-mentioned porcelain substrate with protecting film
Using the high-end Three-angle vancometer of WG68 type in 60 ° of test cured film glossiness；(2) by the above-mentioned porcelain substrate with protecting film
It is impregnated in amyl acetate and has seen whether blistering, elephant skin or obscission for 24 hours；(3) by the above-mentioned porcelain substrate with protecting film
It impregnates in acetone and has seen whether blistering, elephant skin or obscission for 24 hours；(4) by the above-mentioned porcelain substrate with protecting film 5%
It is impregnated in mass fraction ammonium hydroxide and has seen whether blistering, elephant skin or obscission for 24 hours；(5) by the above-mentioned porcelain base with protecting film
Plate impregnates in 5% mass fraction sulfuric acid has seen whether blistering, elephant skin or obscission for 24 hours；(6) there is protecting film by above-mentioned
Porcelain substrate impregnated in 95% mass fraction ethyl alcohol and seen whether blistering, elephant skin or obscission for 24 hours；UVLED condition and
The test result of all-wave length ultraviolet source is respectively in the following table 6 .1 and 6.2:
Table 6.1
Table 6.2
By the above test result it is found that Photocurable composition of the invention is applied to a kind of porcelain class base in field of functional coatings
When material protection type Photocurable composition, all there is good photocuring effect under mercury lamp and LED light source, sensitivity is high, Gu
It is fast to change speed, gained solidify coating glossiness up to 110% or more, with excellent chemical-resistant reagent (amyl acetate, acetone,
Ammonium hydroxide, ethyl alcohol etc.) performance can be suitable for being applicable on the ceramic article surface of profession customization, such as LED light, high-frequency induction welder, power supply
The protection on ceramic material structural unit surface or chemical laboratory porcelain class flume surface, laboratory in module or powerful device
The surfacecti proteon of porcelain class wall brick tile surface etc. is suitable for further genralrlization application.
It as Photocurable composition of the invention in the application of field of functional coatings, can enumerate: a kind of building panels use
Waterproof isolation-type Photocurable composition is preferably formulated as follows in the first kind composition of technical solution of the present invention:
(A1) selected from the compound with structure shown in formula (I)；
Wherein, (A1) is at least one of (I2), (I5), (I7), (I13), (I17), (I21), (I23) or (I26)；
By percentage to the quality, the content of component (A1) in the composition is 0.001-10%；
(B1) first kind performed polymer；
Component (B1) be selected from aliphatic urethane acrylate (B11, NORMIC RJ4235), epoxy acrylate (B12,
NORMIC E58), pure acrylate (B13, NORMIC HK-1018), polyester acrylate (B14, RYOJI RJ544) or three
At least one of hydroxymethyl-propane triacrylate (B15, DSM-AGI Agisyn 2811)；By percentage to the quality, component
(B1) content is 80-98%.
(C1) radical photoinitiator；
Component (C1) is selected from 2- hydroxy-2-methyl phenyl propyl- 1- ketone (C10, Ai Kemu chemical industry), TR-PBG-304,1- hydroxyl
At least one of butylcyclohexyl phenyl ketone (C12), DETX or ITX, by percentage to the quality, component (C1) is in the composition
Content be 0.01-10%；
(D1) auxiliary agent；
Component (D1) is selected from levelling agent (in BYK371 (D101), efka 3778 (D102) or SP-934 (D103 is won sincere)
At least one), adhesion promoter (Castle 6300 (D111), Golsperse-8276 (D112), CD9051 (D113)
At least one of), activating agent (KF-6001 (SHIN-ETSU HANTOTAI's chemistry system, number-average molecular weight 1700) or FM-4411 (CHISSO system, number
At least one of average molecular weight 1000)) and pigment (pigment that Phthalocyanine Blue BGS and No313 are respectively Ecosol), with quality
Percentages, the weight content of each component in the composition are the 0.005- of the sum of (A1), (B1) and (C1) three's additive amount
0.06 times, shown in table 7 specific as follows:
Table 7
The composition of above-described embodiment 25-32 the preparation method comprises the following steps: under yellow safety lamp, first match what above-mentioned A1 included
Side is dispersed with stirring uniformly after from top to bottom successively feeding intake, and the formula that B1 includes is dispersed with stirring uniformly after from top to bottom successively feeding intake,
The formula that C1 includes is dispersed with stirring uniformly after from top to bottom successively feeding intake, and the formula that D1 includes stirs after from top to bottom successively feeding intake
It is uniformly dispersed；It is dispersed with stirring after successively B1, A1, D1, C1 successively feed intake again uniformly, obtains building panels waterproof isolation-type light
Solidification composition filling is kept in dark place.
By the above-mentioned composition prepared, using 20 μm of bar spreaders, once coating forms a film on substrate, then passes through wave
The crawler type ultraviolet source of long 200-450nm is exposed (70201 models, with light intensity 150mJ/cm2Exposure 1 time), exposure
It is tested for the property after placing for 24 hours the building panels that must have protecting film at room temperature afterwards, the substrate is to fly Kou Wenhua
Floor tile in the MX61551 imitation wood line room that the simple ceramic tile of FC- brick red wall brick and one that brick provides provides, below to embodiment 25-32 into
Row test, test method are as follows: (1) using the DM-500 measurement solidification film surface pure water of consonance interface science Co., Ltd. manufacture
Contact angle, specifically: be added dropwise the water droplet of 1.5 μ L on substrate, the contact angle of water after measurement is just added dropwise and after 10min, point
It carry out not measure for 3 times, using its average value as the value of contact angle.(2) solidify the landing angle of film surface water by measurement to evaluate
Slickness, specifically: using the DM-500 and DM-SA of the manufacture of consonance interface science Co., Ltd., it is added dropwise 30 μ L's on substrate
Water droplet is tilted objective table with the speed of 7.5 degrees seconds, and water droplet is started mobile angle as the value for sliding angle, is carried out 2 times
Measurement, using its average value as the value for sliding angle, test result is as shown in table 8.1 and table 8.2.
Table 8.1
Table 8.2
By above-mentioned table 8.1 and table 8.2 it is found that using having after the resulting Photocurable composition solidification of technical solution of the present invention
There are preferable surface smoothness, the higher waterproofness of tolerable degree, resistance to dirt adhesion etc., thus using technical side of the invention
The resulting Photocurable composition of case can be used for the metope, the metope on ground or ceiling and its component of configuration of building, especially
Can be used as premises bathroom bathtub or bathroom furred ceiling, toilet washstand, closestool or the area kitchen basin Deng Shi component table
Face protection, can effectively inhibit using scale as the attachment of the various dirts of representative, and even if using strong containing acid, the irritation of alkali
Cleaning agent, be not easy to produce rotten or deterioration, be suitable for further genralrlization application.
It as Photocurable composition of the invention in the application of ink area, can enumerate: a kind of tank surface photocuring
Composition, the formula in the second class composition of technical solution of the present invention are as follows:
(A1) selected from the compound with structure shown in formula (I)；By percentage to the quality, component (A1) is in the composition
Content is 0.001-10%；
(B2) the second class performed polymer；Selected from B20, B21, B22, B23, B24, B25, B26, B27 or Tronly TCM series
At least one of product, the B27 are Tetrachem TTA26, and by percentage to the quality, component (B2) is in the composition
Content be 80-99%；
(C2) cationic photoinitiator；Selected from least one of C20, C21, C22, C23 or C24, the C24 is
Tronly PAG20002, by percentage to the quality, the content of component (C2) in the composition are 0.001-10%.
(D1) auxiliary agent；Selected from levelling agent (at least one of D101, D102 or D103), filler (Du Pont Ti-pure
R-706 titanium dioxide (D127), BASF blue Heliogen K7090 (D128)), by percentage to the quality, levelling agent is combining
Weight content in object is 0.005-0.06 times of the sum of (A1), (B2) and (C2) three's additive amount, and filler is in the composition
Weight content be 0.001-0.4 times of the sum of (A1), (B2) and (C2) three's additive amount, table 9 specific as follows:
Table 9
The preparation method of composition of above-described embodiment 33-40 are as follows: under yellow safety lamp, first include by A1 in above-mentioned table 5
Formula from top to bottom successively feed intake after be dispersed with stirring uniformly, the formula that B2 includes is dispersed with stirring after from top to bottom successively feeding intake
Even, the formula that C2 includes is dispersed with stirring uniformly, after the formula that D1 includes from top to bottom successively feeds intake after from top to bottom successively feeding intake
It is dispersed with stirring uniformly；It is dispersed with stirring after successively A1, B2, D1, C2 successively feed intake again uniformly, obtains tank surface photocurable composition
Object is kept in dark place.
By the above-mentioned composition prepared using the mode of roller coating in tank body (smooth surface can, Shenzhen Rong Sheng packaging；Light
Face aluminium pot, ten thousand Baolong's metal of Fujian) it forms a film on lateral surface, so that film carrier tank body is passed through the UVLED light source of wavelength 365nm respectively
It is exposed (light intensity 500mJ/cm2, runner removes tank body after exposure) and wavelength 200-450nm ultraviolet source into
Row exposure (light intensity 150mJ/cm2, runner removes tank body after exposure), film carrier tank body is placed for 24 hours at room temperature after exposure
It must paint and be tested for the property after tank body.Above-mentioned tank body film carrier process can also pass through spraying method.
Above-mentioned unlike material, the different cured colouring tank bodies of light source are cut along its vertical centerline direction and to be formed below
The test strip of 3cm × 7cm obtains 32 test strips of corresponding embodiment 33-40, test method are as follows:
(1) flexibility tests test strip referring to GB/T1731-1993, specially by test strip along length
In mandrel 1, mandrel 2, mandrel 3, mandrel 4, mandrel 5, mandrel 6, mandrel 7, magnifying glass successively is used after being bent 2-3s in direction
Above-mentioned solidifying film layer surface is observed, the smallest mandrel before destroying with solidifying film layer indicates the flexibility of solidifying film layer；
(2) adhesion performance uses QFH paint film lattice drawing instrument by the solidifying film layer of test strip referring to GB/T9286-1998
Hand cut is hundred lattice, and the transparent test tape of 3M is sticked on hundred lattice of the different directions pulled, and force glues adhesive tape securely
On solidifying film layer surface and lattice position is drawn, 3M adhesive tape one end is held in 2min, steadily tears off adhesive tape in 1s in 60 ° of angles；
(3) water boiling resistance, which soaks 2/3 area of test strip to boil in the distilled water for hanging over boiling, keeps 2h, and observation applies
Layer situation, test result using: zero (unchanged), ◎ (falling off on a small quantity), × (largely falling off) three grades are evaluated；
(4) wearability adds 500g weight using NO.0000 steel wool as friction media using 228 type abrasion performance testing machines
Code, test strip solidifying film layer surface reciprocating friction 300 times, test result is used: zero (unchanged), × (a small amount of scratch),
● (a large amount of scratches) three grades is evaluated；UVLED condition and the test result of all-wave length ultraviolet source are respectively in following table
10.1 and 10.2:
Table 10.1
Table 10.2
By the above test result it is found that Photocurable composition of the invention is applied in ink area is applied to tank surface
When, all there is preferable photocuring effect under mercury lamp and UV LED light source, curing rate is very fast, flexibility, adhesive force, water-fast
Boiling property, wearability are preferable, are suitable for the three pieces tank body in profession customization or the popularization and application of two panels tank surface, such as easy-to-draw beverage
The external coating of tank, sealed food tank, sealed seed tank etc. or printing are suitable for further genralrlization application.
To sum up, the Photocurable composition disclosed by the invention containing structural formula I is to the light source in 200-500nm wave-length coverage
With preferable response, with host component type alternative, more, zero solvent adds composition, solidification process Diamond Search discharges,
The very fast advantage of curing rate, can apply paint, coating, ink and in terms of, the properties after solidification are equal
Performance is more excellent, so that Photocurable composition of the invention can be further in fields such as paint, coating, ink, moulding materials
It promotes and applies.
Claims (10)
1. a kind of Photocurable composition, it is characterized in that: the composition includes the compound of structure shown in formula (I) and/or with formula (I)
Compound is the macromolecular compound of primary structure:
Wherein, R1、R2, X, Y be independently represented each other hydrogen, C1-C40It is straight
Chain or branched alkyl, C1-C40Alkoxy ,-O-CO-R3At least one of base, nitro, cyano, halogen, R3Represent C3-C20's
Naphthenic base, C4-C20Alkyl-cycloalkyl or cycloalkyl-alkyl, C2-C40Contain ester group or C2-C40Contain cycloalkyl groups,
And acyclic-the CH2- in above-mentioned group is optionally replaced by-O- ,-CO- ,-NH- ,-S- or Isosorbide-5-Nitrae-phenylene.
2. a kind of Photocurable composition as described in claim 1, it is characterized in that: formula (I) compound is having structure shownization
Close at least one of object:
3. Photocurable composition according to claim 1, it is characterized in that: the Photocurable composition be first kind composition,
Second class composition or third class composition, the first kind composition includes following component:
(A1) selected from the compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular chemical combination of primary structure
Object；(B1) first kind performed polymer；(C1) radical photoinitiator；
(B1) in the first kind composition is (methyl) acrylic ester compound and/or alkenyl ether compound；Institute
(C1) stated is Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, benzophenone, benzene
At least one of acyloin class, benzil class, heterocycle arone class or oxime ester lightlike initiating agent；
The second class composition includes following component:
(A1) selected from the compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular chemical combination of primary structure
Object；(B2) the second class performed polymer；(C2) cationic photoinitiator；
(B2) in the second class composition is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, contracting
Water glycerol amine epoxy resin, linear aliphatic same clan epoxy resin, aliphatic category epoxy resin or oxygen heterocycle butane
At least one of；It (C2) is the group of one or more of aryl diazonium salts, salt compounded of iodine, sulfosalt, aryl cyclopentadienyl molysite
It closes；
The third class composition includes following component:
(A1) selected from the compound with structure shown in formula (I) and/or using formula (I) compound as the macromolecular chemical combination of primary structure
Object；
(B1) first kind performed polymer；
(C1) radical photoinitiator；
(B2) the second class performed polymer；
(C2) cationic photoinitiator；
(B1) in the third class composition is (methyl) acrylic ester compound and/or alkenyl ether compound；Institute
(C1) stated is Dialkoxy acetophenones, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, benzophenone, benzene
At least one of acyloin class, benzil class, heterocycle arone class or oxime ester lightlike initiating agent；(B2) is glycidol ether
Based epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan epoxy resin, rouge
At least one of fat same clan epoxy resin or oxygen heterocycle butane.
4. Photocurable composition according to claim 3, it is characterized in that: the cationic photoinitiator is Al [OC
(CF3)3]4-、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-, sulfonate ion, B (C6X5)4-Or
[(Rf)bPF6 -bThe compound that anion is formed in the]-substitution salt compounded of iodine, sulfosalt or aryl cyclopentadienyl molysite, wherein X be F or
Cl, RfThe alkyl that the hydrogen atom of expression >=80% is replaced by fluorine atoms, b indicate the integer of 1-5, and b RfGroup it is identical or mutually not
It is identical；
It also include component (D1), (D1) packet in the first kind composition, the second class composition or third class composition
Include color material, levelling agent, curing accelerator, light heat acid agent, plasticizer, adhesion promoters, filler, defoaming agent, surface adjustment
Agent, antioxidant, ultraviolet absorbing agent, dispersing aid, anticoalescent, catalyst, thickener, sensitizer, crosslinking agent or hot polymerization
Close inhibitor in at least one of methyl phenyl ethers anisole, quinhydrones, pyrocatechol, tert-butyl catechol or phenthazine.
5. Photocurable composition according to claim 3, it is characterized in that: the Photocurable composition is in transition paint field
Using are as follows: a kind of vacuum metal film plating transition paint base composition, the formula in first kind composition are as follows:
(A1) selected from the compound with structure shown in formula (I)；
Wherein, X, Y are independently represented each other hydrogen, R1Represent methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, positive penta
When one of base, n-hexyl, n-heptyl, 1- ethylpentyl or n-octyl, R2Representative and R1Identical group；
(B1) first kind performed polymer；
Component (B1) be selected from aliphatic urethane acrylate (NORMIC RJ4235), epoxy acrylate (NORMIC E58),
Pure acrylate (NORMIC HK-1018), polyester acrylate (RYOJI RJ544) or trimethylolpropane trimethacrylate
At least one of (DSM-AGI Agisyn 2811)；
(C1) radical photoinitiator；
Component (C1) is selected from 2- hydroxy-2-methyl phenyl propyl- 1- ketone (Ai Kemu chemical industry), TR-PBG-305,1- hydroxy-cyclohexyl
At least one of phenyl ketone；
(D1) auxiliary agent；
Component (D1) is selected from levelling agent (at least one of BYK371, efka 3778 or SP-934), adhesion promoter
At least one of (Castle 6300), Golsperse-8276, CD9051) and conductive agent (in BYK-ES80, EA-562
It is at least one)；
A kind of vacuum metal film plating transition paint base composition, the formula in third class composition are as follows:
(A1) selected from the compound with structure shown in formula (I)；
Wherein, X, Y are independently represented each other hydrogen, R1Represent methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, positive penta
When one of base, n-hexyl, n-heptyl, 1- ethylpentyl or n-octyl, R2Representative and R1Identical group；
(B1) first kind performed polymer；Selected from aliphatic urethane acrylate (NORMIC RJ4235；RYOJI RJ429), epoxy
Acrylate (NORMIC E58；RYOJI RJ34714), pure acrylate (NORMIC HK-1018；JAZO JZ-402), it is poly-
Ester acrylate (RYOJI RJ544；Dongtou perseverance founds HL-2238) or trimethylolpropane trimethacrylate (DSM-AGI
At least one of Agisyn 2811)；
(C1) radical photoinitiator；Selected from 2- hydroxy-2-methyl phenyl propyl- 1- ketone (Ai Kemu chemical industry；It is so outstanding that be full of), TR-
At least one of PBG-305,1- hydroxycyclohexyl phenyl ketone；
(B2) the second class performed polymer；It is selected from Celloxide2021, Celloxide3000, structural formulaStructural formula isOr Tronly Thm series
At least one of product；
(C2) cationic photoinitiator；It is selected from structural formulaOr structural formula isAt least one of PAG20001；
(D1) auxiliary agent；Selected from levelling agent (at least one of BYK371, efka 3778 or SP-934), adhesion promoter
(at least one of Castle 6300, Golsperse-8276, CD9051) and conductive agent (BYK-ES80, EA-562, efka
At least one of 6780).
6. Photocurable composition according to claim 3, it is characterized in that: the Photocurable composition is in field of functional coatings
Application are as follows: a kind of porcelain class substrate protection type Photocurable composition, the formula in the second class composition are as follows:
(A1) selected from the compound with structure shown in formula (I)；
Wherein, X, Y are independently represented each other hydrogen, R1Represent methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, positive penta
When one of base, n-hexyl, n-heptyl, 1- ethylpentyl or n-octyl, R2Representative and R1Identical group；
(B2) the second class performed polymer；It is selected from Celloxide2021, Celloxide3000, Celloxide2081, structural formulaStructural formula isStructural formula isStructural formula isOr Tronly Tcm series of products
At least one of；
(C2) cationic photoinitiator；It is selected from structural formulaStructural formula isPAG20001 or structural formula areAt least one of；
(D1) auxiliary agent；Selected from levelling agent (at least one of BYK371, efka 3778 or SP-934)；Adhesion promoter
(at least one of Castle 6300, Golsperse-8276, CD9051)；Filler (oxide powder and zinc, talcum powder, magnesium silicate
At least one of).
7. Photocurable composition according to claim 3, it is characterized in that: the Photocurable composition is in field of functional coatings
Application are as follows: with waterproof isolation-type Photocurable composition, the formula in first kind composition is as follows for a kind of building panels:
(A1) selected from the compound with structure shown in formula (I)；Wherein, (A1) be (I2), (I5), (I7), (I13), (I17),
(I21), at least one of (I23) or (I26)；
(B1) first kind performed polymer；Selected from aliphatic urethane acrylate (NORMIC RJ4235), epoxy acrylate
(NORMIC E58), pure acrylate (NORMIC HK-1018), polyester acrylate (RYOJI RJ544) or trihydroxy methyl third
At least one of alkane triacrylate (DSM-AGI Agisyn 2811)；
(C1) radical photoinitiator；Selected from 2- hydroxy-2-methyl phenyl propyl- 1- ketone (Ai Kemu chemical industry), TR-PBG-304,
At least one of 1- hydroxycyclohexyl phenyl ketone, DETX or ITX；
(D1) auxiliary agent；Selected from levelling agent (at least one of BYK371, efka 3778 or SP-934), adhesion promoter
(at least one of Castle 6300, Golsperse-8276, CD9051), activating agent are (in KF-6001 or FM-4411 extremely
Few one kind) and pigment.
8. Photocurable composition according to claim 3, it is characterized in that: (B1) in the third class composition may include
Or selected from Tronly Thm series of products, specifically: Thm201, Thm202, Thm203, Thm204, Thm205, Thm206,
At least one of Thm207, Thm301, Thm403, Thm401 or Thm404；(B2) in third class composition may include or
Selected from Tronly Tcm series of products, specifically: Tcm101, Tcm102-1, Tcm105, Tcm202, Tcm203EO, Tcm204,
At least one of Tcm205EO, Tcm206EO, Tcm207, Tcm207ME, Tcm208 or Tcm210；In second class composition
(B2) may include or selected from Tronly Tcm series of products, specifically: Tcm101, Tcm102-1, Tcm105, Tcm202,
At least one of Tcm203EO, Tcm204, Tcm205EO, Tcm206EO, Tcm207, Tcm207ME, Tcm208 or Tcm210.
9. Photocurable composition according to claim 3, it is characterized in that: the Photocurable composition answering in ink area
With are as follows: a kind of tank surface Photocurable composition, the formula in the second class composition are as follows:
(A1) selected from the compound with structure shown in formula (I)；
(B2) the second class performed polymer；It is selected from Celloxide2021, Celloxide3000, Celloxide2081, structural formulaStructural formula isStructural formula isStructural formula isTetrachem TTA26 or
At least one of Tronly TCM series of products；
(C2) cationic photoinitiator；It is selected from structural formulaStructural formula isTronly PAG20001, structural formula areOr at least one of Tronly PAG20002；
(D1) auxiliary agent；Selected from levelling agent (at least one of BYK371, efka 3778 or SP-934), filler (Du Pont Ti-
At least one of pure R-706 or BASF blue Heliogen K7090).
10. Photocurable composition according to claim 1, it is characterized in that: the energy that the composition uses when solidifying is penetrated
The light source of line is: ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, deuterium lamp, change
Learn lamp, LED light, fluorescent lamp, tungsten lamp, Nd-YAG3 times of wave laser, He-Cd laser, N_2 laser, Xe-Cl excimer laser, Xe-F
The active light that excimer laser, semiconductor excitation Solid State Laser, i ray, h ray, g ray etc. are 200-500nm with wavelength
Line；Electron beam, alpha ray, β ray, gamma-rays, X-ray and neutron ray energy-curable also can be used in the solidification of composition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021057804A1 (en) * | 2019-09-29 | 2021-04-01 | 常州格林感光新材料有限公司 | Cationic curing composition for plastic substrate, coating material, plastic product and application |
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| CN101457058A (en) * | 2007-12-12 | 2009-06-17 | 深圳市高域化学材料有限公司 | Ultraviolet cured primer special for vacuum coating |
| CN107300829A (en) * | 2016-04-15 | 2017-10-27 | 常州强力先端电子材料有限公司 | A kind of application of novel cation photocuring system and combinations thereof |
| CN107300833A (en) * | 2016-04-15 | 2017-10-27 | 常州强力先端电子材料有限公司 | A kind of application of new free-radical photocuring system and combinations thereof |
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| WO2021057804A1 (en) * | 2019-09-29 | 2021-04-01 | 常州格林感光新材料有限公司 | Cationic curing composition for plastic substrate, coating material, plastic product and application |
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