CN109880434A - Curable composition and use thereof - Google Patents
Curable composition and use thereof Download PDFInfo
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- CN109880434A CN109880434A CN201910135138.5A CN201910135138A CN109880434A CN 109880434 A CN109880434 A CN 109880434A CN 201910135138 A CN201910135138 A CN 201910135138A CN 109880434 A CN109880434 A CN 109880434A
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 14
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The present invention relates to a kind of curable compositions and application thereof.The curable compositions include: 30-70 parts of epoxide；5-25 parts of polyfunctional group vinyl ethers compound；5-30 parts of oxygen heterocycle butane；0.1-2 parts of photosensitizer；With 1-12 parts of cationic initiator.The composition has improved curing performance.
Description
Technical field
The present invention relates to photo-curing material fields, and in particular to a kind of curable compositions and application thereof.
Background technique
In recent years, environmental protection, energy conservation, efficient UVLED (UV LED) light source technology are developed rapidly.With
Traditional mercury lamp is compared, UVLED light source have heavy metal free pollution, low energy consumption, long service life, open i.e. close without preheat,
The advantages that ozone free.
As a kind of cold light source, the light of UVLED light source output is single band ultraviolet light, and wave crest is relatively narrow, is generally focused on
Within the scope of ± the 5nm of specific wavelength.Some UVLED light sources can issue wavelength be 365nm, 385nm, 395nm, 405nm or
The ultraviolet light of 410nm.
Inventors have found that being easy to deposit when the single band ultraviolet light using UVLED light source output is used for cure curable material
In the bad problem of curing performance.
Summary of the invention
The disclosure provides a kind of curable compositions, by weight, including following components:
Epoxide: 30-70 parts (such as 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or 65 parts)；
Polyfunctional group vinyl ethers compound: 5-25 parts (such as 10 parts, 15 parts or 20 parts)；
Oxygen heterocycle butane: 5-30 parts (such as 10 parts, 15 parts, 20 parts or 25 parts)；
Photosensitizer: 0.1-2 parts (such as 0.5 part, 1 part or 1.5 parts)；
Cation light initiator: 1-12 parts (such as 2 parts, 5 parts, 8 parts or 10 parts).
In some embodiments, curable compositions further include: fluoride resin, weight content section are (0,15
Part].
In some embodiments, curable compositions further include: pigment, weight content section be (0,45 part].
In some embodiments, epoxide is containing epoxy group (such as the epoxy group of cationic photocurable
Group) compound.At least contain an epoxy group in epoxide molecule, preferably comprises two epoxy groups.
In some embodiments, the parts by weight of epoxide are 35-70 parts in curable compositions, particularly preferably
40-60 parts.
In some embodiments, epoxide includes cycloaliphatic epoxy resin, divinylbenzene dioxide, lemon
Alkene dioxide, epoxidised soybean oil, epoxidized polybutadiene, or combinations thereof.
In some embodiments, epoxide includes cycloaliphatic epoxy resin, divinylbenzene dioxide, lemon
Alkene dioxide, or combinations thereof.
In some embodiments, curable compositions contain first kind epoxide and the second class epoxide,
The two ratio is 10:1 to 2:1, preferably 8:1 to 3:1.Wherein, first kind epoxide includes cycloaliphatic epoxy resin, diethyl
Alkenyl benzene dioxide, limonene dioxide or combinations thereof；Second epoxide includes that epoxidised soybean oil, epoxidation are poly-
Butadiene or combinations thereof.Based on this, curable compositions have both that curing rate is fast, and resistance to physical and chemical performance is excellent, flexibility is excellent
Advantage.(such as F1-2 of embodiment, F2-4).
In some embodiments, cycloaliphatic epoxy resin includes adipic acid bis- (3,4- epoxycyclohexanecarboxylates), (3,4-
Epoxy group) hexahydrobenzoid acid (3,4- epoxy group) cyclohexylmethyl, 3,4- epoxy group -6- cyclohexanecarboxylic acid -3 ', 4 '-rings
Oxygroup -6- hexahydrotoluene methyl esters, liquid titanium dioxide double cyclopentenyl ether, bis- (2,3- epoxycyclohexyl) ethers, 3,4- epoxy -6
Methylcyclohexylmethyl carboxylate,
Bis- (the 3,4- epoxycyclohexyl methoxyl group) alkane of 1,2-:
Bis- (the 3,4- epoxycyclohexyl methoxyl group) paraxylene of 1,2-:
Epoxidized polybutadiene (for example, PolyBD-605E of Sartomer (Sartomer) company
, PolyBD-600E), or combinations thereof.
It in some embodiments, also include weight content area in epoxide based on the total weight of epoxide
Between for (0,30wt%] bisphenol A epoxide resin, novolac epoxy resin or combinations thereof.Based on this, curable compositions, which have, to be increased
Strong solvent resistance.
In some embodiments, oxygen heterocycle butane is quaternary cyclic ether compounds, can carry out cationic open loop
Polymerization, has the characteristics that viscosity is low, cure shrinkage is low and polymerization speed is fast.
In some embodiments, the active group of oxygen heterocycle butane is oxetanes, one molecule
Inside at least contain an oxetanes, preferably comprises two oxetanes.
In some embodiments, oxygen heterocycle butane is simple function group oxetanes, for example including 3- second
Base -3- methylol-oxetanes (TMPO OXT101), 3- ethyl -3- (2- Ethylhexoxymethyl) oxetanes
(OXT-212)
Or combinations thereof.
In some embodiments, oxygen heterocycle butane is polyfunctional group oxetanes, for example including 3,3 '-
(the double methylenes of oxygroup)-bis--(3- ethyl) oxetanes (OXP OXT221)
1,4 bis- [(3- ethyl -3- Oxymethylene oxetanes) methyl] benzene (OXT121)
3,3 '-[1,4- butyl is bis- (oxygroup methylene)]-bis--(3- ethyl) oxetanes
Or combinations thereof.
In some embodiments, polyfunctional group vinyl ethers compound contains the first active function groups and the second activity
Functional group, the first active function groups are vinyl ether group or propenyl ether group, and the second active function groups are free radical activities
Functional group or cation activity functional group.
In some embodiments, vinyl ether group and propenyl ether group belong to cation activity functional group.
In some embodiments, in polyfunctional group vinyl ethers compound, the second active function groups are vinyl ethers
Group or propenyl ether group (such as F1-1, F1-2, F1-3, F2-1, F2-4, F3-2 of embodiment, F3-3, G1-1, G1-3).
Optional polyfunctional group vinyl ethers compound includes triethylene glycol divinyl ether, 1,4- cyclohexane dimethanol divinyl
Ether, 1,4- butanediol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether or combinations thereof.It, can based on this
Meet the requirement of system solidification rate, and there is certain degree of cross linking, improves printing solvent resistance.
In some embodiments, the first active function groups are vinyl ether group or propenyl ether group, the second activity
Functional group is the free radical activity functional group or cation activity functional group in addition to vinyl ether group and propenyl ether group
(such as F1-5 of embodiment, F2-5, F3-4, G1-2).Based on this, photo-curing rate can be further speeded up, improves conversion ratio.
In some embodiments, polyfunctional group vinyl ethers compound includes
3- ethyl -3- allyl methoxyl oxetanes:
2- acrylic acid 2- [2- (ethyleneoxy) ethyoxyl] ethyl ester:
(3,4- epoxycyclohexyl methoxyl group) propylene:
Or combinations thereof.
In 3- ethyl -3- allyl methoxyl oxetanes, the first active function groups are propenyl ether groups, and second is living
Property functional group is oxetane groups.
In 2- acrylic acid 2- [2- (ethyleneoxy) ethyoxyl] ethyl ester, the first active function groups are vinyl ether groups, the
Two active function groups are (methyl) acrylate groups.
In (3,4- epoxycyclohexyl methoxyl group) propylene, the first active function groups are propenyl ether group, the second active official
Can roll into a ball is cycloaliphatic epoxy groups.
In some embodiments, second functional group is oxetane groups, acrylate group (such as metering system
Acid esters group) or cycloaliphatic epoxy groups.
Inventors have found that the polyfunctional group vinyl ethers compound of specific quantity can effectively facilitate oxetanes and epoxy
The curing reaction of compound improves the whole photo-curing rate of curable compositions and the solvent resistance of printing.Content is lower than one
When definite value, the photo-curing rate of curable compositions declines, too high levels, the solvent resistance decline of curable compositions.
It in some embodiments, also may include 0.5-10 parts of fluoride resin in curable compositions.Fluoride resin can
To include perfluoropolyether, polyfluorourethane acrylate, fluoro epoxies or combinations thereof.Based on this, can further decrease
Curable compositions coating surface energy, enhances its stain resistance and anti-fingerprint property.
It in some embodiments, also include 5-25 parts of hydroxy compounds in curable compositions.Hydroxy compounds can
With include polyester polyol, polyether polyol, acetylbutyrylcellulose, polycaprolactone, castor oil, or combinations thereof.
In some embodiments, also comprising the acrylic acid of 1-20 parts of the group containing free radical activity in curable compositions
Ester compounds.To constitute free radical-cationic hybrid polymerization system.In some embodiments, group containing free radical activity
Acrylate compounds include bisphenol A epoxy acrylate (such as F1-3 of embodiment 1), trimethylolpropane tris acrylic acid
Ester, ethoxyquin trimethylolpropane trimethacrylate, third oxidation trimethylolpropane trimethacrylate, glycerol tri-acrylate,
Glycerol propoxylate triacrylate, or combinations thereof.
Radical UV curing has many advantages, such as that curing rate is fast, materialization patience is excellent, resin types are abundant, but exists simultaneously oxygen
Polymerization inhibitor polymerize the disadvantages of big cubical contraction, poor adhesive force.With volume contraction, small, oxygen hinders small, adhesive force to cation photocuring
The advantages that good, it is slow there are curing rate the disadvantages of.Under certain condition, free radical-cationic hybrid UV curing system can
Free radical and cation photocuring reaction occurs simultaneously, gives full play to free radical and cation photocuring system is respective excellent
Point, generates good synergistic effect, accelerates curing rate, effectively shortens surface drying time, at the same adhesive force and materialization patience not by
It influences.Inventor has found solidification process shadow of the acrylate compounds to hybrid systems of the group containing free radical activity in an experiment
Complexity is rung, good synergistic effect is not necessarily formed.For example, on the basis of the curing system of disclosure curable compositions,
After being added to the urethane acrylate of 15 parts of model CN996 or the polyester acrylate of model CN2264, mix body
System occurs failing to be fully cured instead or even phenomena such as surfaces of tacky.
In some embodiments, curable compositions include 2~20 parts of filler, such as 5,10 or 15 parts.
In some embodiments, filler include calcium carbonate, kaolin, aluminium silicate salt, wax powder and silica flatting silica,
Or combinations thereof.
In some embodiments, cation light initiator includes diaryl iodonium salt, triaryl sulfonium salts, aryl cyclopentadienyl iron
Salt or combinations thereof.The selected photosensitizer that can be matched with photoinitiator through the invention, the length that can emit in UVLED light source
Wave spectrum area generates strong absorption, first absorption UV luminous energy and excites, then by electronics transfer to initiator, and then generates super acids
Cause cation photocuring.
In some embodiments, photosensitizer include thioxanthone derivative, anthraquinone derivative, or combinations thereof.Due to
The absorption peak of salt photoinitiator focuses mostly in 250-300nm, mismatches with the emission spectrum of the UVLED light source of long wave.Pass through
The selected photosensitizer that can be matched with photoinitiator of the present invention, the long wave spectral regions that can emit in UVLED light source generate strong
It absorbs, and absorbs UV luminous energy first and excite, then by electronics transfer to initiator, and then it is solid to generate super acids initiation cationic photopolymerization
Change.
In some embodiments, curable compositions are also containing 2-45 parts of pigment, such as 5-25, and 10-35 parts or 15-
30 parts of pigment.
In some embodiments, pigment be organic pigment and inorganic pigment, organic pigment be azo pigments, phthalocyanine blue,
Phthalocyanine green, quinacridone etc., inorganic pigment are titanium white and carbon black etc..
In some embodiments, pigment is pigment refined substance, and pigment refined substance is to be carried out using vector resin to pigment
Coat the product of processing.The advantages that it has the transparency excellent, and color developing is high, and partial size is small.
In some embodiments, pigment includes effect pigment, pigment changeable colors along with angle, optically variable pigments or combinations thereof.It is optional
Ground, optically variable pigments are multilayered interference film pigment, and when facing and plunderring two different angle observations of view, color change can be presented.
Optionally, effect pigment is the metallic pigments or pearlescent pigment for having certain gloss, such as metal, metal oxide, or with mica, three
Al 2 O etc. is that substrate carries out pigment obtained from multilevel oxide cladding.Optionally, pigment changeable colors along with angle is by humidifying
Pigment prepared by method or chemical vapour deposition (CVD), utilizes the metal oxide of high refractive index layer and low-index layer
Or the mixture of metal oxide carries out alternately cladding to laminar substrate or inner nuclear material.The material of substrate may include cloud
Mother, aluminium oxide, silica, glass, metal etc., high refractive index metal oxide layer or metal oxide mixture layer can material packet
Include TiO2、Fe2O3、ZrO2, ZnO or other compound with a high refractive index, low-refraction metal oxide layer or metal oxidation
The material of object mixture layer may include SiO2、Al2O3Deng.When facing and plunderring two different angle observations of view, color change can be presented
Change.
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some embodiments, curable compositions have formula as below:
In some respects, provide foregoing curable composition as photocurable ink, photocurable coating applications or can light it is solid
Change the purposes of adhesive under ultraviolet light.
In some embodiments, light source of the mercury lamp as ultraviolet light can be used.
In some embodiments, light source of the UVLED as ultraviolet light can be used.The ultraviolet light that UVLED light source generates is logical
It is often single band ultraviolet light.
In some embodiments, ultraviolet light is that a kind of single band ultraviolet light or a variety of (such as 2~10 kinds) single bands are purple
The mixing of outer light.The peak wavelength of single band ultraviolet light can be within the scope of 360~410nm, the peak value wave of single band ultraviolet light
Length can be in 360~365nm, 365~370nm, 370~375nm, 375~380nm, 380~385nm, 385~390nm, 390
Within the scope of~395nm, 395~400nm, 400~405nm or 405~410nm.
In some respects, a kind of method solidifying foregoing curable composition is provided, including uses ultraviolet light above-mentioned
Curable compositions, the ultraviolet light refer to a kind of single band ultraviolet light or several (such as 2~10 kinds) single band ultraviolet lights
Mixing.
In some embodiments, disclosed method includes that curable compositions are printed on matrix, mode of printing
Flexo or rotogravure etc. can be used, when the protective coating used time for being applied to money surface, it is preferred to use flexo mode of printing, base
Paper base can be selected in material or plastic basis material, plastic basis material include Biaxially oriented polypropylene (BOPP), polycarbonate, poly terephthalic acid
Glycol ester (PET) etc..Ink can also be used rotogravure or rotation gravure mode is printed, substrate also can be selected paper base or
Plastic basis material, especially when being printed in BOPP film, ink can express good adhesive force and materialization patience.
Term " polyfunctional group vinyl ethers compound " refers to multifunctional containing vinyl ethers or propenyl ether structure
Group's compound, can be monomer, oligomer and/or polymer.
Term " oxygen heterocycle butane " refers to the compound with oxetanes, is simple function and/or more
Function, it can be monomer, oligomer and/or polymer.
Term " epoxide " is the aliphatic series and/or aromatic compounds with epoxy group, is simple function and/or more officials
Can, it can be monomer, oligomer and/or polymer.
Term " acrylate compounds of the group containing free radical activity " is simple function and/or polyfunctional, be can be
Monomer, oligomer and/or polymer.
Term " free radical activity functional group ", which refers to, may occur from by the functional group of fundamental mode UV curing reaction.
Term " cation activity functional group " is the functional group that cationic UV curing reaction can be transmitted in value.
Term " epoxide " does not include above-mentioned vinyl ethers based compound.
Term " epoxide " does not include above-mentioned oxetanylmethoxy compound.
Term " epoxide is not " does not include above-mentioned " acrylate compounds of the group containing free radical activity ", such as not
Including bisphenol A epoxy acrylate.
Term " tri-(oxetane) compound " does not include above-mentioned vinyl ethers compound.
Term " single band ultraviolet light " refers to spectrum half-peak breadth (FWHM) in 10nm ultraviolet light below, such as 5nm or less
Ultraviolet light.
Term " includes " refers to that weight content is 10~100%, such as 20%, 40%, 60%, 80% or 100%.
Beneficial effect
Curable compositions of the invention have the advantages that following one or more:
(1) curing rate is fast, such as solidification rate >=60m/min；
(2) solvent resistance is good, such as resistance to butanone wipes >=4 grades；
(3) crumpling resistance can be good, such as resistance to rubs >=4 grades.
(4) there is preferable curing performance under single band ultraviolet light.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
Commercially available or voluntarily synthesis acquisition can be passed through.
The ink solidification performance test of following embodiment and ranking method are as follows:
Solidification rate: refer to the maximum rate of uv cure machine conveyer belt when UV ink solidification can be made to reach surface drying, solidification
Ink film is pressed with finger afterwards, without trace is surface drying on finger without viscous sense.
Resistance to butanone wiping: reference standard GB/T 23989-2009 (coating solvent resistant wiping measuring method) carries out resistance to butanone
The test of wiping properties is graded after wiping according to ink dropping situations.
Resistance to rub: reference standard ASTM F 392 carries out the test of crumpling resistance energy, according to ink dropping situations after printing rubbing
It grades.
Grading: being divided into 5 grades according to ink dropping situations after test, is 5 grades without falling off, is substantially 4 grades without falling off, slightly falls off
It is 3 grades, hence it is evident that falling off is 2 grades, and severe detachment is 1 grade.
Above-mentioned three kinds of test methods are known to the field for evaluating the curing performance and materialization patience of ink, resistance to butanone
The superiority and inferiority of wiping reflection ink solvent resistance, resistance to rub the reflection flexible superiority and inferiority of ink, ink flexibility is better, resistance to rub rank
It is higher.
Embodiment 1
It is formulated by shown in table 1, first mixes vinyl ethers based compound and oxetanylmethoxy compound with flatting silica,
20min is stirred under 1000 turns/min revolving speed using high speed disperser, other components is then gradually adding, is finally stirred for
15min。
It uses anilox roll to be coated with instrument for the soft version of 400 lines/inch ink is respectively coated on paper substrate, thickness is about
2 microns.It then is 8W/cm in power2Solidified under the UVLED light source that wavelength is 365nm.Carry out the inspection of materialization patience afterwards for 24 hours
It surveys, curing performance and testing result are shown in Table 1.
The experiment conclusion of table 1:
(1) from the data in table 1, it can be seen that the ink (F1-1~F1-3) of inventive formulation has improved curing performance, exceed
Ink (F1-4) curing performance of formula range is bad；
(2) F1-5 further uses " 3- ethyl -3- allyl methoxyl oxa- ring fourth under ink system of the invention
Alkane " is used as diluent, is based on the component system, obtain >=(uv cure machine passes for the solidification rate of the ink of 100m/min
The maximum rate for sending band is 100m/min, and >=100m/min is to refer to sufficiently solidify under maximum rate), while ink is resistance to
It is also especially excellent to rub up the wiping properties of resistance to butanone.
(3) F1-2 uses adipic acid bis- (3,4- epoxycyclohexanecarboxylates) and epoxidized polybutadiene, PolyBD-605E's
Combination, solidification rate can reach 60m/min, and it is resistance to rub, the wiping of resistance to butanone is at 5 grades.
(4) formula of comparative example F1-4 can not effectively solidify under single band ultraviolet light not within the scope of inventive formulation.
Embodiment 2
It is formulated by shown in table 2, first mixes vinyl ethers based compound and oxetanylmethoxy compound with flatting silica,
20min is stirred under 1000 turns/min revolving speed using high speed disperser, other components is then gradually adding, is finally stirred for
15min。
It uses anilox roll to be coated with instrument for the soft version of 400 lines/inch ink is respectively coated on paper substrate, thickness is about
2 microns.It then is 8W/cm in power2Solidified under the UVLED light source that wavelength is 365nm.Carry out the inspection of materialization patience afterwards for 24 hours
It surveys, curing performance and testing result are shown in Table 2.
The experiment conclusion of table 2:
(1) F2-4 uses (3,4- epoxy group) hexahydrobenzoid acid (3,4- epoxy group) cyclohexylmethyl and epoxidized soybean oil
Combination is based on the component system, and solidification rate can reach 60m/min, and it is resistance to rub, the wiping of resistance to butanone is at 5 grades.
(2) F2-5 has used " (3,4- epoxycyclohexyl methoxyl group) propylene " as reactive diluent, based on this at fission
System obtains the >=solidification rate of 100m/min.
(3) formula of comparative example F2-2 is not within the scope of inventive formulation, resistance to butanone after solidifying under single band ultraviolet light
Wiping properties are bad.
(4) formula of comparative example F2-3 can not effectively solidify under single band ultraviolet light not within the scope of inventive formulation.
Embodiment 3
It is formulated by shown in table 3, first by above-mentioned epoxide, vinyl ethers, oxetanes class, polyester, dispersion
Agent is mixed with carbon black or phthalocyanine blue, after mixing evenly, is ground to fineness less than 5 microns through sand mill, photosensitizer is then added
And initiator, finally stir 15min.It uses anilox roll to be coated with instrument for the soft version of 200 lines/inch and shown ink is coated on PET
On film.It then is 16W/cm in power2Solidified under the UVLED light source that wavelength is 385nm.Carry out materialization patience afterwards for 24 hours
Detection, curing performance and testing result are shown in Table 3.
The experiment conclusion of table 3:
(1) it is dilute as activity to use " 2- acrylic acid 2- [2- (ethyleneoxy) ethyoxyl] ethyl ester " by ink F3-1 and F3-4
Agent is released, the component system is based on, obtains >=the solidification rate of 100m/min, resistance to rub up resistance to butanone wiping be 5 grades.
(2) ink F3-2 uses diethylene glycol divinyl ether as reactive diluent, is based on the component system, obtains
The solidification rate of 80m/min, resistance to rub is 4 grades, and resistance to butanone wiping is 5 grades.
Embodiment 4
Be formulated by shown in table 4, above-mentioned will be removed under agitation using high speed disperser first photosensitizer and initiator it
Outer component mixes, and under the revolving speed of 1000 turns/min, stirs 20min, photosensitizer and initiator is then added, is stirred for
15min.It is 180 lines/inch gravure machine that anilox roll, which can be used, in above-mentioned ink, is printed on BOPP film or BOPP base
On plastic basis material.Then it uses in power as 16W/cm2Solidified under the UVLED light source that wavelength is 385nm.It carries out afterwards for 24 hours
The detection of materialization patience, curing performance and testing result are shown in Table 4.
The experiment conclusion of table 4:
(1) ink G1-1 all has improved curing performance to ink G1-3.Ink G1-2 uses " 3- ethyl -3- alkene
Propylmethoxy oxetanes " is used as reactive diluent, is based on the component system, obtains >=the solidification of 100m/min speed
Rate.
(2) G1-2 further uses " 3- ethyl -3- allyl methoxyl oxa- ring fourth under ink system of the invention
Alkane " is used as diluent, is based on the component system, the solidification rate of ink is very fast, while the resistance to of ink rubs up the wiping of resistance to butanone
It can be also especially excellent.
(3) ink G1-1 contains Huayang optical color variable pigmentShow color changeable effect.Ink G1-2 contains
Merck Iriodin 9201, in interference gold bead light effect.G1-1 and G1-2 can print the perspective in printable plastic basis material
On window, that is, it is directly printed in BOPP film.Also it can print on through opaque treated printable plastic basis material.It can also
On plastic basis material window, another part is printed on through on opaque treated plastic basis material printed portions.
Although a specific embodiment of the invention has obtained detailed description, those skilled in the art will appreciate that root
According to all introductions having disclosed, details can be carry out various modifications and be changed, and these change in guarantor of the invention
Within the scope of shield.Full scope of the invention is given by the appended claims and any equivalents thereof.
Claims (19)
1. a kind of curable compositions, by weight, comprising:
2. curable compositions according to claim 1, it is living that the polyfunctional group vinyl ethers compound contains first
Property functional group and the second active function groups；
First active function groups are vinyl ether group or propenyl ether group；
Second active function groups are free radical activity functional group or cation activity functional group.
3. curable compositions according to claim 2, it is characterised in that any one of following:
Second active function groups are vinyl ether group or propenyl ether group；
Second active function groups be free radical activity functional group in addition to vinyl ether group and propenyl ether group or
Cation activity functional group.
4. composition according to claim 2, wherein the second functional group is oxetane groups, aliphatic ring
Oxygen groups, acrylate group or methacrylate group.
5. curable compositions according to claim 1, wherein the polyfunctional group vinyl ethers compound includes
Triethylene glycol divinyl ether,
1,4- cyclohexane dimethanol divinyl ether,
1,4- butanediol divinyl ether,
Diethylene glycol divinyl ether,
Ethylene glycol divinyl ether,
3- ethyl -3- allyl methoxyl oxetanes:
2- acrylic acid 2- [2- (ethyleneoxy) ethyoxyl] ethyl ester:
(3,4- epoxycyclohexyl methoxyl group) propylene:
Or combinations thereof.
6. curable compositions according to claim 1, the epoxide includes cycloaliphatic epoxy resin, divinyl
Base benzene dioxide, citric acid dioxide, epoxidised soybean oil, epoxidized polybutadiene, or combinations thereof.
7. curable compositions according to claim 6, the cycloaliphatic epoxy resin includes bis- (3, the 4- epoxies of adipic acid
Cyclohexylmethyl), (3,4- epoxy group) hexahydrobenzoid acid (3,4- epoxy group) cyclohexylmethyl, 3,4- epoxy group -6- methyl ring
Hexane formic acid -3 ', 4 '-epoxy group -6- hexahydrotoluene methyl esters, liquid titanium dioxide double cyclopentenyl ether, bis- (2,3- epoxy hexamethylenes
Base) ether, -6 methylcyclohexylmethyl carboxylate of 3,4- epoxy,
Bis- (the 3,4- epoxycyclohexyl methoxyl group) alkane of 1,2-:
Bis- (the 3,4- epoxycyclohexyl methoxyl group) paraxylene of 1,2-:
Epoxidized polybutadiene, or combinations thereof.
8. curable compositions according to claim 1, curable compositions contain the first kind that weight ratio is 2~10:1
Epoxide and the second class epoxide；First kind epoxide includes cycloaliphatic epoxy resin, divinylbenzene two
Oxide, limonene dioxide or combinations thereof；Second epoxide include epoxidised soybean oil, epoxidized polybutadiene or
A combination thereof.
9. curable compositions according to claim 1, the oxygen heterocycle butane include
3- ethyl -3- hydroxymethyl-oxetane,
Bis- [(3- ethyl -3- oxetanylmethoxy) methoxyl group] benzene of 1,4-,
3,3 '-(the double methylenes of oxygroup)-bis--(3- ethyl) oxetanes (OXP OXT221)
1,4 bis- [(3- ethyl -3- Oxymethylene oxetanes) methyl] benzene (OXT121)
3,3 '-[1,4- butyl is bis- (oxygroup methylene)]-bis--(3- ethyl) oxetanes
Or combinations thereof.
10. curable compositions according to claim 1, further include:
2-20 parts of filler；
Preferably, the filler include fumed silica, wax powder, flatting silica, or combinations thereof.
11. curable compositions according to claim 1 further include by weight
5-25 parts of hydroxy compounds；
The hydroxy compounds include polyester polyol, polyether polyol, acetylbutyrylcellulose, polycaprolactone, castor oil or
A combination thereof.
12. curable compositions according to claim 1 further include by weight
1-20 parts of the acrylate compounds of the group containing free radical activity；
The acrylate compounds of the group containing free radical activity include bisphenol A epoxy acrylate, trimethylolpropane tris
Acrylate, ethoxyquin trimethylolpropane trimethacrylate, the third oxidation trimethylolpropane trimethacrylate, three propylene of glycerol
Acid esters, glycerol propoxylate triacrylate, or combinations thereof.
13. curable compositions according to claim 1, the photosensitizer includes anthraquinone analog compound or thioxanthones
Compound, or combinations thereof.
14. curable compositions according to claim 1, the cationic initiator includes diaryl iodonium salt, three virtues
Base sulfosalt, iron arene complexes, or combinations thereof.
15. curable compositions according to claim 1, wherein also containing
Pigment, weight content section be (0,45 part].
16. curable compositions according to claim 1, with following any formula:
Formula 1:
Formula 2:
Formula 3:
Formula 4:
Formula 5:
Formula 6:
Formula 7:
Formula 8:
17. the described in any item curable compositions of claim 1~16 are used for the cured purposes under ultraviolet radiation；
Preferably, the ultraviolet light refers to the group of a kind of single band ultraviolet light or a variety of (such as 2~10 kinds) single band ultraviolet lights
It closes；
Preferably, the light source of the ultraviolet light is UVLED.
18. a kind of method for solidifying the described in any item curable compositions of claim 1~16, including with ultraviolet light institute
State curable compositions；
Preferably, the ultraviolet light refers to the group of a kind of single band ultraviolet light or a variety of (such as 2~10 kinds) single band ultraviolet lights
It closes；
Preferably, the light source of the ultraviolet light is UVLED.
19. a kind of curable ink, hardenable coatings or curable adhesive, described in any item containing claim 1~16
Curable compositions；
Preferably, the curable ink, hardenable coatings or curable adhesive are for cured under ultraviolet radiation
Ink, coating or adhesive；
Preferably, the ultraviolet light refers to the group of a kind of single band ultraviolet light or a variety of (such as 2~10 kinds) single band ultraviolet lights
It closes；
Preferably, the light source of the ultraviolet light is UVLED.
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| CN201910135138.5A CN109880434B (en) | 2019-02-25 | 2019-02-25 | Curable composition and use thereof |
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| CN109880434B CN109880434B (en) | 2022-04-19 |
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Cited By (3)
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| CN112126275A (en) * | 2020-09-16 | 2020-12-25 | 四川乐凯新材料有限公司 | Photocurable composition for PCB containing alkenyl ether and/or oxetane and radical polymerizable compound |
| CN112143284A (en) * | 2019-06-28 | 2020-12-29 | 常州强力电子新材料股份有限公司 | Radiation-curable ink and use thereof |
| CN114524785A (en) * | 2022-01-22 | 2022-05-24 | 江苏泰特尔新材料科技股份有限公司 | High-purity high-thermal-stability alicyclic epoxy resin monomer and preparation method thereof |
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| CN114524785A (en) * | 2022-01-22 | 2022-05-24 | 江苏泰特尔新材料科技股份有限公司 | High-purity high-thermal-stability alicyclic epoxy resin monomer and preparation method thereof |
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| CN109880434B (en) | 2022-04-19 |
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Address after: 100070 8th floor, building 2, No.5 Zhonghe Road, Fengtai Science City, Fengtai District, Beijing Patentee after: China Banknote Printing Technology Research Institute Co.,Ltd. Patentee after: China Banknote Printing and Minting Group Co.,Ltd. Address before: 100070 8th floor, building 2, No.5 Zhonghe Road, Fengtai Science City, Fengtai District, Beijing Patentee before: China Banknote Printing Technology Research Institute Co.,Ltd. Patentee before: CHINA BANKNOTE PRINTING AND MINTING Corp. |
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