CN103901725A - Light-cured resin composition - Google Patents
Light-cured resin composition Download PDFInfo
- Publication number
- CN103901725A CN103901725A CN201410158610.4A CN201410158610A CN103901725A CN 103901725 A CN103901725 A CN 103901725A CN 201410158610 A CN201410158610 A CN 201410158610A CN 103901725 A CN103901725 A CN 103901725A
- Authority
- CN
- China
- Prior art keywords
- methyl
- resin composition
- compound
- light curing
- curing resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a light-cured resin composition which at least comprises the following components: (a) 20-90 mass percent of adhesive polymer; (b) 5-60 mass percent of one or more photopolymerizable compounds which can be compatible with the component (a), namely the adhesive polymer and have ethylene unsaturated bonds; (c) 0-20 mass percent of additive and/or aids; and (d) 0.01-20 mass percent of photopolymerization initiator, wherein the photopolymerization initiator comprises at least one compound with the following structural general formulas which are as shown in the specification (1). The light-cured resin composition has excellent performance in ultraviolet (UV) yellowing resistance and high-temperature yellowing resistance, and the problem that the light-cured resin composition is easily subjected to UV yellowing and high-temperature yellowing due to an OXE-01 photopolymerization initiator is solved.
Description
Technical field
The invention belongs to photocuring technology field, be specifically related to a kind of light curing resin composition.
Background technology
Color filter is indispensable structure member in LCD assembly and solid-state image pickup assembly.As display device, LCD assembly, than kinescope (cathode-ray tube (CRT) (Cathode RayTube:CRT)) more small-sized (compact) and not a halfpenny the worse at aspect of performance, therefore replaces CRT as television image, computer picture and other display equipment just gradually.And in recent years, it is large and require to have TV (TV) purposes of high-quality image quality that the exploitation trend of LCD assembly develops into picture from the smaller monitor purposes of picture in the past.For compared with the LCD assembly of monitor, required have higher-quality image quality for the LCD assembly of TV with in the past.In addition, the monitor dimension of the LCD assembly that mobile phone and auto-navigation system (car navigation system) use is now more and more less, also needs the display module that resolution is higher.On the other hand, also need the higher degree that becomes more meticulous for the color filter of solid-state image pickup assembly.
In color filter, the colorant of solidification compound (organic pigment etc.) can improve above-mentioned high image quality contrast (for example Japanese Patent the 3120547th communique) after reaching more tiny particle requirement, be colorant and the Pigments dosage that strengthening excitation needs to improve solidification compound in color filter, i.e. Photoepolymerizationinitiater initiater in necessary reduction solidification compound and the content of photopolymerization monomer, and improve yellowing resistance matter.But, when the content of above-mentioned Photoepolymerizationinitiater initiater and monomer reduces, can cause sensing optical activity to decline and then produce harmonic analysis rate and increase pattern line-width, and the problem of other negative effect display modules.In commercial Application, this influential effect for giant display size assembly is more obvious.
Therefore, research and develop high sensing optical activity light-cured resin formula, utilize Photoepolymerizationinitiater initiater to provide excellent UV resistant and capable of resisting high-temperature yellowing to meet the demands such as above-mentioned high image quality contrast (contrast) and excitation, there is very high economy and social value.
And light-cured type resin combination can be used for light-emitting diode component, can provide in response to the design of high integration higher luminous power.In addition, light-cured type resin combination manufacture method is simple, therefore can reduce costs, and improves industrial competitiveness application.Moreover the homogeneity of controlling light-cured type resin combination thickness meets the advantage of lightening design and can realize more easily the industrialization of light fixture.
Current, there are many reports about the R&D work of light-cured type resin combination, in component, published structure comprises but not only in following three kinds of aspects, illustrates here.
The first, the replacement structure that carboxyl is other, for example: JP2006028127-A, US2011256457-A1, JP2011228103-A, CN102222798-A, JP2007233136-A, JP2004325785-A, JP2007119685-A, JP4650211-B2, JP2007119686-A, JP4650212-B2, JP2008076852-A, JP2007248516-A, JP2003121997-A, JP3913022-B2, 2011-M90139, 2011-D76227, JP2008076852-A, JP2007248516-A, SU1321730-A, JP2002311586-A, JP2008076852-A, JP2008064890-A, JP2007248516-A, WO200177070-A, WO200177070-A1, AU200158308-A, JP4650211-B2 etc.
The second, for example, at the open report of ketone group side or substituted-phenyl structure: US2008180503-A1, EP1958994-A1, JP2008208321-A, JP2008064890-A, JP2007248516-A, US2008180503-A1, EP1958994-A1, JP2008208321-A, JP2008064890-A, JP2007248516-A etc.
The third, the replacement structure that imido grpup is other, for example: WO2009068322-A1, EP2065039-A1, WO2002102336-A, WO2002102336-A1, DE10129545-A1, DE20211496-U1, JP2008102486-A, CN101149562-A, JP2008064890-A, P2008076852-A, JP2007310027-A, JP2007119686-A, JP4650212-B2, JP2011033793-A, JP2008076852-A, JP2007248516-A, WO2009068322-A1, EP2065039-A1, JP2007119686-A, JP4650212-B2, JP2004325785-A etc.
Previously in document (referring to Taiwan patent I279645 publication number), existing report utilization is drawn look triphenyl methane and is added in dry film photoresistance, while making photoresistance produce color after ultraviolet exposure whether to be exposed for identification, can not cause because the thermal stability of colour forming agents is not enough un-desired color when laminated to produce, and reduce through exposure and without the color contrast of exposure area, but this patent documentation does not provide and is applicable to transparent and component formula white light gel-type resin constituent.
Previously in document, (referred to US20050531482, US2006100298A1), the new component of existing report research and development is applicable to improve the dissolubility of specific light initiating agent in preparation, therefore improve the storage stability that contains light trigger and preparation, can strengthen invention transparent and the white light gel-type resin constituent xanthochromia of resistance to UV and high temperature xanthochromia but do not provide.Previously in document, (referred to US20090995699, US2011134554A1), existing being reported in their invention, this Photoepolymerizationinitiater initiater potpourri can improve resolution and the lightsensitivity after light-cured type resin combination develops, promote curing rate, can strengthen invention transparent and the white light gel-type resin constituent xanthochromia of resistance to UV and high temperature xanthochromia but do not provide.
Previously in document, (referred to US20020088222, US6803392B1), existing being reported in their invention, this Photoepolymerizationinitiater initiater potpourri comprises a kind of moisture, stable storing, non-settling photoinitiator suspended matter, applicable to the formula of water soluble photo-curable type resin combination, can strengthen invention transparent and the white light gel-type resin constituent xanthochromia of resistance to UV and high temperature xanthochromia but do not provide.
Previously in document, (referred to US19960754708, US5807905A), in the existing invention that is reported in them, find that poly-borate is except can doing germifuge and fungicide, can include Photoepolymerizationinitiater initiater compositions of mixtures in, utilize poly-borate and uses as a kind of Photoepolymerizationinitiater initiater with initiating agent or electron accepter respectively or separately, can strengthen invention transparent and the white light gel-type resin constituent xanthochromia of resistance to UV and high temperature xanthochromia but do not provide.
In the application of transparent type and white type light-cured type resin combination, if the not resistance to UV of the component of interpolation and high temperature xanthochromia, for example Photoepolymerizationinitiater initiater, because of its thermal stability deficiency, can cause light-cured type resin combination on base material, to present the aberration of color.This is the problem that utmost point wish solves.
In order to promote to some extent aspect production efficiency and permanance, light-cured type resin combination need have high sensing optical activity, resistance to xanthochromia and excellent engineering properties.For example, form pattern or utilize while entirely exposing into insulating protective film in photolithography (photolithography), high sensing optical activity is played the part of very important role.In addition, damage in order to avoid liquid crystal display to be subject to external shock, and show its intrinsic performance, just must have excellent engineering properties as the column separation material of support applications and as the protection of diaphragm purposes with dope layer and passivating film.Therefore,, in the time using a kind of Photoepolymerizationinitiater initiater with excellent sensing optical activity, can address the above problem fast and preferably.In addition, in the time using this to there is the Photoepolymerizationinitiater initiater of excellent sensing optical activity, even if be conducive in the time using a small amount of Photoepolymerizationinitiater initiater, also can obtain enough photocuring degree, so likely reduce the pollution source of liquid crystal, the conservation rate (retention rate) of enhancement pattern.
In the light trigger of white or transparent feel optical activity composition; the most typical commercially available Photoepolymerizationinitiater initiater is 2; 4; 6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO); because it has very wide absorption region; its effective absorption peak is 350-400nm, absorbs 420nm left and right always, and its more general common light trigger of absorption peak is partially long.After illumination, can generate two free radicals of benzoyl and phosphoryl; can bring into play the function of initiated polymerization; it also has photobleaching, can make the characteristic of not flavescence of coating, has low volatilization; be used for White system; but, because effectively absorption peak is partially long, therefore; laser curing velocity under ultraviolet ray is slow, uses upper its use amount in the application of sensing optical activity composition that promotes and cause.
In recent years, commercially available oxime ester Photoepolymerizationinitiater initiater, Irgacure OXE01 and Irgacure OXE02 (can buy by chemical company from Ciba spy) have relatively improved many in photocuring degree, so focus is placed on as the application of coloured sensing optical activity composition, but because these Photoepolymerizationinitiater initiaters are very expensive, with the consideration of economic aspect, cannot be used to being enough to show enough photocuring degree, and if the consumption of this Photoepolymerizationinitiater initiater promote and will have influence on the not xanthochromia characteristic of Photocurable composition.
Summary of the invention
For solving the technical matters of above-mentioned transparent and the white light gel-type resin constituent xanthochromia of resistance to UV and high temperature xanthochromia, the invention provides a kind of light curing resin composition.
It should be noted that, " (methyl) acrylate " in this instructions means " acrylate " and " methacrylate " corresponding with it.Similarly, " (methyl) acrylic acid " means " acrylic acid " and " methacrylic acid " corresponding with it, and " (methyl) acryloyl group " means " acryloyl group " and " methacryl " corresponding with it.
As light curing resin composition of the present invention, comprise following component:
(a) the binder polymkeric substance of 20 to 90 quality %;
(b) 5 to 60 quality % one or more can with the optical polymerism compound with ethylene unsaturated bond of the described binder polymkeric substance of component (a) compatibility;
(c) adjuvant of 0 to 20 quality %; And
(d) Photoepolymerizationinitiater initiater of 0.01 to 20 quality %, described Photoepolymerizationinitiater initiater comprises compound shown in following formula (1):
Wherein When exposure energy is lower than 350mj/cm
2time, described light curing resin composition tool is lower than 4 Yellow degree values.
As (a) binder polymkeric substance, can list, such as acryl resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenolics, ester resin, urethane resin, by epoxy resin and (methyl) acrylic acidly react the Epocryl that obtains, by the sour modified epoxy acrylic ester resin that reacts acquisition of Epocryl and acid anhydrides etc.These resins can be with independent a kind or combine mode of more than two kinds and use.Consider from the viewpoint of alkali-developable and film formative excellence, preferably use acryl resin, more preferably this acryl resin contains the monomer unit that is derived from (methyl) acrylic acid and (methyl) alkyl acrylate as structural unit.Herein, " acryl resin " means a kind of polymkeric substance, and described polymkeric substance mainly contains the monomeric unit that is derived from the polymerizable monomer with (methyl) acryloyl group.In addition, " (methyl) acrylic acid " in this instructions means " acrylic acid " and " methacrylic acid " corresponding with it, and " (methyl) alkyl acrylate " means " alkyl acrylate " and " alkyl methacrylate " corresponding with it.
With regard to aforesaid propylene acid resin, can use by the polymerizable monomer with (methyl) acryloyl group is carried out to the resin that free radical polymerization is manufactured.This acryl resin can be with independent a kind or combine mode of more than two kinds and use.
As the above-mentioned polymerizable monomer with (methyl) acryloyl group, for example can list: the acrylic amine such as diacetone acrylamide, (methyl) alkyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid dimethylaminoethyl ester, (methyl) acrylic acid diethyllaminoethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid-2, 2, 2-trifluoroethyl ester, (methyl) acrylic acid-2, 2, 3, 3-tetrafluoro propyl diester, (methyl) acrylic acid, α-smelling (methyl) acrylic acid, α-chlorine (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid etc.
In addition, with regard to aforesaid propylene acid resin, except the polymerizable monomer with (methyl) acryloyl group as described above, one kind or two or more polymerizable monomer in also can the following polymerizable monomer of copolymerization: styrene, vinyltoluene, α-methyl styrene etc. are substituted polymerisable styrene derivative in alpha-position or aromatic ring, vinyl cyanide, the ester class of the vinyl alcohols such as vinyl n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, the maleic acid monoesters such as maleic acid list isopropyl ester, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid etc.
As above-mentioned (methyl) alkyl acrylate, for example, list: the compound being represented by following general formula (2) can replace and have hydroxyl, epoxy radicals, halogen etc. on the alkyl of these compounds.
CH
2=C(R
1)-COOR
2(2)
Herein, R
1represent hydrogen atom or methyl, R
2represent the alkyl of carbon number 1-12.As the alkyl of above-mentioned carbon number 1-12, for example, can list methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their constitutional isomer.
As the compound being represented by above-mentioned general formula (2), for example, list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecane ester, (methyl) acrylic acid undecane ester.They can be with independent a kind or combine mode of more than two kinds and use.
In addition, with regard to (a) binder polymkeric substance, from making the viewpoint that alkali-developable is better consider preferably there is carboxyl.
With regard to the ratio of the carboxyl having with regard to binder polymkeric substance, consider from the viewpoint that realizes alkali-developable and alkali tolerance balance, there is the polymerizable monomer of carboxyl with respect to the ratio of used whole polymerizable monomers, be preferably 20-90 quality %, more preferably 20-80 quality %, be particularly preferably 20-70 quality %, be extremely preferably 20-60 quality %.If the ratio less than 20 quality % that this has the polymerizable monomer of carboxyl, exist the poor tendency of alkali-developable, if exceed 90 quality %, there is the poor tendency of alkali tolerance.
With regard to the weight-average molecular weight of binder polymkeric substance, from realize physical strength and alkali-developable balance viewpoint consider, be preferably 5000-300000, more preferably 20000-150000, is particularly preferably 30000-100000.With regard to weight-average molecular weight, if micropodia 5000,, if exceed 300000, there is the elongated tendency of development time in the tendency that exists resistance to development fluidity to reduce.It should be noted that, the weight-average molecular weight in the present invention is: the value of measuring by gel permeation chromatography (GPC), converse according to the typical curve that uses polystyrene standard to make.
These binder polymkeric substance can be used alone a kind or combine mode of more than two kinds and use.At the binder polymkeric substance by two or more combination and under service condition, for example, can list: the binder polymkeric substance of more than two kinds that comprises the binder polymkeric substance of more than two kinds of the binder polymkeric substance of more than two kinds of different copolymer composition, different weight-average molecular weight, different dispersion degree.
Then the optical polymerism compound that, (b) is had to an ethylene unsaturated bond describes.
As the optical polymerism compound with ethylene unsaturated bond, the monomer that comprises tool ethylene unsaturated bond, for example can list: by making α, thereby beta-unsaturated carboxylic acid reacts the compound obtaining with polyvalent alcohol, as 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-, 2, two (4-(methyl) acryloxy the gathers propoxyl group) phenyl of 2-) propane, 2, bisphenol-A system (methyl) acrylate compounds such as two (4-((methyl) acryloxy polyethoxy the gathers propoxyl group) phenyl) propane of 2-, by making α, beta-unsaturated carboxylic acid and the compound obtaining containing the compound of glycidyl reacts, there is the carbamate monomers such as (methyl) acrylate compounds of urethane bond, γ-chloro-β-hydroxy propyl-Beta '-(methyl) acryloxy ethyl phthalic ester, beta-hydroxyethyl-β '-(methyl) acryloxy ethyl phthalic ester, β-hydroxy propyl-Beta '-(methyl) acryloxy ethyl phthalic ester, (methyl) alkyl acrylate etc.They can be used alone or combine two or more and use.
As above-mentioned 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-, for example can list: 2, two (4-((methyl) acryloxy diethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy tetraethoxy) phenyl) propane of 2-, 2, two (4-(methyl) acryloxy tetraethoxy) phenyl of 2-) propane, 2, two (4-(methyl) the acryloxy five ethoxys) phenyl of 2-) propane, 2, two (4-((methyl) propylene acyloxy six ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy seven ethoxys) phenyl) propane of 2-, 2, two (4-(methyl) the acryloxy eight ethoxys) phenyl of 2-) propane, 2, two (4-(methyl) the acryloxy nine ethoxys) phenyl of 2-) propane, 2, two (4-(methyl) the acryloxy ten ethoxys) phenyl of 2-) propane, 2, two (4-(methyl) the acryloxy 11 ethoxys) phenyl of 2-) propane, 2, two (4-((methyl) acryloxy ten diethoxies) phenyl) propane of 2-, 2, two (4-(methyl) the acryloxy ten triethoxies) phenyl of 2-) propane, 2, two (4-(methyl) the propylene acyloxy ten tetraethoxies) phenyl of 2-) propane, 2, two (4-((methyl) propylene acyloxy 15 ethoxys) phenyl) propane of 2-, 2, two (4-(methyl) the acryloxy 16 ethoxys) phenyl of 2-) propane.Among them, with regard to 2, two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-, can commercially obtain " BPE-500 " (chemical industry Co., Ltd. of Xin Zhong village system, trade name), with regard to two (4-(the methacryloxy 15 ethoxys) phenyl) propane of 2,2-, can commercially obtain " BPE-1300 " (chemical industry Co., Ltd. of Xin Zhong village system, trade name).They can be used alone or combine two or more and use.
As above-mentioned by making α, thereby beta-unsaturated carboxylic acid react with polyvalent alcohol obtain compound, for example can list: polyglycol two (methyl) acrylate that the quantity of ethylidene is 2-14, the quantity of propylidene is polypropylene glycol two (methyl) acrylate of 2-14, the quantity of ethylidene is polyglycol polypropylene glycol two (methyl) acrylate that the quantity of 2-14 and propylidene is 2-14, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethoxy three (methyl) acrylate, trimethylolpropane diethoxy three (methyl) acrylate, trimethylolpropane tris ethoxy three (methyl) acrylate, trimethylolpropane tetraethoxy three (methyl) acrylate, trimethylolpropane five ethoxy three (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, the quantity of propylidene is polypropylene glycol two (methyl) acrylate of 2-14, dipentaerythritol five (methyl) propylene vinegar, dipentaerythritol six (methyl) acrylate.
As above-mentioned carbamate monomer, for example can list: (methyl) acrylic monomers and the isophorone diisocyanate, 2 in β position with hydroxyl, 6-toluene diisocyanate, 2,4-toluene diisocyanate, 1, the addition reaction of the diisocyanate cpds such as 6-hexamethylene diisocyanate, three [(methyl) acryloxy TEG isocyanato-] hexa-methylene isocyanuric acid ester, EO modified amido formic ether two (methyl) acrylate, EO, PO modified amido formic ether two (methyl) acrylate etc.It should be noted that, " EO " representative ring oxidative ethane, EO modification compound there is the block structure (block structure) of Oxyranyle.In addition, " PO " representative ring Ethylene Oxide, PO modification compound there is the block structure of epoxypropane base.As EO modified polyurethane two (methyl) acrylate, for example, can enumerate " UA-11 " (chemical industry Co., Ltd. of Xin Zhong village system, trade name).In addition, as EO, PO modified amido formic ether two (methyl) acrylate, for example, can enumerate " UA-13 " (chemistry Xia Ye Co., Ltd. of Xin Zhong village system, trade name).
As the monomer with glycidyl, can enumerate (methyl) glycidyl acrylate, to ethenylphenyl glycidol ether etc.As the monomer with carboxyl, can enumerate the unsaturated monoacid such as (methyl) acrylic acid, monoesters, the monoamides etc. of the unsaturated dibasic acids such as itaconic acid, fumaric acid, maleic acid and acid anhydrides thereof and these unsaturated dibasic acids.As thering is sulfonic monomer, can enumerate (methyl) acrylic acid sulphur ethyl ester, (methyl) acrylamido methyl propane sulfonic acid, vinyl sulfonic acid, vinyl pyrovinic acid, isopropenyl pyrovinic acid, sulfuric ester (the trade name work RS-30 that for example Sanyo Chemical Industries, Ltd. manufactures) to the alcohol after (methyl) acrylic acid addition of ethylene oxide or epoxypropane, (methyl) acryloxy ethylsulfonic acid, monoalkyl sulfosuccinate and the ester with allylic compound, the resultant of reaction of monoalkyl sulfosuccinate and (methyl) glycidyl acrylate etc.As the polymerism unsaturated monomer with phosphonate group, can enumerate list (2-hydroxyethyl) (methyl) acrylate of vinyl phosphoric acid, mono phosphoric acid ester (2-hydroxyethyl) (methyl) acrylate, mono alkyl phosphate etc.
These carboxyls, sulfonic group also can neutralize with alkaline metal, earth alkali metal or amine.Can enumerate sodium, potassium, lithium etc. as the alkaline metal for neutralizing; Can enumerate calcium, magnesium etc. as earth alkali metal; Can enumerate ammonia, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine etc. as amine.
In the time of polymerization, can be further as required and with can with the monomer of above-mentioned these monomer copolymerizations.As monomer that can copolymerization, can enumerate for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate, (methyl) benzyl acrylate, isophorone base (methyl) acrylate, adamantyl (methyl) acrylate, (methyl) cyclohexyl acrylate, styrene, α-methyl styrene, vinyl cyanide, vinyl acetate ester etc.
In addition, also can use the multifunctional type monomer with two or more pairs of keys.As the concrete example of these multifunctional type monomers, can enumerate methylene diacrylamine, methylene diacrylamine, ethylene acrylamide, ethylene Methacrylamide, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, divinylbenzene, diallyl acrylamide, triallyl isocyanurate, three acrylic acid pentaerythrites etc.With respect to the whole monomers that form hydrophilic resin, the amount of these multifunctional type monomers is preferably 5-60 quality %, more preferably 5-50 quality %.
Containing of optical polymerism compound is proportional, with respect to total amount 100 mass parts of binder polymkeric substance and optical polymerism compound, is preferably 5-60 mass parts, more preferably 5-50 mass parts.If should, containing proportional less than 5 mass parts, easily there is the not good tendency of film, if exceed 60 mass parts, under the collection batching as film, there is the tendency that is difficult to preservation.
Then (d) Photoepolymerizationinitiater initiater is described.
As the Photoepolymerizationinitiater initiater of unsaturated allyl compound system photopolymerization reaction, component (d) comprises compound shown in following formula (1) (, PBG-325):
Except compound shown in formula (1), component (d) can also contain other Photoepolymerizationinitiater initiater to be combined with, for example, can list: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, benzophenone, N, N '-tetramethyl-4,4 '-diaminobenzophenone (Michler's keton (Michler's ketone)), N, N '-tetraethyl-4,4 '-diaminobenzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl mercapto) phenyl)-2-morpholino-acetone-1 aromatic ketone such as grade, 2-ethyl green onion quinone, phenanthrenequione, 2-tert-butyl group green onion quinone, prestox green onion quinone, 1,2-benzo green onion quinone, 2,3-benzo green onion quinone, 2-phenyl green onion quinone, 2,3-diphenyl green onion quinone, l-chlorine green onion quinone, 2-methyl green onion quinone, 1,4-naphthoquinone, 9,10-phenanthrenequione, 2-MNQ, the quinones such as 2,3-dimethyl green onion quinone, benzoin methylether, benzoin ethyl ether, the benzoin ether compounds such as benzoin phenylate, benzoin, methylbenzene acyloin, the benzoin compounds such as ethylbenzene acyloin, 1,2-octane diketone-1-[4-(phenyl sulfo-) phenyl)-2-(0-benzoyl oximes), l-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] oxime ester compound such as ethyl ketone 1-(0-acetyl group oxime), the benzil derivants such as benzil dimethyl ketal, 2-Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-bis-(methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc. 2,4,5-triarylimidazoles dipolymer, 9-phenylacridine, the acridine derivatives such as two (9, the 9 '-acridinyl) heptane of 1,7-, N-phenylglycine, N-phenylglycine derivant, coumarin series compounds, oxazole based compound.In addition, 22,4, thus the aryl substituent of 5-triarylimidazoles can identically produce symmetrical compound, produces asymmetric compound thereby also can be difference.In addition, as the combination of diethyl thioxanthone and dimethylaminobenzoic acid, thioxanthones based compound capable of being combined and tertiary amine compound.Wherein, from transparent viewpoint, more preferably 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 compound such as aromatic ketone such as grade, 1,2-octane diketone-1-[4-(phenyl sulfo-) phenyl] oxime ester compound such as-2-(0-benzoxy oxime).They separately with or combine two or more and use.
Containing of Photoepolymerizationinitiater initiater is proportional, with respect to total amount 100 mass parts of binder polymkeric substance and optical polymerism compound, is preferably 0.01 to 20 mass parts, and more preferably 0.01-15 mass parts, is particularly preferably 0.01-10 mass parts.If should, containing proportional less than 0.01 mass parts, exist photo sensitivity to become inadequate tendency; If exceed 20 mass parts, thereby exist the inner photocuring of absorption increase of the surface of photaesthesia resin bed in exposure to become inadequate tendency.
Light curing resin composition can contain (c) adjuvant, can be as required, contain individually a kind or combine following material of more than two kinds: the plastifier such as para toluene sulfonamide, filling agent, defoamer, fire retardant, stabilizing agent, adaptation imparting agent, levelling agent, peel off promoter, antioxidant, spices, preparation, thermal cross-linking agent etc.With regard to the addition of these adjuvants, with respect to total amount 100 mass parts of binder polymkeric substance and optical polymerism compound, be preferably separately 0 to 20 mass parts.
With regard to light curing resin composition, (c) adjuvant can contain a kind or combine two or more following solvent as required: methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve (methyl cellosolve), ethyl cellosolve (ethyl cellosolve), toluene, N, N '-dimethyl formamide, propylene glycol monomethyl ether etc.By forming with solvent the solution that solid constituent is the light curing resin composition of 0 to 20 quality % left and right, and then the dry composition that forms.But, in the case, for the remaining organic solvent amount in dried light curing resin composition, in order to prevent the diffusion of organic solvent in operation below, be preferably below 2 quality %.
Light curing resin composition of the present invention can be by mixing each component to be prepared from.
Then, the manufacturing process of light curing resin composition of the present invention is described.
With regard to coating, can be coated with the known methods such as method, scraper rubbing method, spraying rubbing method by such as rolling method, comma rubbing method, intaglio plate rubbing method, airblade coating method, mould and carry out.After coating, for removing the dry of organic solvent etc., can utilize hot wind convection type dryer within 5-30 minute, to carry out 70-150 DEG C of processing.
With regard to the dried thickness of light curing resin composition, because purposes is different, dried thickness is preferably 1-200 μ m, and more preferably 1-15 μ m is particularly preferably 1-10 μ m.If the not enough l μ of this thickness is m, there is the tendency of physical strength deficiency, if exceed 200 μ m, exist because the reduction of light transmission causes sensitivity and become insufficient, the tendency that causes the mixed photo-curable of light curing resin composition to reduce.
With regard to exposure process, by irradiating active ray, light curing resin composition is solidified.As the light source of active ray, can use known light source, such as carbon arc lamp, mercury vapor arc lamp, extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, ammonia lamp etc. radiate the light source of ultraviolet ray, visible ray etc. effectively.In addition, also can use Ar ion laser, semiconductor laser etc. effectively to radiate the light source of ultraviolet ray, visible ray etc.Further also can use photography floodlight bulb (flood light bulb), Solar lamp (solar lamp) etc. effectively to radiate the lamp of visible ray, thereby or also can adopt the method for irradiating active ray by using the direct picture image shapes such as laser explosure method.
Through above-mentioned operation, thereby can obtain a kind of light curing resin composition that possesses resistance to xanthochromia.For the manufacturing process of light curing resin composition of the present invention, also can, by the light curing resin composition of formed thereby (after developing), carry out as required heating or the 0.2-10J/cm of 60-250 DEG C of left and right
2the exposure of left and right, thus further solidify.
So, light curing resin composition of the present invention can form one patterned easily on the base materials such as glass, plastics, pottery, metal.
With regard to light curing resin composition of the present invention, after solidifying, the result of resistance to UV and high temperature xanthochromia utilizes Lab color model to carry out xanthochromia judgement, and Lab color model is that tri-key elements of b form by illumination (L) with about a of color.L represents illumination (Luminosity), is equivalent to brightness, and a represents that, from carmetta to green scope, b represents from yellow to blue scope.
Use the light curing resin composition of PBG-325 through <350mJ/cm
2energy-curable after, then, again through 200 DEG C of Temperature Treatment after 6 hours, yellow value degree (YI) is less than or equal to 4.
Use the light curing resin composition of PBG-325 through <350mJ/cm
2energy-curable after, then again through adding the 4J/cm that exposes to the sun
2, yellow value degree (YI) is less than or equal to 4.
Advantage and effect:
Experimental result shows, light curing resin composition of the present invention is excellent performance aspect the xanthochromia of resistance to UV and high temperature xanthochromia, is easier to produce the problem of UV xanthochromia and high temperature xanthochromia after can causing light curing resin composition to solidify unlike the Photoepolymerizationinitiater initiaters such as OXE-01.
Embodiment
So that the present invention is described in further detail, but should not be understood as limiting the scope of the invention below with reference to embodiment.
< self-control binder polymkeric substance, quality %>
| Binder polymkeric substance | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 |
| Methacrylic acid | 27.00% | 27.00% | 20.00% | 24.10% | 27.70% | 27.70% |
| Yue base acrylic acid Yue ester | 36.00% | 30.00% | 30.60% | 32.80% | 35.60% | 40.60% |
| Butyl acrylate | 10.10% | 5.10% | 12.90% | 14.70% | 12.90% | 10.90% |
| Benzyl acrylate | 0.00% | 5.00% | 14.90% | 12.90% | 14.90% | 12.90% |
| Butyl methacrylate | 0.00% | 6.00% | 7.90% | 0.00% | 7.90% | 6.90% |
| Acrylic acid 2-Octyl Nitrite | 23.60% | 23.60% | 11.7% | 9.60% | 0.00% | 0.00% |
| Styrene | 0.00% | 2.30% | 1% | 0.00% | 0.00% | 0.00% |
| 2,2--azobis isobutyronitrile | 3.30% | 1.00% | 1.00% | 5.90% | 1.00% | 1.00% |
| Total | 100% | 100% | 100% | 100% | 100% | 100% |
< Photocurable composition >
B1: three Yue alcohol propane triacrylate of ethoxy upgrading (
4155, Cognis)
B2: fatty amine carbamate oligomer
B3: three Yue alcohol propane triacrylate (
231, Changxing chemical industry)
B4: trihydroxymethyl propane three Yue base acrylate (
331, Changxing chemical industry)
B5: standard bisphenol-A-epoxy diacrylate (
621A-80, Changxing)
C1:PBG-325, i.e. compound shown in formula (1) (Changzhou potenxin electronic material)
C2:Irgacure OXE01 (Ciba spy's chemical company)
C3:TPO (2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide)
D1: acetone
Find according to above-mentioned experiment, if binder polymkeric substance or have in the optical polymerism compound of vinyl unsaturated link and have benzene ring structure, amido epoxy radicals, Photocurable composition can be easier to xanthochromia, but still possesses good resistance to xanthochromia characteristic while using Photoepolymerizationinitiater initiater PGB325.
Find according to above-mentioned experiment, utilize PGB-325 as Photoepolymerizationinitiater initiater, the characteristic that can promote the resistance to xanthochromia of Photocurable composition also can have high photosensitivity concurrently.
In industry, utilize possibility
The invention provides a kind of novel light curing resin composition, there is the character of the better xanthochromia of resistance to UV, capable of resisting high-temperature yellowing and high photosensitivity.
Claims (8)
1. a light curing resin composition, at least comprises following component:
(a) the binder polymkeric substance of 20 to 90 quality %;
(b) 5 to 60 quality % one or more can with the optical polymerism compound with ethene unsaturated link of the described binder polymkeric substance of component (a) compatibility;
(c) adjuvant of 0 to 20 quality % and/or assistant;
(d) Photoepolymerizationinitiater initiater of 0.01 to 20 quality %, described Photoepolymerizationinitiater initiater comprises compound shown at least one following general structural formula:
Wherein low what 350 mj/cm of When exposure energy
2time, the low what 4 Yellow degree values of described light curing resin composition tool.
2. light curing resin composition claimed in claim 1, it is characterized in that, as component (a) binder polymkeric substance, be selected from acryl resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenolics, ester resin, urethane resin, by the acrylic acid Epocryl obtaining, the sour modified epoxy acrylic ester resin that reacts acquisition by Epocryl with acid anhydrides of reacting of epoxy resin and (methyl).
3. light curing resin composition claimed in claim 3, it is characterized in that, as component (a) binder polymkeric substance, be selected from acryl resin, this acryl resin contains the monomer unit that is derived from (methyl) acrylic acid and (methyl) alkyl acrylate as structural unit.
4. light curing resin composition claimed in claim 1, it is characterized in that, as component (b) optical polymerism compound, be selected from by making α, thereby beta-unsaturated carboxylic acid reacts the compound obtaining with polyvalent alcohol, by making α, beta-unsaturated carboxylic acid and the compound obtaining containing the compound of glycidyl reacts, carbamate monomer, γ-chloro-β-hydroxy propyl-Beta '-(methyl) acryloxy ethyl phthalic ester, beta-hydroxyethyl-β '-(methyl) interior alkene acyloxy ethyl phthalic ester, β-hydroxy propyl-Beta '-(methyl) acryloxy ethyl phthalic ester, (methyl) alkyl acrylate.
5. light curing resin composition claimed in claim 5, it is characterized in that, as component (b) optical polymerism compound, be selected from 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane, 2 of 2-, two (4-(methyl) acryloxy the gathers propoxyl group) phenyl of 2-) propane, 2, two (4-((methyl) acryloxy polyethoxy the gathers propoxyl group) phenyl) propane of 2-.
6. light curing resin composition claimed in claim 1, it is characterized in that, as component (c) adjuvant and/or assistant, be selected from plastifier, filling agent, defoamer, fire retardant, stabilizing agent, adaptation imparting agent, levelling agent, peel off promoter, antioxidant, spices, preparation, thermal cross-linking agent.
7. light curing resin composition claimed in claim 1, is characterized in that, as component (d) Photoepolymerizationinitiater initiater, also can contain the Photoepolymerizationinitiater initiater compound of other kind, is combined with compound shown in general structure 1.
8. light curing resin composition claimed in claim 1, is characterized in that, with respect to total amount 100 mass parts of binder polymkeric substance and optical polymerism compound, Photoepolymerizationinitiater initiater containing proportional be 0.01-10 mass parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410158610.4A CN103901725B (en) | 2014-04-19 | 2014-04-19 | A kind of light curing resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410158610.4A CN103901725B (en) | 2014-04-19 | 2014-04-19 | A kind of light curing resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103901725A true CN103901725A (en) | 2014-07-02 |
| CN103901725B CN103901725B (en) | 2017-07-28 |
Family
ID=50993134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410158610.4A Active CN103901725B (en) | 2014-04-19 | 2014-04-19 | A kind of light curing resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103901725B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709371A (en) * | 2015-12-28 | 2018-02-16 | 积水化学工业株式会社 | The manufacture method of Photocurable composition and electronic unit |
| CN107850841A (en) * | 2015-07-22 | 2018-03-27 | 荣昌化学制品株式会社 | For forming the KrF laser negative photoresist compositions of semiconductor pattern |
| CN110221520A (en) * | 2018-03-02 | 2019-09-10 | 常州强力电子新材料股份有限公司 | The modified dry film photoresist of graphene and its application in printed wiring board |
| CN111971597A (en) * | 2018-04-13 | 2020-11-20 | 住友化学株式会社 | Polymerizable liquid crystal composition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003226718A (en) * | 2002-02-07 | 2003-08-12 | Mitsubishi Gas Chem Co Inc | Photo-curing composition of high refractive index and its cured substance |
| US20050158659A1 (en) * | 2004-01-19 | 2005-07-21 | Chun-Hsien Lee | Photosensitive resin composition for black matrix |
| CN101960380A (en) * | 2008-03-10 | 2011-01-26 | 富士胶片株式会社 | Colored curable composition, color filter and solid-state imaging device |
| CN102206443A (en) * | 2010-03-31 | 2011-10-05 | 富士胶片株式会社 | Active radiation curable ink composition, ink composition for inkjet recording, printed matter, and method of producing molded article of printed matter |
| CN102417756A (en) * | 2010-09-24 | 2012-04-18 | 富士胶片株式会社 | Printing ink compound, ink jet recording method and ink jet printed object |
| CN102667531A (en) * | 2010-01-20 | 2012-09-12 | 富士胶片株式会社 | Black curable composition for wafer-level lens, and wafer-level lens |
| CN103374259A (en) * | 2012-04-19 | 2013-10-30 | 富士胶片株式会社 | Active energy ray-curable ink composition, inkjet recording method, decorative sheet, decorative sheet molded product, method for producing in-mold molded product, and in-mold molded product |
-
2014
- 2014-04-19 CN CN201410158610.4A patent/CN103901725B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003226718A (en) * | 2002-02-07 | 2003-08-12 | Mitsubishi Gas Chem Co Inc | Photo-curing composition of high refractive index and its cured substance |
| US20050158659A1 (en) * | 2004-01-19 | 2005-07-21 | Chun-Hsien Lee | Photosensitive resin composition for black matrix |
| CN101960380A (en) * | 2008-03-10 | 2011-01-26 | 富士胶片株式会社 | Colored curable composition, color filter and solid-state imaging device |
| CN102667531A (en) * | 2010-01-20 | 2012-09-12 | 富士胶片株式会社 | Black curable composition for wafer-level lens, and wafer-level lens |
| CN102206443A (en) * | 2010-03-31 | 2011-10-05 | 富士胶片株式会社 | Active radiation curable ink composition, ink composition for inkjet recording, printed matter, and method of producing molded article of printed matter |
| CN102417756A (en) * | 2010-09-24 | 2012-04-18 | 富士胶片株式会社 | Printing ink compound, ink jet recording method and ink jet printed object |
| CN103374259A (en) * | 2012-04-19 | 2013-10-30 | 富士胶片株式会社 | Active energy ray-curable ink composition, inkjet recording method, decorative sheet, decorative sheet molded product, method for producing in-mold molded product, and in-mold molded product |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107850841A (en) * | 2015-07-22 | 2018-03-27 | 荣昌化学制品株式会社 | For forming the KrF laser negative photoresist compositions of semiconductor pattern |
| CN107850841B (en) * | 2015-07-22 | 2021-04-02 | 荣昌化学制品株式会社 | Negative photoresist composition for KrF laser for forming semiconductor pattern |
| CN107709371A (en) * | 2015-12-28 | 2018-02-16 | 积水化学工业株式会社 | The manufacture method of Photocurable composition and electronic unit |
| CN110221520A (en) * | 2018-03-02 | 2019-09-10 | 常州强力电子新材料股份有限公司 | The modified dry film photoresist of graphene and its application in printed wiring board |
| CN110221520B (en) * | 2018-03-02 | 2021-10-08 | 常州强力电子新材料股份有限公司 | Graphene modified dry film photoresist and application thereof in printed circuit board |
| CN111971597A (en) * | 2018-04-13 | 2020-11-20 | 住友化学株式会社 | Polymerizable liquid crystal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103901725B (en) | 2017-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6134440B2 (en) | Acrylate-based photocurable composition | |
| CN102124529B (en) | Photosensitive conductive film, method for forming conductive film, method for forming conductive pattern, and conductive film substrate | |
| JP4628260B2 (en) | Photosensitive resin composition, method for producing the same, and dry film resist containing the same | |
| CN104950572B (en) | blue photosensitive resin composition for color filter and application thereof | |
| JP5660200B2 (en) | Photosensitive resin composition, photosensitive element using the same, method for forming partition of image display device, and method for manufacturing image display device | |
| KR20140142262A (en) | Triarylmethane compound, colored resin composiiton, color filter, liquid crystal display device, and organic el display device | |
| CN103901725B (en) | A kind of light curing resin composition | |
| CN107479327A (en) | Manufacture method, color conversion substrate and the display device of color conversion substrate | |
| KR100842168B1 (en) | Photosensitive resin composition and liquid crystal display device using the same | |
| KR20010052666A (en) | Photopolymerizable Resin Composition and Use Thereof | |
| TW201808874A (en) | Flourene multifunctional photoinitiator, method of production, and the use thereof, and photopolymer comprising the same and the use thereof | |
| JP5178737B2 (en) | Radiation-sensitive resin composition for spacer formation, spacer, spacer formation method, and liquid crystal display element | |
| JP2017155228A (en) | Colored composition for color filter, color filter and display device | |
| US7927781B2 (en) | Photosensitive resin composition, method for preparing the same, and dry film resist comprising the same | |
| JP5363844B2 (en) | Alkali-soluble photosensitive coloring composition and color filter | |
| JP2011075685A (en) | Colored resin composition, photosensitive coloring resin composition for color filter, and color filter | |
| JP5723091B2 (en) | Resin composition for yellow colored layer for color filter, photosensitive resin composition for yellow colored layer for color filter, and color filter | |
| CN112764315A (en) | Photosensitive composition suitable for no-prebaking process and preparation method thereof | |
| JP2004077773A (en) | Light hardening resin composition and display element using the composition | |
| CN101604120B (en) | Photosensitive composition | |
| TW201243497A (en) | Photosensitive resin composition for color filter and color filter using the same | |
| TWI261728B (en) | Photosensitive resin composition for a color filter | |
| JP6157111B2 (en) | Colored photosensitive resin composition, color filter, and color liquid crystal display element | |
| JP3356749B2 (en) | Photosensitive resin composition | |
| KR20130108759A (en) | Black colored photosensitive resin composition, black matrix manufactured by the composition and color filter comprising the black matrix |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |