CN101395533A - Curable compositions for providing a cured composition with enhanced water resistance - Google Patents
Curable compositions for providing a cured composition with enhanced water resistance Download PDFInfo
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- CN101395533A CN101395533A CNA200780007302XA CN200780007302A CN101395533A CN 101395533 A CN101395533 A CN 101395533A CN A200780007302X A CNA200780007302X A CN A200780007302XA CN 200780007302 A CN200780007302 A CN 200780007302A CN 101395533 A CN101395533 A CN 101395533A
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Abstract
The invention is an energy-curable composition which contains a dual functional component which has at least one ethylenically unsaturated group and at least one carboxylic acid-functional group and a nanoparticle metal oxide component. The curable composition can optionally contain initiators (photoinitiators and/or free radical initiators), components which can react with the dual functional component and additives generally present in energy-curable compositions.
Description
Related application
The application to submitted on March 1st, 2006, sequence number is that 60/778,053 provisional application requires right of priority, the full content of this provisional application is quoted as a reference herein.
Technical field
The present invention relates to a kind of energy-curable composition, be specifically related to the radiation curable composition, said composition can be used as bonding agent, coating, ink formulations, compound substance etc.The present composition provides bond strength, adhesion and moisture resistance that improved polymkeric substance is all arranged.
Summary of the invention
The present invention relates to energy-curable composition, said composition comprises a kind of compound, oligomer or low-molecular weight polymer with polymerizable ethylene linkage formula unsaturated group and carboxylic acid functional (di-functional component).Preferably, ethylenic unsaturated polymerizable group comprises vinyl ether group, (methyl) acrylic acid groups, allyl or alpha-olefin group, and this alpha-olefin group is preferably in the end of polymer chain part or on the polymer chain side group.The unsaturated component of curable ethylenic also contains carboxyl, and this carboxyl preferably in the end position of compound, oligomer or low-molecular weight polymer, perhaps can be included in the side chain of polymkeric substance.Preferably, carboxyl does not neutralize or esterification.Preferably, the number-average molecular weight of polymerisable di-functional component (polymerizable ethylene linkage formula unsaturated group and carboxyl) is about 150 to about 10,000, and preferred about 200 to about 5,000, and most preferably from about 250 to about 3,000 scope.
In addition, said composition can contain the lower-molecular-weight component and/or the oligomer that can mix with the unsaturated component of difunctionality ethylenic, and contain can with the group of di-functional component polymerization.
The other key component of the present invention comprises the metal oxide of nano particle size, is preferably zinc paste.The metal oxide of this nano particle size improves the bond strength and the moisture-proof of cured polymeric material.
Detailed Description Of The Invention
This dual functional (ethylenic is undersaturated and carboxyl-functional) component, well-known in this technical field, and be used for the energy-curable preparation many years.Dual functional energy-curable composition has been disclosed in U.S.5, and in 912,381, U.S.6,429,235, U.S.6,908,665, U.S.6,472,056 and U.S.6,565,696, the full content of each patent document is incorporated herein by reference.Each patent document that is incorporated herein by reference discloses the method, helper component and the adjuvant that can be used for implementing the different types of di-functional component of the present invention, the preparation that contains this component, hardening composition, and the preparation method of useful constituent.
The key character that can be used for implementing difunctionality polymerizable components of the present invention is that they contain at least one polymerizable ethylene linkage formula unsaturated group and at least one carboxyl functional group.Di-functional component can be a molecular weight at 150 dalton or the compound of the lower molecular weight of scope still less, perhaps can be oligomer, and its molecular weight (Mn) is about 10,000 at the most, and is preferably about at the most 5,000, most preferably in about at the most 2,000 the scope.
The scope that di-functional component exists can be the energy-curable composition general assembly (TW) about 1% to about 99%, preferred about 10% to about 90%, most preferably from about 25% to about 75%.
Energy-curable composition of the present invention can be chosen wantonly and contain various components and oligomer, this component and oligomer have the undersaturated functional group of polymerizable ethylene linkage formula, have the functional group that contains the hydrogen atom that can react, perhaps have can with the group that reacts such as the hydrogen atom that can react in each group such as hydroxyl, carboxyl, amide group, isocyanate group, vinyl ether, epoxy radicals.
Suitable di-functional component comprises such as with 1 of hydroxyethyl acrylate modification, 2-cyclohexane dicarboxylic acid acid anhydride, hydroxyethyl acrylate with caprolactone modification, phthalic anhydride with the hydroxyethyl acrylate modification, with the alkyl succinic anhydride of hydroxyethyl acrylate modification or the alkenyl succinic anhydrides of hydroxyethyl acrylate modification, dimer acid with the modification of double trimethylolpropane triacrylate, maleic anhydride with the hydroxyethyl acrylate modification, material with the allyl compound class of the dimer acid of trimethylolpropane diacrylate modification and similar (homologous).Make acid and anhydride modification by the reaction of the unsaturated component of part carboxyl and ethylenic (composition) only.Usually, have only one to react in two carboxyls of formation acid anhydride, perhaps have only one in the dimer acid group and be able to modification.Above-mentioned enumerating is exemplary, more illustrates in each patent document that the useful constituent of wide region then is incorporated herein by reference.
The optional components that can be used for the present composition comprises that molecular weight (Mn) is about 1,000 to about 3, aliphatic urethane acrylate in 000 scope, isobornyl acrylate, propoxylation trimethylolpropane triacrylate, propoxylation nonylphenol acrylate etc.More than cited only be exemplary rather than be included in whole compounds in the present composition.The amount of these optional components be the energy-curable composition general assembly (TW) about 5% to about 75%, preferred about 10% to about 60%, most preferably from about 15% to about 50%.
Can be used to implement the particle that metal oxide of the present invention comprises the nanoscale size of metal oxide.The particle mean size of nano-scale particle is less than 1 micron.The particle mean size of nano-scale particle is more preferably less than about 500nm preferably less than about 800nm, most preferably at the most in about 400nm scope.Metal oxide comprises the material such as aluminium oxide, titania, zinc paste etc.The amount scope of these metal oxide nanoparticles, for about 0.01% weight of energy-curable composition to about 15% weight, preferably curable compositions 0.1% to about 10% weight range, most preferably in 0.5% weight to 5% weight range of said composition.
When using zinc paste as metal oxide, to decide on the particle diameter of Nano-class zinc oxide, the present composition can be transparent material when solidifying, because zinc paste transmissive visible light in a certain nano particle size scope.Yet some Zinc oxide nanoparticle is visible light transmissive not, thereby can provide muddy or opaque character to cured compositions.
The zinc paste that is the nano particle size of pellucidity can be from Elementis company by trade name TECYLOXYL
TMUV buys.If the transparency is not a problem, for example when curable compositions of the present invention is used as the bonding agent of opaque material, can use the zinc paste of other nano particle size of other grades.
Well-known in this technical field, the nano particle of some metal oxide filters or absorbs the ultraviolet ray of some frequency in certain particle size range.This can make with the ultraviolet irradiation method curing present composition and become difficult, unless the illumination wavelength of selecting is within the scope that the irradiation that is used for hardening composition is not absorbed or reflects by metal oxide nanoparticles.Yet, because normally incomplete, so the present composition can be cured by the ultraviolet irradiation intensity that raising is used for hardening composition to the absorption of ultraviolet radiation or reflection.The zinc paste of nano particle size is preferred metal oxide.
The present composition can with electron beam (EB) irradiation be cured and not with composition in the Nano-class zinc oxide particle absorb or the relevant difficulty of reflected illumination.It is opaque object that electronic beam curing also can be used for ultraviolet irradiation.Therefore usually, electronic beam curing can carry out under lower temperature, and the distortion because of the goods due to the heating does not take place.
The least method of preferred (least preferred) of solidifying the present composition is at high temperature to utilize the polymerization initiator (polymerized initiators) that helps the composition polymerization.Curing can at high temperature use radical initiator to carry out, or if temperature when enough high, can not use radical initiator to carry out.In the chosen temperature scope, can select radical initiator to come hardening composition.
Energy-curable composition of the present invention can contain those materials that can carry out copolymerization with useful in the embodiment of this invention difunctionality energy-curable component.Auxiliary material can be added in the composition, with the characteristic of composition of control polymerization.That is to say that the polymerizable material that is used to control such as character such as flexible, hardness, temperature tolerance, solvent resistance, moisture-proofs can be included in the energy polymerisable compound of the present invention.Auxiliary material contain, the group that can react with at least a group in the dual-functional materials.Because di-functional component comprises at least one polymerizable double bond and at least one carboxyl functional group, can be included in the energy-curable composition with the material that polymerizable unsaturated group and/or free carboxyl group react so contain.The structure of selecting auxiliary polymerizable material is to improve at least a characteristic of hardening composition.But can influence characteristic such as flexible, hardness, solvent resistance, resistance to impact and bounding force by these auxiliary copolymeric materials.
Auxiliary material can comprise such as modified polyamide, Mn about 1,000 material to the interior modified epoxy acrylic ester of about 10,000 scopes, isobornyl acrylate, propoxylation trimethylolpropane triacrylate, decanediol diacrylate, the aliphatic polyester resin that contains 60% hexanediyl ester, propoxylation acrylic acid nonyl phenolic ester etc.These auxiliary material can contain reactive group, for example polymerizable ethylene linkage formula unsaturated group, hydroxyl, amino etc.These auxiliary material, should contain can with the di-functional component of composition or the group that carries out polymerization with itself or with other adjuvants of composition.Preferably, auxiliary material can pass through ethylenic unsaturated group and di-functional component copolymerization.
Polymerisable compound can contain the material such as plastifier, with flexible, the fragility of improving hardening composition, hardness etc.Plastifier should careful selection, so that they do not produce harmful effect to the particular substrate of using composition such as fusible character.Usually be present in the auxiliary material in the energy-curable composition, for example polymerization inhibitor, stabilizing agent, rheology modifier, thinning agent, oxidation inhibitor, anti-aging component, pigment etc. all can be present in the present composition.
By the functionality (functionality) of the helper component that added in the composition, also can improve the characteristic of solidifying polymeric compositions.The functionality of helper component affects the crosslinked amount of composition, and can make cure polymer have higher hardness and/or low fragility, improved temperature tolerance, improved flexible, improved solvent resistance etc.
The combination of difunctionality polymerizable components and nanosize metal oxide has improved the bounding force and the moisture resistance of cure polymer.
The heating that the present composition can be used in combination catalyzer (radical initiator) is solidified, available ultraviolet light polymerization, and available electron bundle (EB) solidifies.The method of most preferred hardening composition is an electronic beam method, and this method can be used to solidify and the relevant composition of the opaque film of possibility, and essential the assurance thoroughly solidified.The curable extremely wherein cure polymer of the present composition contains very hypotonic degree of moving thing (migrant) concentration, and this can make said composition be used for the product relevant with food.Said composition is used in particular for the lamination (laminating) of food and the polymer packaging of sealing.
The present composition can particularly be used as surface coating, and be solidified, to improve the water tolerance of matrix at matrix on the paper shape matrix.The present composition can be applied on the paper shape matrix, makes it keep in touch a period of time, so that the present composition permeates the film/base body that it is coated with, and preferably solidifies said composition with ultraviolet light or electron beam irradiation method.
Also the present composition can be contained in the ink formulations that contains different pigment and other components, in the printing-ink preparation, to provide desirable characteristics.The present composition has improved the bounding force of printing ink to matrix, but also has improved the water-fast and moisture-proof of printing material.When essential improvement moisture-proof or water tolerance, it is useful that matrix and the printing ink water tolerance when composition applies and solidify strengthens.
In a preferred embodiment of this invention, said composition is solidified with electron beam irradiation method, does not just need light trigger in the composition.But when said composition is solidified with ultraviolet irradiation, need light trigger usually.The light trigger that ultraviolet-ray curing composition is used is known in this technical field, and can be used as initiating agent usually in the present composition.To move thing be problem if ooze, and when for example being associated with food, then light trigger can be the high molecular type, perhaps can be the type of mixing polymkeric substance in the solidification process.Use high molecular light trigger and polymerizable light trigger can prevent effectively that light trigger from oozing the surface that moves on to hardening composition.When cured article will be united use with food, this was useful especially.That is to say, when stack adhesive that is used for packaging for foodstuff or diaphragm seal agent.
The present composition is to producing good bounding force such as different matrixes such as poly alpha olefin, metal, polyamide, polyester, polyethers, polyurethane.
Prepare the present composition according to following method, and it is tested.Each preparation to be tested is coated in 10～12 micron coatings on 6 inches * 8 inches the metallized foil matrix.Mylar (Dupont Teijin Films 48 LBT, size 12) is close on the surface of the bonding agent coating that is put into the metallized foil matrix, and makes it by the card laminate machine.Then, the gained laminated film is cured with 100 feet/min with 30 kilograys (kilogray) with electron-beam radiation source.Respectively be 1 inch coupons from solidifying that laminate specimen cuts immediately after the curing, on Thwing-Albert Friction/PeelTester (model 225-1), measure peel strength numerical value then with 12 inches/min.The coupons that makes electronic beam curing is balance 2 days at room temperature.After 2 days, coupons was immersed in 60 ℃ of water 1 hour, after coupons is taken out, carry out disbonded test immediately from water.Adhesive composition and disbonded test the results are shown in
Table 1:
Table 1
*ECX 6026 aliphatic urethane acrylate (2,000Mn)
*Nano particle ZnO particle mean size 50～70nm
* *CDAHA is with 1 of the Hydroxyethyl Acrylate modification, 2-cyclohexane dicarboxylic acid acid anhydride
Can see from the test findings shown in the table 1, add nano particle ZnO, significant effects be arranged for the dipping 1 hour in 60 ℃ of water and the peel strength of film of after from water-bath, taking out, carrying out the adhesives of disbonded test immediately.
In composition, add nano particle ZnO, improved the bonding peel strength behind the dipping in 60 ℃ of water greatly.It seems that by prior art the improvement of peel strength and moisture-proof is unexpected.
Claims (16)
1. the composition of energy-curable, said composition comprises dual functional energy polymerizable components, nano particle metal oxide, and optional polymerization initiator.
2. the described composition of claim 1, said composition comprise the dual functional energy polymerizable components of about 1% weight to about 99% weight.
3. the described composition of claim 2, said composition comprises the dual functional energy polymerizable components of 10% weight to 90% weight.
4. the described composition of claim 3, said composition comprises the dual functional energy polymerizable components of 25% weight to 75% weight.
5. the described composition of claim 1, said composition comprise the nano particle metal oxide of about 0.01% weight to about 20% weight.
6. the described composition of claim 5, said composition comprises the nano particle metal oxide of 0.1% weight to 15% weight.
7. the described composition of claim 2, said composition comprises dual functional energy polymerizable components, nano particle zinc paste, and can with the copolymerization of dual functional energy polymerizable components functional components, the amount of this functional components is that about 5% weight of energy-curable composition is to about 75% weight.
8. the described composition of claim 7, but the amount of wherein copolymerization component is 10% weight to 60% weight of energy-curable composition.
9. the described composition of claim 8, but the amount of wherein copolymerization component is 15% weight to 50% weight of energy-curable composition.
10. the described composition of claim 1, wherein the nano particle metal oxide comprises at least a metal oxide that is selected from zinc paste, titania and aluminium oxide.
11. the described energy-curable composition of claim 1, said composition comprises the adjuvant of about at the most 30% weight.
12. the described energy-curable composition of claim 1, but said composition comprises about 10% weight to the dual functional energy polymerizable components of about 75% weight, about 5% weight to about 75% weight and the functional components of dual functional energy polymerizable components copolymerization, 0.01% weight to 20% weight nano particle metal oxide, the adjuvant and the polymerization initiator of 30% weight at the most.
13. the described energy-curable composition of claim 12, wherein the nano particle metal oxide comprises zinc paste.
14. the described composition of the claim 1 of electronic beam curing.
15. the described composition of the claim 7 of electronic beam curing.
16. the described composition of the claim 12 of electronic beam curing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77805306P | 2006-03-01 | 2006-03-01 | |
| US60/778,053 | 2006-03-01 | ||
| US11/680,097 | 2007-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101395533A true CN101395533A (en) | 2009-03-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200780007302XA Pending CN101395533A (en) | 2006-03-01 | 2007-03-01 | Curable compositions for providing a cured composition with enhanced water resistance |
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| CN (1) | CN101395533A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102667962A (en) * | 2010-01-21 | 2012-09-12 | 株式会社藤仓 | Electroconductive paste for electron beam curing and circuit board production method using same |
| CN104067172A (en) * | 2012-01-26 | 2014-09-24 | 东京应化工业株式会社 | Photosensitive composition, pattern, and display device having pattern |
-
2007
- 2007-03-01 CN CNA200780007302XA patent/CN101395533A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102667962A (en) * | 2010-01-21 | 2012-09-12 | 株式会社藤仓 | Electroconductive paste for electron beam curing and circuit board production method using same |
| CN104067172A (en) * | 2012-01-26 | 2014-09-24 | 东京应化工业株式会社 | Photosensitive composition, pattern, and display device having pattern |
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