CN101034258B - Liquid light curing resin composition - Google Patents
Liquid light curing resin composition Download PDFInfo
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- CN101034258B CN101034258B CN2006100632863A CN200610063286A CN101034258B CN 101034258 B CN101034258 B CN 101034258B CN 2006100632863 A CN2006100632863 A CN 2006100632863A CN 200610063286 A CN200610063286 A CN 200610063286A CN 101034258 B CN101034258 B CN 101034258B
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Abstract
The invention discloses a liquid photo-curable resin combination, comprising modified polyurethane (methyl) acrylate polymer, (methyl) acrylate monomer, photo initiator, and silicane crosslinking agent. After photo-cured, it can generate a cured product with excellent acid and alkali resistance, water resistance and impact resistance, excellent mechanical intensity, excellent adhesiveness, etc. And it is suitable to use as photo-cured adhesive, photo-curable sealing material and photo-cured coating.
Description
Technical field
The present invention relates to liquid light curing resin composition, more particularly, the present invention relates to liquid light curing resin composition, it can produce the cured article of a kind of resistance to acids and bases, water tolerance, impact resistance of Excellence in Performance, excellent physical strength and outstanding characteristics such as cohesive behind photocuring.Be suitable as Photocurable adhesive, photocurable encapsulant and photo-cured coating.
Technical background
In the middle of liquid light curing resin composition, the resin combination of having developed based on (methyl) acrylate, wherein modified acrylic ester resin (claiming prepolymer again) is wherein to the composition of performance impact maximum, and modification (methyl) acrylate resin two kinds of most important resins (claiming prepolymer) are arranged is exactly modified polyurethane modification (methyl) acrylate (being called for short PUA) and epoxide modified (methyl) acrylate (abbreviation EA).Wherein EA is relatively cheap owing to price, and good to most of base materials (particularly polar substrates) adhesion, laser curing velocity is fast, and chemical resistance is good, the intensity height, thus obtained using the most widely in the photocuring field.And PUA synthesis technique simple and flexible can be regulated resin property by MOLECULE DESIGN, therefore can design control in advance with regard to many-sided performances such as flexibility, hardness, tolerances, and the resin dirigibility is very strong.Owing to better elastic, water tolerance, impact resistance are often added in bonding agent, the encapsulant to improve water tolerance, shock resistance as adjuvant at polybutadiene rubber.
Yet because the toughness deficiency, cold-resistant thermal shock resistance properties is relatively poor based on the Photocurable resin composition of EA, and often water tolerance is also good inadequately; Photocurable resin composition resistance to acids and bases, thermotolerance based on PUA are bad; The compatibility of polybutadiene rubber and PUA and EA is bad.Still do not know to have concurrently the material of this three classes material behavior so far.
Therefore, the purpose of this invention is to provide a kind of liquid light curing resin composition, it has resistance to acids and bases, water tolerance, impact resistance, the physical strength of excellence and outstanding cohesive behind photocuring.Be suitable as Photocurable adhesive, photocurable encapsulant and photo-cured coating.
Summary of the invention
This purpose of the present invention can adopt according to a kind of liquid light curing resin composition of the present invention and reach, and it comprises,
(1) modified polyurethane (methyl) acrylate polymer,
(2) (methyl) acrylate monomer,
(3) light trigger,
(4) silane coupling agent.
Detailed Description Of The Invention and preferred embodiment:
The preferred embodiment of above-mentioned modified polyurethane (methyl) acrylate polymer (1) comprises that its structure is A-B-C/D.Wherein, A is a hydroxyl terminated polybutadiene rubber, and B is a polyisocyanates, and C is a hydroxy functional acrylate, and D is epoxy (methyl) acrylate.
The preferred synthetic schemes of above-mentioned modified polyurethane (methyl) acrylate polymer (1) comprises, with above-mentioned hydroxyl terminated polybutadiene rubber (A) and polyisocyanates (B) reaction, NCO group among the B and the reaction of the terminal hydroxy group among the A form ammonia ester bond, wherein B is excessive, obtains the product A-B of NCO end-blocking.In A-B, add C or D or C, D then and add in proportion together, allow remaining NCO reacts among hydroxyl and the A-B in C or the D structure.NCO among the relative A-B of hydroxy radical content that wherein preferred proportioning is C or D is excessive.Thereby obtain polymer A-B-C/D.
Obtain the hydroxyl terminated polybutadiene rubber modification and the PUA EA copolymerization through said process.Because hydroxyl terminated polybutadiene rubber enters in the polymeric system by reaction, thereby solved consistency problem, EA enters by copolymerization that the influence to polymer property has better effect than EA and PUA blend in the polymeric system.Thereby obtained having the PUA polymkeric substance of elastomer structure and EA unit.Make the water tolerance of PUA, resistance to acids and bases, impact resistance and cohesive are optimized.
The preparation method of liquid light curing resin composition of the present invention comprises, by polyurethane (methyl) acrylate polymer with above-mentioned A-B-C/D structure, (methyl) acrylate monomer, light trigger, silane coupling agent, mix according to certain ratio,, thereby obtain liquid light curing resin composition of the present invention through fully stirring.Wherein each component is by weight proportion:
(1) modified polyurethane (methyl) acrylate polymer, 20%-80%,
(2) (methyl) acrylate monomer, 5%-70%,
(3) light trigger, 1%-10%,
(4) silane coupling agent, 1%-5%.
Above-mentioned light trigger can be 2; 4, a kind of in 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester, 2-methyl-2-hydroxyl-1-phenylacetone, 2-hydroxyl-cyclohexyl benzene ketone, benzoin dimethylether and 2-methyl-2-hydroxyl-1-(the 4-the tert-butyl group)-phenylacetone or their arbitrary composition.
Above-mentioned silane coupling agent can be a kind of in gamma-aminopropyl-triethoxy-silane, γ-glycidoxypropyltrime,hoxysilane, γ methacryloxypropyl trimethoxy silane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanjiayangjiguiwan, γ-glycidoxy propyl-triethoxysilicane and the phenylamino methyl triethoxysilane or their arbitrary composition.
The span of the molecular weight of above-mentioned hydroxyl terminated polybutadiene rubber HTPB is 1000-20000, and the span of hydroxyl value is 0.1-2.0mmol/g.
Above-mentioned polyisocyanates is diisocyanate or triisocyanate.
Above-mentioned diisocyanate be toluene diisocyanate TDI, methyl diphenylene diisocyanate MDI, hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, hydrogenated diphenyl methane diisocyanate HMDI ,-a kind of in Xylene Diisocyanate XDI, hexamethylene diisocyanate biuret and the hexamethylene diisocyanate trimer or their arbitrary composition.
Above-mentioned hydroxy functional acrylate is a kind of in (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, trimethylolpropane diacrylate and the pentaerythritol triacrylate or their arbitrary composition.
Above-mentioned epoxy acrylate is a kind of in standard bisphenol A epoxy acrylate, soybean oil modified epoxy acrylate and the anhydride modified epoxy acrylate or their arbitrary composition.
Above-mentioned modified polyurethane (methyl) acrylate polymer C: the span of D is 0: 100 to 100: 0.
Except above-mentioned described various compositions, need, also can in resin combination, add various adjuvants, examples of such additives can comprise, as antioxidant, and surfactant, colorant, ultraviolet light absorber, light stabilizer, polymerization inhibitor, levelling agent, antiseptic, plastifier, solvent, filler, wetting improver etc.
Liquid light curing resin composition of the present invention can be used as Photocurable adhesive, photocurable encapsulant and photo-cured coating.
Embodiment 1
At first, HTPB (MW=3000, hydroxyl value=0.60) obtain the product of above-mentioned A-B structure with TDI reaction, HEA: EA (standard bisphenol-A epoxy acryl resin)=50: 50 (mol ratio) and above-mentioned A-B reaction then, thus obtain the polymkeric substance of HTPB-TDI-HEA/EA structure.
Then, above-mentioned polymkeric substance 68wt%, trimethylolpropane triacrylate 8wt%, hexanediyl ester 8wt%, Isooctyl acrylate monomer 8wt%, 2-methyl-2-hydroxyl-1-phenylacetone 5%, gamma-aminopropyl-triethoxy-silane 3% mixed 1 hour.Thereby obtain a kind of photo curable composition of liquid state, viscosity is 3000 centipoises (20 ℃).Said composition can be used as the Photocurable adhesive of furniture industry.Using method is, the photo curable composition of preparation is coated on the plane of stainless steel socket cap (diameter 40mm), then with a thick 10mm, above the tempered glass of diameter 500mm is pressed in, after eliminating bubble, (365nm 80w/cm) shines 30-60 and just can finish solidification process second, and bonding strength can reach request for utilization fully with uviol lamp.Compare with using AB type epoxy adhesive, can save set time greatly.
Claims (1)
1. a liquid light curing resin composition is characterized in that, it comprises the component of following weight ratio example:
(1) modified polyurethane (methyl) acrylate polymer: 20%-80%,
(2) (methyl) acrylate monomer: 5%-70%,
(3) light trigger: 1%-10%,
(4) silane coupling agent: 1%-5%;
The structure of described modified polyurethane (methyl) acrylate polymer is a kind of among A-B-C, A-B-D and the A-B-C-D, wherein: A is hydroxyl terminated polybutadiene rubber HTPB, the span of its molecular weight is 1000-20000, and the span of hydroxyl value is 0.1-2.0mmol/g; B is a polyisocyanates, this polyisocyanates is diisocyanate or triisocyanate, wherein diisocyanate be toluene diisocyanate TDI, methyl diphenylene diisocyanate MDI, hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, hydrogenated diphenyl methane diisocyanate HMDI ,-a kind of in Xylene Diisocyanate XDI, hexamethylene diisocyanate biuret and the hexamethylene diisocyanate trimer or their arbitrary composition; C is a hydroxy functional acrylate, and this hydroxy functional acrylate is a kind of in (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, trimethylolpropane diacrylate and the pentaerythritol triacrylate or their arbitrary composition; D is epoxy (methyl) acrylate, and this epoxy acrylate is a kind of in standard bisphenol A epoxy acrylate, soybean oil modified epoxy acrylate and the anhydride modified epoxy acrylate or their arbitrary composition; Wherein the span of C: D is 50: 50 to 100: 0;
Described light trigger is 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester;
Described silane coupling agent is a kind of in gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanjiayangjiguiwan and the phenylamino methyl triethoxysilane or their arbitrary composition.
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| CN2006100632863A CN101034258B (en) | 2006-10-25 | 2006-10-25 | Liquid light curing resin composition |
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| CN2006100632863A CN101034258B (en) | 2006-10-25 | 2006-10-25 | Liquid light curing resin composition |
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| CN101034258A CN101034258A (en) | 2007-09-12 |
| CN101034258B true CN101034258B (en) | 2011-06-01 |
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| KR20120072163A (en) * | 2010-12-23 | 2012-07-03 | 제일모직주식회사 | Adhesive film for optically clear adhesive film |
| CN102628971A (en) * | 2011-05-03 | 2012-08-08 | 京东方科技集团股份有限公司 | Color filter and method and apparatus for manufacturing the same |
| CN102766428B (en) * | 2012-08-08 | 2014-08-13 | 番禺南沙殷田化工有限公司 | Ultraviolet curable resin composition and application thereof |
| CN103333276B (en) * | 2013-06-08 | 2015-07-29 | 新丰博兴聚合材料有限公司 | Longwave absorption light trigger of a kind of silicone-containing group and preparation method thereof |
| CN110423311A (en) * | 2014-01-13 | 2019-11-08 | 顶科股份有限公司 | Photo curable resin combination and its application method for being used to manufacture artificial tooth and basal seat area in 3D printing |
| CN103881031B (en) * | 2014-02-20 | 2016-05-25 | 常州市嘉诺有机硅有限公司 | A kind of photocureable coating special-purpose organic silicon resin and preparation technology thereof |
| CN104119539B (en) * | 2014-06-24 | 2016-08-24 | 京东方科技集团股份有限公司 | Modification acrylate resin glue and preparation method thereof, Photosensitve resin composition, display base plate, liquid crystal panel |
| CN104479098A (en) * | 2014-12-19 | 2015-04-01 | 江南大学 | Preparation method of polyfunctional UV (Ultraviolet)-cured organic silicon resin |
| CN106087580B (en) * | 2016-06-14 | 2017-08-01 | 昆明瑞丰印刷有限公司 | A kind of double-deck holographic false proof transfer paper and preparation method thereof |
| CN111378080A (en) * | 2020-04-02 | 2020-07-07 | 山东圣佑高科新材料有限公司 | Nano micro needle and photosensitive material composition for micro needle array production and preparation method thereof |
| CN113248652B (en) * | 2020-11-11 | 2022-09-16 | 浙江华显光电科技有限公司 | Photocurable composition for sealing organic light-emitting device |
| CN112778881A (en) * | 2021-01-06 | 2021-05-11 | 阜阳师范大学 | Epoxy acrylate ultraviolet curing material and preparation method thereof |
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