CN1616514A - Allyl ether modified polyurethane acrylate and its use - Google Patents
Allyl ether modified polyurethane acrylate and its use Download PDFInfo
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- CN1616514A CN1616514A CN 200410051591 CN200410051591A CN1616514A CN 1616514 A CN1616514 A CN 1616514A CN 200410051591 CN200410051591 CN 200410051591 CN 200410051591 A CN200410051591 A CN 200410051591A CN 1616514 A CN1616514 A CN 1616514A
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Abstract
The present invention provides allyl ether modified polyurethane acrylate and the application of the resin in compounding form maintaining paint. The allyl ether modified polyurethane acrylate features that the molecular chain contains optical active acylyloxy radical or methyl acylyloxy radical as well as allyloxy radical endowing the resin with air/oxygen curing performance, and thus has both light curing and air curing performance. The form maintaining paint compounded with the allyl ether modified polyurethane acrylate may be cured through cross-linking under the initiation of light and oxygen in the air. The form maintaining paint is used mainly to protect electronic circuit board with electronic elements soldered, and may be used also in other fields needing double curing.
Description
Technical field
The present invention relates to resin---the allyl ethers modified urethane acrylate that a class has light/air dual cure characteristic, and this resinoid is in the particularly two application of solidifying in the conformal coating of light/air of preparation conformal coating (electronic line plate protective cover).
Background technology
The protective coating that is coated on the printed-wiring board (PWB) that welds plug connector elements is commonly referred to conformal coating (conformal coating).It can make electronic product avoid the erosion of extraneous hostile environment, scrape manual operation mistakes such as damage, short circuit as dust, moisture, pharmaceutical chemicals, mould corrosive nature and foreign object, can prolong the life-span of electron device again, the performance of electronic product be improved thereby improve the stability of using.
The curing mode of conformal coating is divided into photocuring, thermofixation, moisture solidification, electricity curing and air curing.The conformal coating of light-cured type have curing speed fast, be applicable to that the ground of thermo-sensitivity, initial outlay are low, low voc solvent content, save advantage such as space.Adopt the photocuring conformal coating, can improve the application production efficiency of wiring board greatly, and be convenient to wiring board is repaired and local ready coating protection.But the zonule shade is solidified into the key issue that this technology of restriction is applied to all kinds of complicated wiring boards.Therefore; the conformal coating of development all adopts dual cure mechanism all curable under light, the dark condition now; it both can guarantee that solidified rapidly in most of zone on the wiring board; be convenient to the enforcement of subsequent technique; can guarantee a small amount of shadow region completion of cure in a short time again; not only improved wiring board application production efficiency, and guaranteed comprehensive curing of conformal coating, applicable to the coating protection of various complicated type wiring boards.Common dual cure has light-thermofixation, light-moisture and light-air curing etc.Moisture solidification is to utilize the functional group's effect in airborne moisture (water vapour) and the filmogen and crosslinking reaction takes place, thereby forms the curing cross-linked film.U.S. Pat 5,516,812 have proposed light/moisture solidification conformal coating of a class silicone-containing macromer.Its moisture solidification is to utilize silicone functionalities and airborne moisture (water) that hydrolysis reaction takes place to form silicon-oxygen-silicon cross-linked network.The reaction that another kind can be used for moisture solidification is that isocyanic ester-NCO group and water react and crosslinked, and a significant disadvantages of this reaction is that solidification process has carbonic acid gas to emit, and it is acid that its aqueous solution is, and hardware is had corrosive nature.In addition, a common shortcoming of moisture solidification is to want air that suitable humidity is arranged, to be provided for the solidified water molecules.
Another dark curing mechanism is thermofixation, usually handles under the temperature about 80 ℃ 0.5～2 hour and solidifies.This curing means are easier to realize comparatively speaking, but shortcoming is to need heating, for heat sensitive electronic line plate and be not suitable for.But also to consume the additional energy source that is used to heat.
Air curing in light-air dual cure systems is to utilize the curing mechanism that is similar to siccative oil.Siccative oil is a kind of unsaturated long-chain ester, contains-CH=CH-CH
2-CH=CH-chain link is in the presence of suitable catalyzer, easily by airborne dioxygen oxidation and crosslinking curing.Allyl ethers structure (O-CH
2-CH=CH-) also have similar air curing character.U.S. Pat 5,712,321 propose polyenoid propoxy-linking agent (as Santolink XI-100) and catalyzer are added in the photocuring system characteristic of giving its air curing.The structure of XI-100 is as follows:
Unsaturated double-bond light-cured performance in this linking agent is lower.Simultaneously, when dark curing, light-cured components (oligopolymer or the monomer that contain acryloxy) participates in the limited in one's ability of air curing.
Summary of the invention
The purpose of this invention is to provide a class allyl ethers modified urethane acrylate, and this resinoid is in the two application of solidifying in the conformal coating (electronic line plate protective cover) of preparation light/air.Contain allyloxy and (methyl) acryloxy in the molecule of this class allyl ethers modified urethane acrylate simultaneously, the former gives air (oxygen) curing performance of resin, and the latter then gives the light-cured performance of resin.
Its chemical structure of allyl ethers modified urethane acrylate provided by the present invention is as shown in the formula shown in (I).
In the formula (I): m=1～10 (being generally 3～6), n=0～10 (being generally 1～5); R
1For
R
2For
Or
I=2～6 wherein, j=1～25, k=1～25; R
3For
Or
R
4For-CH
2-CH
2-or
R
5For-CH
3Or H.
Allyl ethers modified urethane acrylate of the present invention can synthesize (code name of raw material and product is referring to formula 1) by the following method: add raw material (II) in exsiccant three neck round-bottomed flasks, raw material (III), catalyzer (0.05～1wt% dibutyl tin laurate), middling speed stirs and slowly drips raw material (IV) down, after dropwising, heating systems to 40～65 ℃, when isocyanate concentration does not change (variation of isocyanate concentration in available appropriate means such as the Di-n-Butyl Amine method monitoring system) substantially in time, the cooling system is to room temperature, obtain intermediate product (V), in system, slowly drip raw material (VI) again, after dropwising, heating systems to 40～65 ℃, (available infrared spectra detects the basic complete reaction of isocyanic ester in reaction system, 2274cm
-1The absorption peak completely dissolve), termination reaction obtains product (I), is allyl ethers modified urethane acrylate of the present invention.Concrete reaction process as shown in Equation 1.
Raw material in the formula 1 (II) is the TriMethylolPropane(TMP) mono allyl ether, and its structural formula is as follows:
Raw material in the formula 1 (III) is not for containing the dibasic alcohol or the polyvalent alcohol of allyloxy, is used to regulate the performance of the allyloxy content and the coating dry film of product.Typical raw material (III) is ethylene glycol, hexylene glycol, a condensed ethandiol or polyoxyethylene glycol etc.
Raw material in the formula 1 (IV) is for containing at least two isocyanate group (compound N-C=O), typical raw material has tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4,4 '-dicyclohexyl methane diisocyanate (claims hydrogenated diphenyl methane diisocyanate again, HMDI).Their structure as following various shown in:
OCN·(CH
2)
6-NCO HDI
Intermediate product in the formula 1 (V) has the oligopolymer of isocyanate group for molecular chain-end.Wherein m can be 1～10, and is better with 3～6; N is 0～10, and is better with 1～5.The value of m and n changes by control raw material (II) and add-on (III).When not adding raw material (III) in synthetic, n=0 then, the reaction process of this moment is as shown in Equation 2.Raw material code name in the formula 2 is identical with formula 1, but the product I ' that wherein obtains expression.
The building-up reactions of formula 1. allyl ethers modified urethane acrylates
The building-up reactions of formula 2. allyl ethers modified urethane acrylates [not adding raw material (III)]
Raw material in the formula 1 (VI) is class hydroxy-functional (methyl) acrylate, wherein contains the compound of at least one hydroxyl and at least one (methyl) acryloxy.Proper hydroxy-functional (methyl) acrylate comprises 2-hydroxyethyl methacrylate (HEMA), vinylformic acid-2-hydroxyl ethyl ester (HEA), methacrylic acid-2-hydroxypropyl acrylate (HPMA), vinylformic acid-2-hydroxypropyl acrylate (HPA), trimethylolpropane diacrylate (TMPDA) or pentaerythritol triacrylate (PETRA), their structure respectively as following various shown in:
Allyl ethers modified urethane acrylate of the present invention can be used for preparing the two conformal coatings that solidify of urethane light/air.
Solidifying in the conformal coating with the light/air of allyl ethers modified urethane acrylate preparation of the present invention is two, described allyl ethers modified urethane acrylate is as the resene component of coating, and other component can be identical with the general two curing of light/air conformal coating.Allyloxy contained in the allyl ethers modified urethane acrylate molecule carries out the air crosslinking reaction under catalyst action, and the carbon-carbon double bond of (methyl) acryloxy carries out photocuring reaction under the effect of light trigger.The advantage of this dual cure systems is no matter to obtain enough crosslinkedly under photocuring or air curing condition, forms the satisfactory protection dry film of performance.
Usually, mainly constitute with the two conformal coatings that solidify of the light/air of allyl ethers modified urethane acrylate preparation of the present invention: (A) suc as formula the allyl ethers modified urethane acrylate of the present invention shown in (II) by following component; (B) reactive thinner; (C) light trigger; (D) siccative.Except above-mentioned four kinds of main ingredients, can also add the coatings additive(s) of various routines in case of necessity, as flow agent, defoamer, coupling agent etc.
Described component (A) allyl ethers modified urethane acrylate is the urethane that a class contains allyloxy and (methyl) acryloxy.Compare with the light-cured polyurethane of common only containing (methyl) acryloxy, except (methyl) acryloxy, also have allyloxy on the molecular chain of this class urethane.When illumination, the carbon-carbon double bond of (methyl) acryloxy issues living radical polymerization in the effect of light trigger, thereby makes the coating crosslinking curing.It is crosslinked that the carbon-carbon double bond of allyl ethers also can the polymerization of subparticipation photocuring.In the time of in being exposed to air, the methyne-CH in the allyloxy between oxygen and the carbon-carbon double bond
2-under the effect of catalyzer by the oxidation of airborne oxygen institute, the free radical polymerization of formation is crosslinked, thereby makes curing of coating.The consumption (weight percentage, down together) of component (A) in the prescription of coating can be between 20%～75%, and more suitable consumption is 35%～65%.Actual amount depends primarily on the viscosity and the execution conditions of whole system.
Described component (B) is a class reactive thinner, contains carbon-carbon double bond, and the available reactive thinner has (methyl) acrylate, N-vinyl pyrrolidone, N-caprolactam, vinylbenzene and derivative, vinyl ether etc.Wherein effect is preferably (methyl) acrylate, and vinyl ether can be used as auxiliary reactive thinner, except can significantly reducing the viscosity, can also promoter action be arranged to dark curing.The N-vinyl pyrrolidone is because of suspecting that toxicity has seldom adopted; Vinylbenzene and derivative thereof also are seldom to adopt because of toxicity and irritating smell.The consumption of component (B) can be 10%～70%, and more suitable consumption is 30%～60%.Actual amount depends primarily on the viscosity and the execution conditions of whole system.
Described component (C) is a free radical photo-initiation.The light trigger of the light-initiated radical polymerization that is useful on all can adopt.IRGACURE 184, the IRGACURE 651 of typical light trigger such as Ciba company, DAROCUR 1173 etc.The consumption of component (C) can be 0.2%～15%, and more suitable consumption is 1%～5%, and actual amount depends primarily on execution conditions such as curing speed, used curing light source.
Described component (D) is a class air curing catalyzer, is commonly called as siccative.The siccative of the siccative oil that is useful on and unsaturated polyester all can adopt.Typical siccative has the naphthenate and the 2-ethylhexoate of metals such as cobalt, manganese.Except above-mentioned siccative, the salt that can also add metals such as zirconium, calcium, zinc, barium is as saturating dried agent in this component, and effect is to stablize above-mentioned siccative and increase its efficient, and makes the film coated surface uniform drying.Siccative consumption in the component (D) is calculated as 0.0001%～1% with the percentage composition that metallic element accounts for prescription, and more suitable consumption is 0.0001%～0.2%, and typical consumption is about 0.005%.The saturating consumption of doing agent is 0.1%～2%, and typical consumption is about 0.6%.
In order to guarantee that the coating finished product has enough shelf-times, the above-mentioned two conformal coatings that solidify of light/air of the present invention should be deposited with the double pack form, wherein the allyl ethers modified urethane acrylate is that component (A) is deposited as a packing (first packing), mix during for the ease of use, can in this packing, add an amount of component (B) reactive thinner, mechanical stirring mixes, and makes the lower resin solution of viscosity.Another packing (second packing) contains the active dilution of component (B), component (C) light trigger, component (D) siccative and saturating dried agent, and other coatings additive(s)s.These components are placed mixing vessel, and mechanical stirring mixes.Evenly can obtain the two conformal coatings that solidify of light/air to the mixing of materials of two packings by a certain percentage during use.When adopting above-mentioned double pack to preserve, can stablize and deposit more than half a year.After the component of two packings is mixed, place the air will gel about 8 hours; Secluding air then can be stablized to deposit and reaches about a week.
The two conformal coatings that solidify of light/air that the present invention is above-mentioned, the condition of photocuring can be visible light or UV-light, and is better with UV-light.Curing light source comprises visible light or/and the light source of ultraviolet wavelength light wave as medium pressure mercury lamp, low pressure mercury lamp, high voltage mercury lamp, electrodeless lamp, xenon lamp, metal halide lamp etc., also can use solar light irradiation to solidify for sending.Be generally set time 0.5～1800 second, and decided on used light source kind and intensity.Be 5～60 seconds typical set time.
The two conformal coatings that solidify of light/air that the present invention is above-mentioned, the condition of air curing is to be exposed to naturally in the air under the normal temperature, and atmospheric moisture is not had special requirement.Be generally set time 18～72 hours, be 24～48 hours typical set time.
Embodiment
The synthetic method of one to six pair of allyl ethers modified urethane acrylate of the present invention is described further by the following examples, and wherein said proportioning raw materials is weight ratio.
Embodiment one
The raw material (II) that present embodiment adopts is the TriMethylolPropane(TMP) mono allyl ether, and raw material (III) is a poly(oxyethylene glycol) 400, and raw material (IV) is 2,4 tolylene diisocyanates, and raw material (VI) is Jia Jibingxisuanβ-Qiang Yizhi (HEMA).The raw material consumption of present embodiment is raw material (II): raw material (III): raw material (IV): raw material (VI)=2: 1: 4: 2.Synthesis step is: add raw material (II) and raw material (III) in exsiccant three neck round-bottomed flasks, middling speed stirs dibutyl tin laurate (catalyzer) mixed solution that drips raw material (IV) and 5 ‰ (massfractions) down, (rate of addition is 4 seconds /), after dropwising, system is warmed up to 50 ℃, react 4 hours to isocyanate concentration not over time, in system, slowly drip raw material (VI) (rate of addition is 4 seconds /) again, after dropwising, system is warmed up to 45 ℃, and the basic complete reaction of isocyanic ester (detects 2274cm with infrared spectra in reaction system
-1The absorption peak completely dissolve), thereby obtain final product (I).Entire reaction is carried out in exclusion of water (vapour) with under nitrogen or the protection of other non-reactive gas.
Embodiment two
The raw material consumption of present embodiment is raw material (II): raw material (III): raw material (IV): raw material (VI)=5: 0: 7: 4, and all the other are identical with embodiment one.
Embodiment three
The raw material of present embodiment (IV) adopts isophorone diisocyanate (IPDI), and all the other raw materials and synthesis step are identical with embodiment one.With respect to the TDI of embodiment one, present embodiment adopts IPDI as polyisocyanate component, and experiment condition is better controlled, and the product shelf stability is better, but cost of material is slightly higher than adopting TDI.
Embodiment four
The raw material of present embodiment (IV) adopts hexylene glycol vulcabond (HDI), and all the other raw materials and synthesis step are identical with embodiment one.With respect to the TDI of embodiment one, present embodiment adopts HDI as polyisocyanate component, does not contain phenyl ring, therefore be difficult for xanthochromia takes place, but cost of material is slightly higher than adopting TDI.
Embodiment five
The raw material of present embodiment (III) adopts Triethylene glycol, and all the other raw materials and synthesis step are identical with embodiment one.Because adopted short dibasic alcohol segment, the products therefrom flexibility is lower than embodiment one products therefrom.
Embodiment six
The raw material of present embodiment (VI) adopts propenoic acid beta-hydroxy ethyl ester (HEA), and all the other raw materials and synthesis step are identical with embodiment one.The chain end of products therefrom is an acrylate, and with respect to the methacrylic ester of embodiment one, laser curing velocity is very fast.But the pungency of HEA is bigger than HEMA in the building-up process.
Seven to ten further specify allyl ethers modified urethane acrylate of the present invention in the two application of solidifying in the conformal coating of preparation light/air by the following examples, wherein said proportioning raw materials is weight ratio.
Embodiment seven
In the present embodiment, component (A) resin adopts synthesis of allyl ether modified urethane acrylate among the embodiment one; Component (B) reactive thinner adopts the Viscoat 295 (being called for short EB160) and the triethylene glycol divinyl ether (being called for short DVE-3) of ethoxyquin; Component (C) light trigger adopts the Darocur 1173 of CIBA company; Component (D) siccative adopts cobalt naphthenate.The consumption of each component is listed in table 1.
Compound method is that whole components (A) are mixed with 5 parts of EB160, and mechanical stirring mixes, and obtains the first packing.Remaining EB160 mixes with all the other component mechanical stirring, obtains the second packing.First, second packing mixed with 1: 1 during use.
Embodiment eight
The raw material of present embodiment and embodiment seven are similar, but reactive thinner does not contain DVE-3.The prescription of present embodiment is listed in table 1.
Compound method is that whole components (A) are mixed with 20 parts of EB160, and mechanical stirring mixes, and obtains the first packing.Remaining EB160 mixes with all the other component mechanical stirring, obtains the second packing.First, second packing mixed with 1: 1 during use.
The light-cured performance of present embodiment is better than embodiment seven, and the dark curing performance is lower than embodiment seven.
Embodiment nine
The prescription of present embodiment and embodiment seven are similar, but the component in the raw material (A) changes two synthetic allyl etherss of embodiment modified urethane acrylate into, and all the other raw materials are identical with embodiment seven.The prescription of present embodiment is listed in table 1.
Compound method is that whole components (A) are mixed with 5 parts of EB160, and mechanical stirring mixes, and obtains the first packing.Remaining EB160 mixes with all the other component mechanical stirring, obtains the second packing.First, second packing mixed with 1: 1 during use.
Embodiment ten
The prescription of present embodiment and embodiment eight are similar, but the component in the raw material (A) changes two synthetic allyl etherss of embodiment modified urethane acrylate into, and all the other raw materials are identical with embodiment eight.The prescription of present embodiment is listed in table 1.
Compound method is that whole components (A) are mixed with 20 parts of EB160, and mechanical stirring mixes, and obtains the first packing.Remaining EB160 mixes with all the other component mechanical stirring, obtains the second packing.First, second packing mixed with 1: 1 during use.
The light-cured performance of present embodiment is better than embodiment eight, and the dark curing performance is lower than embodiment eight.
Dry film performance to embodiment seven and embodiment nine gained coating is tested.The photocuring condition is that (light intensity is 37.5mW/cm at the 2400W medium pressure mercury lamp
2) exposed 30 seconds down; The air curing condition is to place 48 hours in air under 25 ℃.Press the listed testing method of table 2 (national standard) and measure the physical and mechanical properties of gained cured film, the results are shown in table 3.Every performance all reaches the requirement of using on electronic line plate.
Embodiment eight compares with embodiment nine with embodiment seven with embodiment ten, and mainly at the viscosity and the curing performance of coating finished product, the physicals of dry film changes little difference.Nine of embodiment eight and embodiment are better than other embodiment aspect photolytic activity.
The prescription of four kinds of conformal coatings of preparation among table 1 embodiment seven to ten
Allyl ethers modified polyurethane vinylformic acid EB160 DVE-3 Darocur alkanoic acid cobalt
Resin 1173
7 45 parts of (resins of embodiment one) 40 parts 10 parts 5 parts 0.2 part of embodiment
8 30 parts of (resins of embodiment one) 65 parts 05 parts 0.2 part of embodiment
9 45 parts of (resins of embodiment two) 40 parts 10 parts 5 parts 0.2 part of embodiment
10 parts of (resins of embodiment two) 65 parts 05 parts 0.2 part of embodiment
The method that the curing membrane performance test of table 2 embodiment seven and nine gained coating is adopted
Performance methodology
Glossiness GB 1743-79
Pencil hardness GB/T1730-93
Sticking power GB 1720-79
Shock strength GB/T1732-93
Snappiness GB/T1731-93
The cured film physical and mechanical properties test result of table 3 embodiment seven and nine gained coating
Sample glossiness shock strength pencil hardness sticking power flexible film resistance volume resistance
(60 °) (kg/cm
2) (level) (mm) (Ω) (Ω cm)
Ultraviolet light polymerization
Embodiment 7 100.9 50 H 11 1.42 * 10
161.31 * 10
14
Embodiment 9 98.1 50 2H 11 1.20 * 10
163.28 * 10
14
Air curing
Embodiment 7 106.5 50 4H 21 7.69 * 10
159.81 * 10
13
Embodiment 9 107.4 50 5H 21 5.13 * 10
153.04 * 10
13
Claims (5)
1. a class allyl ethers modified urethane acrylate, its structure is suc as formula shown in (I):
In the formula (I): m=1～10, n=0～10; R
1For
R
2For
Or
I=2～6 wherein, j=1～25, k=1～25;
R
3For
Or
R
4For-CH
2-CH
2-or
R
5For-CH
3Or H.
2. according to the described allyl ethers modified urethane acrylate of claim 1, it is characterized in that m=3～6 in the formula (I), n=1～5.
3. claim 1 or 2 described allyl ethers modified urethane acrylates are in the two application of solidifying in the conformal coating of preparation urethane light/air.
4. according to the described application of claim 3, it is characterized in that the consumption of described allyl ethers modified urethane acrylate accounts for 20%～75%wt of coating composition total amount.
5. according to the described application of claim 4, it is characterized in that the consumption of described allyl ethers modified urethane acrylate accounts for 35%～65%wt of coating composition total amount.
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| CN 200410051591 CN1616514A (en) | 2004-09-24 | 2004-09-24 | Allyl ether modified polyurethane acrylate and its use |
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|---|---|---|---|
| CN 200410051591 CN1616514A (en) | 2004-09-24 | 2004-09-24 | Allyl ether modified polyurethane acrylate and its use |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424109C (en) * | 2006-04-27 | 2008-10-08 | 华南理工大学 | Preparation method of amino silane modified urethane acrylate resin |
| CN102504174A (en) * | 2011-12-19 | 2012-06-20 | 烟台德邦科技有限公司 | Polyurethane acrylic acid ester and preparation method and application thereof |
| CN101743287B (en) * | 2007-07-13 | 2014-02-19 | 威士伯采购公司 | Coating composition with accelerated low temperature cure |
| CN106752754A (en) * | 2017-03-14 | 2017-05-31 | 浙江世窗光学薄膜制造有限公司 | A kind of gum polyurethane protective film and preparation method thereof |
| CN109943221A (en) * | 2019-04-03 | 2019-06-28 | 王春阳 | A kind of modification acrylate water-repellent paint and preparation method thereof for road and bridge |
-
2004
- 2004-09-24 CN CN 200410051591 patent/CN1616514A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424109C (en) * | 2006-04-27 | 2008-10-08 | 华南理工大学 | Preparation method of amino silane modified urethane acrylate resin |
| CN101743287B (en) * | 2007-07-13 | 2014-02-19 | 威士伯采购公司 | Coating composition with accelerated low temperature cure |
| CN102504174A (en) * | 2011-12-19 | 2012-06-20 | 烟台德邦科技有限公司 | Polyurethane acrylic acid ester and preparation method and application thereof |
| CN106752754A (en) * | 2017-03-14 | 2017-05-31 | 浙江世窗光学薄膜制造有限公司 | A kind of gum polyurethane protective film and preparation method thereof |
| CN109943221A (en) * | 2019-04-03 | 2019-06-28 | 王春阳 | A kind of modification acrylate water-repellent paint and preparation method thereof for road and bridge |
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