CN1269871C - Allyl ether modified unsaturated polyester and its use - Google Patents
Allyl ether modified unsaturated polyester and its use Download PDFInfo
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- CN1269871C CN1269871C CN 200410051590 CN200410051590A CN1269871C CN 1269871 C CN1269871 C CN 1269871C CN 200410051590 CN200410051590 CN 200410051590 CN 200410051590 A CN200410051590 A CN 200410051590A CN 1269871 C CN1269871 C CN 1269871C
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- unsaturated polyester
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- solidification
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Abstract
The present invention provides modified allyl ether unsaturated polyester expressed by the formula (I) and the application thereof to the preparation of conformal coatings. The modified allyl ether unsaturated polyester is characterized in that besides unsaturated carbon-carbon double bonds, a molecular chain simultaneously contains allyloxy groups, and thus, the unsaturated polyester has the performance of both light solidification and air (oxygen) solidification. Conformal coatings prepared from the modified allyl ether unsaturated polyester have double solidification performance of light and air, namely that the conformal coatings can have crosslinking polymerization under light initiation so as to solidify, and positions of shadows or insufficient illumination can also have crosslinking solidification under the action of the oxygen in the air. The conformal coatings are mainly used for the coating protection of electronic circuit board with welded elements, and can also be used for other occasions having the requirements of double solidification. The definitions of m, n and R1 to R5 in the formula (I) are disclosed in the specification.
Description
Technical field
The present invention relates to resin---the allyl ethers modified unsaturated polyester that a class has light/oxygen dual cure characteristic, and the application of this resinoid in 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 unsaturated polyester, and the application of this resinoid in preparation conformal coating (electronic line plate protective cover).Contain allyloxy and unsaturated carbon-carbon double bond simultaneously in this class allyl ethers modified unsaturated polyester molecule, the former gives air (oxygen) curing performance of resin, and the latter then gives the light-cured performance of resin.
Allyl ethers modified unsaturated polyester provided by the present invention has as shown in the formula the chemical structure shown in (I):
In the formula (I): m=1～10 (being generally 3～6), n=0～10 (being generally 1～5); R
1Be H or CH
3R
2Be H or CH
3
R
3For
R
4For
Or
The polyvalent alcohol (contain dibasic alcohol, down with) that allyl ethers modified unsaturated polyester of the present invention can contain allyloxy by utilization with contain unsaturated alkyl polyprotonic acid and/or multi-anhydride carry out esterification and obtain, be connected to allyloxy in its molecular chain.Its typical reaction is shown below:
In the top reaction equation, raw material (II) is unsaturated multi-anhydride, also can replace with corresponding polyprotonic acid, wherein R
1And R
2Be respectively hydrogen atom or methyl.Typical raw material (II) is toxilic acid and acid anhydrides, fumaric acid etc.For regulating the degree of unsaturation of product, also can sneak into other polyprotonic acid or the acid anhydrides of suitable proportion, for example phthalic acid or its acid anhydrides, tetrahydrophthalic acid or its acid anhydrides, hexahydrophthalic acid or its acid anhydrides, m-phthalic acid, terephthalic acid, hexanodioic acid, Succinic Acid etc.
In the top reaction equation, raw material (III) in other words just contains the dibasic alcohol or the polyvalent alcohol of allyloxy for containing the compound of at least one allyloxy and at least two hydroxyls.Typical raw material (III) is the TriMethylolPropane(TMP) mono allyl ether, and its structural formula is as follows:
In the top reaction equation, raw material (IV) 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 (IV) is ethylene glycol, hexylene glycol, a condensed ethandiol, polyoxyethylene glycol etc.
M in the product (I) can be 1～10, and with 3～6 better, too little then allyloxy content is low, causes curing cross-linked degree deficiency; Too big then degree of crosslinking may be too high and influence the flexibility of dry film, and can cause resin viscosity too high.N is 0～10, and is better with 1～5.
Above-mentioned related esterifying reaction method of the present invention and condition and general unsaturated polyester synthetic method are similar.Key of the present invention is one of raw material that has added the synthetic unsaturated polyester of polyvalent alcohol conduct that contains allyloxy, thereby introduces allyloxy in unsaturated polyester.As an example, the building-up process of allyl ethers modified unsaturated polyester of the present invention is: raw material (II), raw material (III) and raw material (IV) place in the reactor with catalyzer (0.1wt%～1wt% tosic acid), stopper (0.1wt%～2wt% Resorcinol or p methoxy phenol), the gained mixture under continuously stirring 150～200 ℃ of following reflux 2～5 hours, then system is evacuated to about 20～60mmHg, and is warming up to 180～200 ℃ of continuation reactions 1-3 hour.Under 20～60mmHg left and right sides pressure and 120～180 ℃ of temperature, keep 0.5～2 hour (to remove the water in the reaction system), thereby obtain target product (I).Entire reaction is carried out under nitrogen or the protection of other non-reactive gas.
Allyl ethers modified unsaturated polyester of the present invention can be used for preparing the two conformal coatings that solidify of light/air.
Solidifying in the conformal coating with the light/air of allyl ethers modified unsaturated polyester preparation of the present invention is two, described allyl ethers modified unsaturated polyester is as the resene component of coating, and other component can be identical with the general two curing of light/air conformal coating.
In with the two curing of allyl ethers modified unsaturated polyester preparation light/air of the present invention conformal coating, the contained allyloxy of allyl ethers modified unsaturated polyester molecule carries out the air crosslinking reaction under catalyst action, and the carbon-carbon double bond on the unsaturated polyester chain can cooperate with vinyl ether and/or vinylbenzene thinner and carries out photocuring reaction.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 allyl ethers modified unsaturated polyester preparation light/air of the present invention: (A) suc as formula the allyl ethers modified unsaturated polyester of the present invention shown in (I) by following component; (B) reactive thinner; (C) light trigger; (D) siccative; (E) other auxiliary agent.Except that above-mentioned four kinds of main ingredients, can also add other conventional coatings additive(s) in case of necessity, as flow agent, defoamer, thixotropic agent, coupling agent, pigment, dyestuff etc., its consumption can be decided with reference to material supplier's guide or by actual requirement.
Described component (A) is a class allyl ethers modified unsaturated polyester.Compare with common unsaturated polyester, have allyloxy on the molecular chain of this class allyl ethers modified unsaturated polyester.When illumination, the carbon-carbon double bond of the unsaturated carbon-carbon double bond of unsaturated polyester, the carbon-carbon double bond of reactive thinner and allyl ethers issues living radical copolymerization in the effect of light trigger, thereby makes the coating crosslinking curing.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 the two curing of the light/air conformal coating that the present invention proposes can be between 35%～80%, and more suitable consumption is 45%～70%.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 acrylate, N-vinyl pyrrolidone, N-caprolactam, vinylbenzene and derivative, vinyl ether etc.Wherein effect is preferably vinylbenzene, vinyl ether, and this two classes reactive thinner carbon-carbon double bond easy and unsaturated polyester takes place free-radical polymerized.And vinyl ether is because significant hypotoxicity, low odor property and preferential the employing.The consumption of component (B) can be 10%～60%, and more suitable consumption is 25%～50%.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 two conformal coatings that solidify of light/air that the present invention proposes should be deposited with the double pack form, wherein the allyl ethers modified unsaturated polyester 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 0.5～1800 second set time, decides 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 18～72 hours set time, and be 24～48 hours typical set time.
Embodiment
The synthetic method of one to embodiment six pair of allyl ethers modified unsaturated polyester 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 this example adopts is a maleic anhydride, and raw material (III) is a trihydroxy methyl-propane-allyl ether, and raw material (IV) is polyoxyethylene glycol (400).Synthesis step is: raw material (II), raw material (III) and raw material (IV) are pressed 2: 1: 1 mixed, place in the reactor with 0.05 gram tosic acid (catalyzer), 0.5 gram Resorcinol (stopper) then, the gained mixture under continuously stirring 160 ℃ of following reflux 3 hours, then system is evacuated to 40mmHg, and is warming up to 190 ℃ of continuation reactions 2 hours.40mmHg keeps 1 hour (to remove the water in the reaction system) under 40mmHg pressure and 160 ℃ of temperature, thereby obtains the thick final product of little yellow (I).Entire reaction is carried out under nitrogen or the protection of other non-reactive gas.
Embodiment two
Present embodiment and embodiment one are basic identical, but the ratio of raw material (II), raw material (III) and raw material (IV) is 3: 2: 1.Thereby obtain the thick final product of little yellow (I).
Embodiment three
Present embodiment and embodiment one are basic identical, but the ratio of raw material (II), raw material (III) and raw material (IV) is 4: 3: 1.Thereby obtain the thick final product of little yellow (I).
Embodiment four
Present embodiment and embodiment one are basic identical, but raw material (IV) changes Triethylene glycol into, and the ratio of raw material (II), raw material (III) and raw material (IV) is 2: 1: 4 simultaneously.Thereby obtain little yellow final product (I).
Embodiment five
Present embodiment and embodiment one are basic identical, but raw material (II) changes fumaric acid into, and other raw material, proportioning and synthesis step are identical with embodiment one.The product characters that obtains, outward appearance are similar to embodiment's one.
Embodiment six
Present embodiment and embodiment one are basic identical, but raw material (IV) changes butyleneglycol into, and the ratio of raw material (II), raw material (III) and raw material (IV) is 2: 1: 4 simultaneously.Thereby obtain little yellow final product (I).
Seven to nine further specify allyl ethers modified unsaturated polyester 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
Component (A) resin adopts synthetic allyl ethers modified unsaturated polyester resin among the embodiment one; Component (B) reactive thinner adopts triethylene glycol divinyl ether (being called for short DVE-3); Component (C) light trigger adopts the Darocur 1173 of CIBA company; Component (D) siccative adopts cobalt naphthenate.
Component (A) is packed as first separately.0.2 part of 30 parts of components (B), 5 parts of components (C) and component (D) mix as second by mechanical stirring and pack.With two packings of mixed of 2: 1 (first packing ratio second packing), it is standby to stir during use.
Embodiment eight
Component (A) resin adopts synthetic allyl ethers modified unsaturated polyester resin among the embodiment two, rest part and using method and
Embodiment five is identical.
Embodiment nine
Component (A) resin adopts synthetic allyl ethers modified unsaturated polyester resin among the embodiment three, rest part and using method and
Embodiment five is identical.
Embodiment seven arrives the coating of embodiment nine gained at 2400W medium pressure mercury lamp (light intensity 37.5mW/cm
2) exposed 30 seconds down; The air curing condition is to place 24 hours in air under 25 ℃.Solidify the back dry film is carried out performance test.The results are shown in table 1.Testing method sees Table 2.
The physical and mechanical properties test result (testing method sees Table 2) of the cured film of table 1 embodiment five to embodiment seven gained coating
| Sample | Glossiness (60 °) | Shock strength (kg/cm 2) | Pencil hardness | Sticking power (level) | Snappiness (mm) | Surface resistivity (Ω) | Volume resistance (Ω cm) |
| Ultraviolet light polymerization embodiment seven embodiment eight embodiment nine | 104.3 104.4 104.5 | 20 15 15 | 2H 3H 5H | 3 1 1 | 2 2 4 | 3.69×10 13 1.6×10 14 2.31×10 13 | 6.22×10 12 2.45×10 13 3.27×10 14 |
| Air curing embodiment seven embodiment eight embodiment nine | 106.5 107.4 107.9 | 40 45 50 | 3H 5H 6H | 4 4 2 | 1 2 2 | 4.41×10 11 1.02×10 12 3.35×10 12 | 9.81×10 10 5.03×10 11 2.18×10 12 |
The method that the test of table 2 curing membrane performance is adopted
| Performance | Method |
| Glossiness pencil hardness sticking power shock strength snappiness | GB 1743-79 GB/T1730-93 GB 1720-79 GB/T1732-93 GB/T1731-93 |
Claims (4)
1. a class allyl ethers modified unsaturated polyester, its structure is suc as formula shown in (I):
In the formula (I): m=1～10, n=0～10; R
1Be H or CH
3R
2Be H or CH
3R
3For
R
4For
Or
I=2～10 wherein, j=1～25, k=1～25.
2. according to the described allyl ethers modified unsaturated polyester 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 unsaturated polyesters are in the two application of solidifying in the conformal coating of preparation light/air.
4. according to the described application of claim 3, it is characterized in that the consumption of described allyl ethers modified unsaturated polyester accounts for 35%～80%wt of coating composition total amount.
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|---|---|---|---|
| CN 200410051590 CN1269871C (en) | 2004-09-24 | 2004-09-24 | Allyl ether modified unsaturated polyester and its use |
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|---|---|---|---|
| CN 200410051590 CN1269871C (en) | 2004-09-24 | 2004-09-24 | Allyl ether modified unsaturated polyester and its use |
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| CN1269871C true CN1269871C (en) | 2006-08-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634765A (en) * | 2016-12-16 | 2017-05-10 | 深圳市华星光电技术有限公司 | Black sealing compound and LCD (liquid crystal display) special-shaped screen, and manufacturing method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404580C (en) * | 2005-11-23 | 2008-07-23 | 上海氯碱化工股份有限公司 | Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization |
| CN101565493A (en) * | 2009-06-09 | 2009-10-28 | 上海新天和树脂有限公司 | High-tenacity self-dried hand-feeling unsaturated polyester resin and preparation method thereof |
| CN102643597B (en) * | 2012-05-08 | 2014-04-30 | 合众（佛山）化工有限公司 | High-compactness poly ethylene (PE) white primer and construction method and detection method thereof |
| CN104529762B (en) * | 2014-12-25 | 2016-08-31 | 合肥工业大学 | A kind of quick-dry type double cured resin and preparation method and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634765A (en) * | 2016-12-16 | 2017-05-10 | 深圳市华星光电技术有限公司 | Black sealing compound and LCD (liquid crystal display) special-shaped screen, and manufacturing method thereof |
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