CN101875715B - Epoxy modified polyurethane, UV-curing coat and preparation method thereof - Google Patents
Epoxy modified polyurethane, UV-curing coat and preparation method thereof Download PDFInfo
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- CN101875715B CN101875715B CN 200910107176 CN200910107176A CN101875715B CN 101875715 B CN101875715 B CN 101875715B CN 200910107176 CN200910107176 CN 200910107176 CN 200910107176 A CN200910107176 A CN 200910107176A CN 101875715 B CN101875715 B CN 101875715B
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Abstract
The invention discloses epoxy modified polyurethane, a UV-curing coat and a preparation method thereof. The UV-curing coat comprises base resin, photoinitiator and diluent, wherein the base resin contains epoxy modified polyurethane; and the photoinitiator is cationic photoinitiator. The UV-curing coat has high coat mechanical performance and strong bonding force with base materials, when the UV-curing coat is cured in the conventional condition. When the base materials are deformed, the coat cannot be subject to falling off and other problems.
Description
[technical field]
The present invention relates to a kind of epoxide modified urethane and coating and preparation method thereof, in particular for epoxide modified urethane and this ultraviolet-curing paint and preparation method thereof of ultraviolet-curing paint.
[background technology]
Ultraviolet-curing paint (UV coating) is a kind of environment-friendly type energy-saving coating of nineteen sixty-eight by Bayer A.G's exploitation; Mainly form by prepolymer, monomer, light trigger and auxiliary agent; Having does not have or low VOC (VOC) discharging, save energy, curing speed are fast, excellent performance, be applicable to characteristics such as heat-sensitive material, is widely used in field of materials such as timber, plastics, optical fiber, paper.Along with the high speed development of modern science and technology, for satisfying global requirement on environmental protection, limit the discharging of the volatile organic constituents in the coating, make coating material solidified research and development of UV and application the good impetus occur.And plentiful, bright by the prepared coating of ultraviolet-curing paint, the coating mechanical property is good; Chemical-resistant is good, from the seventies in 20th century so far, the UV technology has obtained the development of advancing by leaps and bounds; The market share increases sharply; Some developed countries and area are in the world developed especially rapidly, might become one of leading green coating product of 21 century.
But existing photo-cured coating, because light-cured performance fast, coating solidified within the very short time, and coating is inner can to exist bigger string stress, causes the coating mechanical property, and especially sticking power significantly descends.
In order to overcome the problems referred to above, improve through following two aspects in the prior art: the one, reduce the ultraviolet ray intensity when solidifying, mainly can be through regulating light source distance, using spectral filter or use low intensive ultraviolet source to realize; The 2nd, the velocity of initiation of reduction light-cured resin mainly can be realized through the content that reduces light trigger.
But, more than two kinds of methods effect of improving coating performance unsatisfactory, and processing condition are wayward.
[summary of the invention]
In order to overcome the problem that prior art medium ultraviolet photo-cured coating solidifies back coating poor mechanical property; The invention provides a kind of epoxide modified urethane and ultraviolet-curing paint; Coating mechanical property, the especially sticking power and the good toughness that solidify to form by this ultraviolet-curing paint.
Epoxide modified urethane disclosed by the invention, contain as shown in the formula 1 or formula 2 shown in structure:
Formula 1:
Wherein, n is the integer of 1-10;
R
1Contain following structural formula:
Wherein, Z
1Be selected from a kind of in hydrogen, methyl, ethyl, the halogen, i is the integer of 1-6;
R
2Be selected from
In one or more;
Formula 2:
Wherein, R
0Be alkyl, m is the integer of 1-10;
R
4Contain following structural formula:
R
3Be selected from
In one or more.
Ultraviolet-curing paint provided by the invention comprises matrix resin, light trigger, thinner, and said matrix resin contains epoxide modified urethane, and said light trigger is a cationic photoinitiator.
The invention also discloses the preparation method of this ultraviolet-curing paint, comprise the matrix resin that contains epoxide modified urethane, cationic photoinitiator, mixing diluents are got final product.
Ultraviolet-curing paint disclosed by the invention is after solidifying under the condition of routine, and the coating mechanical property that obtains is good, and is strong with the base material bonding force.When deformation appearred in base material, coating can not produce problem such as come off yet.
[embodiment]
In order to make technical problem to be solved by this invention, technical scheme and beneficial effect clearer, below the present invention is further elaborated.
Epoxide modified urethane disclosed by the invention can obtain epoxide modified urethane through hydroxy-end capped urethane resin under the katalysis of basic catalyst and epichlorohydrin reaction.Select divalent alcohol: the mol ratio of isocyanic ester is at 1.1-1.5, and reaction generates hydroxy-end capped urethane resin under the katalysis of catalyzer.Then, in system, add epoxy chloropropane, the basic catalyst katalysis obtains epoxide modified urethane.If alicyclic end capped modified polyurethane resin; The general isocyanic ester of selecting: the mol ratio of divalent alcohol is reacted under the katalysis of catalyzer at 1.1-1.5, and the later stage of reaction (for example adds a certain amount of alcohols modification cycloalkanes alkene class; Tetrahydrobenzene-3-methyl alcohol); The reaction certain hour adds the Peracetic Acid catalyzed reaction again, obtains epoxide modified urethane.
Under the preferable case, above-mentioned epoxychloropropane modified urethane has the structure of formula 1 expression:
Formula 1:
Wherein, n is the integer of 1-10;
R
1Contain following structural formula:
R
2Be selected from
In one or more.
The urethane of above-mentioned alicyclic epoxy modification has the structure of formula 2 expressions:
Formula 2:
Wherein, R
0Be alkyl, m is the integer of 1-10;
R
4Contain following structural formula:
Wherein, Z
2Be selected from a kind of in hydrogen, methyl, ethyl, the halogen, r is the integer of 1-6;
R
3Be selected from
In one or more.
Disclosed radicals R in the said structure formula
1, R
2, R
3, R
4Be in the epoxide modified urethane process of preparation, introduce, in the art, can think usually, when preparing epoxide modified urethane, with the R of raw material introducing by raw material
1, R
2, R
3, R
4Also exist in the product that after reaction, obtains, as to R
1And R
4Qualification, i and r also can control when selecting raw material.For number of repeat unit m and n; Can obtain through the epoxide modified urethane for preparing is tested; As adopt the method for GB4612-84 regulation to measure its epoxy equivalent (weight), and adopt GPC to detect its molecular weight and MWD, analyze the value that obtains m and n.Among the present invention, can think to have said structure through the epoxide modified urethane that obtains after the method for preparing.
Usually, macromolecular material inside is a large amount of molecular chains that twine each other, and molecular chain is mainly formed by the various atoms that couple together through covalent linkage.Various covalent linkage all have certain bond energy, and when the reactive force that receives when molecular chain was higher than the bond energy of covalent linkage, molecular chain promptly ruptured, when the deformation that promptly shows as macromolecular material on the macroscopic view appears breaking in a large amount of molecular chains, even fracture.
All can have interaction between the molecule segment of macromolecular material inside, when there was internal stress in macromolecular material inside, molecule segment was in tight state, and each interatomic covalent linkage of molecule intrachain also receives certain function power.And the bond energy of covalent linkage is certain, and when internal stress was big more, the power that covalent linkage receives was also big more, and energy required during molecular rupture is also just more little.It is little on macroscopic view, to show as the power that material can bear, and promptly mechanical property is relatively poor.So the internal stress that reduces material helps improving the mechanical property of material.
In coating, after coating was coated on substrate surface, resin in the coating and base material generation effect were bonded on the base material coating.At solidification process, resin reacts, and its molecular chain produces motion, if solidification process is too fast, molecular chain has little time to produce and shrinks, and promptly shows bigger internal stress problem behind the paint solidification.
In order effectively to solve in the paint solidification process; Because the motion of molecular chain is restricted the internal stress problem that causes; Thereby improve the mechanical property of coating, the invention discloses a kind of ultraviolet-curing paint, comprise matrix resin, light trigger, thinner; Said matrix resin contains epoxide modified urethane, and said light trigger is a cationic photoinitiator.The epoxide modified urethane that in ultraviolet-curing paint disclosed by the invention, is adopted is the epoxide modified urethane of process; Be the epoxychloropropane modified urethane or the urethane of alicyclic epoxy modification under the preferable case, further be preferably above-mentioned formula 1 or formula 2 disclosed epoxide modified urethane.Its preparation method such as preamble are said, are not giving unnecessary details at this.
The ultraviolet-curing paint that will contain above-mentioned composition is coated on substrate surface, after the conventional method of employing is cured, and the coating mechanical property that obtains, especially sticking power is good.
The contriver finds, when in matrix resin, containing epoxide modified urethane, forms a large amount of hydrogen bonds in the coating that can after curing, form, and improves the mechanical property of coating.Especially, when the second-order transition temperature (Tg) of above-mentioned epoxide modified urethane is-40～40 ℃, in the time of particularly-30～20 ℃, more favourable to the mechanical property that improves coating.The epoxide modified urethane that satisfies above-mentioned requirements can be commercially available, and its second-order transition temperature can be selected when buying.If obtain epoxide modified urethane, can pass through the second-order transition temperature that DSC (DSC, the DSC that plum Teller-Tuo benefit group produces) is tested the epoxide modified urethane for preparing through self-control.
Because the solidification process of coating also is the reaction process of a matrix resin; The second-order transition temperature (Tg) of the epoxide modified urethane that adopts as the present invention is in above-mentioned scope the time; Help the motion of molecular chain when curing reaction of matrix resin; Reduce the generation of internal stress, thereby improve the mechanical property of the coating that obtains behind the paint solidification.
The cationic photoinitiator that is adopted in the ultraviolet-curing paint provided by the present invention is selected from one or more in diazonium salt, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and the triaryl silica ether; Above-mentioned diazonium salt, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ether are conventionally known to one of skill in the art, can be two dodecylbenzene salt compounded of iodine, asymmetric long-chain alkoxy base diphenyl iodnium, Fluorenone base phenyl salt compounded of iodine like diaryl group iodized salt.Under the preferable case, said cationic photoinitiator contains iron arene salt, further is preferably Irgacure261 and/or Irgacure250 (production of Switzerland vapour Bagong department).
Above-mentioned thinner is selected from (methyl) propenoate, Dipentaerythritol five propenoate (DPPA), dipentaerythritol acrylate (DPHA), Viscoat 295 (TMPTA), pentaerythritol triacrylate (PETA), 1, one or more in 6-pinakon propenoate (HDDA) and tripropylene glycol diacrylate (TPGDA), N-vinyl pyrrolidone, N-caprolactam, vinylbenzene and verivate thereof, the vinyl ether.Wherein, the vinyl ethers thinner is selected from hydroxy butyl vinyl ether (HBVE), triethylene glycol divinyl ether (DVE-3), 1, one or several in 4-cyclohexyl dimethanol divinyl ether (CHVE), the butyl vinyl ether (BVE) etc.Above-mentioned thinner is this area thinner commonly used, can be commercially available, like the hydroxy butyl vinyl ether of BASF AG's production.The kind of thinner and consumption should be able to fully dissolve matrix resin, and will have suitable volatility, and solvency power is too strong, end phenomenon then possibly occur stinging, and vaporator rate too greatly then possibly cause the paint film unfairness.
In ultraviolet-curing paint provided by the invention, each components contents can change in a big way, under the preferable case; With the ultraviolet-curing paint gross weight is benchmark; The content of matrix resin is 20-80wt%, and the content of light trigger is 1-10wt%, and surplus is a thinner; The content that further is preferably matrix resin is 40-60wt%, and the content of light trigger is 5-10wt%, and surplus is a thinner.
In addition, can also contain unmodified ZGK 5 in the matrix resin of ultraviolet-curing paint provided by the invention, the second-order transition temperature of this unmodified ZGK 5 (Tg) is-30～10 ℃, is preferably-20～0 ℃.Above-mentioned unmodified ZGK 5 is conventional ZGK 5, and the unmodified ZGK 5 that meets this condition can be commercially available, like the TSR116 of organosilicon company of GE Toshiba production.With the ultraviolet-curing paint gross weight is benchmark, and the content of said unmodified ZGK 5 is 0-20wt%, is preferably 5-15wt%.
Tg when coating
0During＞room temperature, coating is for harder, and along with Tg
0Rising, hardness increases, corresponding coating becomes fragile.Same Tg when coating
0During＜room temperature, coating is for softer, and along with Tg
0Reduction, coating can be more and more softer, coating can become sticky accordingly.So Tg
0Control very big for the influence of the mechanical property of coating.The Tg of coating for a change
0, the blend that the present invention selects unmodified polyorganosiloxane resin to participate in whole network realizes.Through containing the adding of hanging down the unmodified ZGK 5 of Tg; When in matrix resin disclosed by the invention, containing epoxide modified urethane; Can firm combining between epoxide modified urethane and the unmodified ZGK 5; After film forming was crosslinked, the internal stress that can be good at avoiding existing was shunk, and strengthens impact resistance of system or the like simultaneously.
Simultaneously, can also contain epoxide modified ZGK 5 in the matrix resin of ultraviolet-curing paint disclosed by the invention.Especially the epoxide modified ZGK 5 that has the structure of formula 3 expressions.
Formula 3:
R wherein
5Can be epoxide group or alicyclic epoxy group, R
6, R
7, R
8, R
9Independently be selected from hydrogen, methyl, phenyl, methoxyl group, the oxyethyl group one or more separately; X and y are integer and x+y≤10.
Under the preferable case, said epoxide modified ZGK 5 is the epoxide modified ZGK 5 of 1-4 functionality.Above-mentioned functionality is to be the characteristic group with the epoxide group.The epoxide modified ZGK 5 that meets above-mentioned condition can be commercially available, like the TSR194 of organosilicon company of GE Toshiba production.Above-mentioned substituent R
6, R
7, R
8, R
9Performance of products is not had much affect.
For number of repeat unit x and y sum; Can obtain through the epoxide modified urethane for preparing is tested; As adopt the method for GB4612-84 regulation to measure its epoxy equivalent (weight), and adopt GPC to detect its molecular weight and MWD, analyze the value that obtains x and y sum.
With the ultraviolet-curing paint gross weight is benchmark, and the content of above-mentioned epoxide modified ZGK 5 is 10-40wt%, is preferably 20-30wt%.
As coating of the prior art, also contain auxiliary agent in the ultraviolet-curing paint disclosed by the invention; With the ultraviolet-curing paint gross weight is benchmark, and the content of said auxiliary agent is 1-10wt%, is preferably 2-8wt%.
Above-mentioned auxiliary agent contains one or more in flow agent, skimmer, coupling agent, the adhesion promoter.
Flow agent disclosed by the invention can be flow agent commonly used in the prior art, and the trade mark of producing like German BYK company is that the flow agent of BYK333 or BYK331 or the trade mark that Dutch AFCONA company produces are the flow agent of AFCONA3034 or AFCONA3770.With the ultraviolet-curing paint gross weight is benchmark, and the consumption of flow agent can be 0-5wt%, is preferably 1.5-2.5wt%.
Skimmer disclosed by the invention can be skimmer commonly used in the prior art, for example saturated alcohol, lipid acid and ester class thereof, higher fatty acid metallic soap class, sulphonated oil and organic silicone oil.The preferred skimmer of the present invention can be the skimmer of AFCONA2045, AFCONA2022, BYK052 or BYK065 for the trade mark that Dutch AFCONA company produces.With the ultraviolet-curing paint gross weight is benchmark, and the consumption of skimmer can be 0-5wt% among the present invention, is preferably 1.5-2.5wt%.
The coupling agent that the present invention discusses can be coupling agent commonly used in the prior art, for example silicone based coupling agent.The preferred coupling agent of the present invention can be the coupling agent of KH550, KH560 or KH570 for the trade mark that the friendly auxiliary agent chemical industry in Nanjing Ltd produces.With the ultraviolet-curing paint gross weight is benchmark, and the consumption of coupling agent can be 0-5wt% among the present invention, is preferably 1.5-2.5wt%.
The adhesion promoter that the present invention discusses can be adhesion promoter commonly used in the prior art.For example Silok Chemical Co., Ltd. Guangzhou grades for Silok
-628, Silok
-621S adhesion promoter or Hemmings specialty chemicals company produces grades for Adherant1031 adhesion promoter.With the ultraviolet-curing paint gross weight is benchmark, adheres among the present invention to make every effort to promote urgent consumption and can be 0-5wt%, is preferably 1.5-2.5wt%.
It doesn't matter each other for the content of above flow agent, skimmer, coupling agent, adhesion promoter, only needs the auxiliary agent gross weight in above-mentioned scope, to get final product.
The preparation method of ultraviolet-curing paint of the present invention can proceed step by step mix disposable the mixing also of said matrix resin, thinner and light trigger.Under preferable case, earlier with light trigger and part mixing diluents, light trigger is fully dissolved, obtain containing the solution of light trigger; Then that matrix resin and another part mixing diluents is even, obtain the resinous principle slurries; The solution that then will contain light trigger mixes with the slurries that contain resinous principle, and it is even to add remaining solvent at last.Above-mentioned mixing is carried out usually at normal temperatures, in case of necessity, can mild heat to 30-60 ℃, mix quickening.
When containing unmodified ZGK 5 and/or epoxide modified ZGK 5 in the ultraviolet-curing paint disclosed by the invention; The interpolation order of each component does not require; Under the preferable case, earlier ZGK 5 and/or epoxide modified ZGK 5 are mixed with epoxide modified urethane.Equally, when containing auxiliary agent in the ultraviolet-curing paint of disclosure of the Invention, when especially auxiliary agent comprised multiple material, the interpolation of each composition order and auxiliary agent did not require with the interpolation of matrix resin, thinner, light trigger in proper order.
Under the preferable case, the preparation method of ultraviolet-curing paint disclosed by the invention preferred embodiment is:
(1) with light trigger and part mixing diluents, is stirred to abundant dissolving, obtains containing the solution of light trigger;
(2) matrix resin and another part mixing diluents is even, obtain containing the slurries of matrix resin;
(3) the above-mentioned resulting solution that contains light trigger is mixed with the slurries that contain matrix resin, obtain mixture;
(4) one or more in continuation adding flow agent, skimmer, coupling agent, the adhesion promoter in resulting mixture, and mix;
(5) remove by filter the residue that the dust that brings in the operating process and impurity produce then, remaining diluent is all added and mixes.
Finally obtain preferred ultraviolet-curing paint of the present invention.
After preparing ultraviolet-curing paint disclosed by the invention, it is coated on the base material, adopts UV-light to be cured.Curing light source comprises visible light or/and the light source of ultraviolet wavelength light wave for sending, like medium pressure mercury lamp, and low pressure mercury lamp, high voltage mercury lamp, electrodeless lamp, xenon lamp, metal halide lamp etc.Be generally 0.5-2000s set time.
Ultraviolet-curing paint disclosed by the invention is specially adapted to plastics or caoutchouc elasticity surface, also is applicable to metallic substrate surface simultaneously.Mechanical property, the especially sticking power of the coating that forms after above-mentioned ultraviolet-curing paint solidifies are good.
Through embodiment the present invention is further described below.
Embodiment 1
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
1, the epoxide modified urethane of preparation
In the 500ml there-necked flask, add 8 weight part Ucar 35 and 150ml N-Methyl pyrrolidone as reaction solvent; Treat that above-mentioned reactant dissolves the DBTL (dibutyl tin dilaurate) that the back adds 0.2 weight part fully; Drip 24 weight parts 2 down at 25 ℃; The 4-tolylene diisocyanate reacted 3 hours, when the isocyano-content of detection architecture remains unchanged; In system, add 4 weight parts tetrahydrobenzene-3-methyl alcohol, and the DBTL (dibutyl tin dilaurate) of additional 0.1 weight part reacted 3 hours down at 30 ℃.When the isocyano-content of detection architecture remains unchanged once more, in system, add 0.3 weight part Peracetic Acid again, 50 ℃ of following catalyzed reactions 2 hours, when the epoxy equivalent (weight) of detection architecture remained unchanged, reaction finished.Obtain epoxide modified urethane A1.
Adopt the method for GB4612-84 regulation to measure the epoxy equivalent (weight) that contains A1, adopt the method for HG/T 2709-95 regulation to measure the A1 hydroxy radical content.Adopt the method for GB6743-86 regulation to detect the NCO content that contains A1, adopt GPC to detect molecular weight and the MWD of A1.Epoxy equivalent (weight) is 750, and molecular weight is 1550, and MWD is 1.08, and its number of repeat unit is 5.(DSC, the DSC that plum Teller-Tuo benefit group produces) tests its glass transition temperature Tg through DSC
-A1It is 42 ℃.
2, preparation ultraviolet-curing paint
70 weight part A1,3 weight part light triggers (Irgacure261 that Switzerland vapour Bagong department produces) and 27 weight part hydroxy butyl vinyl ethers (BASF AG's production) are joined in the impeller; Rotating speed with 1000rad/min stirs 10min, obtains ultraviolet-curing paint S1.
Embodiment 2
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
1, the epoxide modified urethane of preparation
In the 500ml there-necked flask, add 8 weight part polyoxyethylene glycol (molecular weight 200) and 150ml N-Methyl pyrrolidone as reaction solvent; Treat that above-mentioned reactant dissolves the DBTL (dibutyl tin dilaurate) that the back adds 0.2 weight part fully; Drip 13 weight part isoflurane chalcone diisocyanates down at 40 ℃; Reacted 3 hours; When the isocyano-content of detection architecture remains unchanged, in system, add 1.5 weight parts tetrahydrobenzene-3-methyl alcohol, and the DBTL (dibutyl tin dilaurate) of additional 0.1 weight part reacted 2 hours down at 40 ℃.When the isocyano-content of detection architecture remains unchanged, in system, add 0.3 weight part Peracetic Acid again, 50 ℃ of following catalyzed reactions 2 hours, when the epoxy equivalent (weight) of detection architecture remained unchanged, reaction finished.Obtain epoxide modified urethane A2.
Method according to embodiment 1 is tested, and obtaining the A2 epoxy equivalent (weight) is 1330, and molecular weight is 2670, and MWD is 1.05, and obtaining its number of repeat unit is 5.(DSC, the DSC that plum Teller-Tuo benefit group produces) tests its glass transition temperature Tg through DSC
-A2It is 27 ℃.
2, preparation ultraviolet-curing paint
The preparation method of ultraviolet-curing paint is identical with embodiment 1, obtains ultraviolet-curing paint S2.
Embodiment 3
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
1, the epoxide modified urethane of preparation
In the 500ml there-necked flask, add 8 weight part polyoxyethylene glycol (molecular weight 600) and 150ml N-Methyl pyrrolidone as reaction solvent; Treat that above-mentioned reactant dissolves the DBTL (dibutyl tin dilaurate) that the back adds 0.2 weight part fully; Drip 9 weight part hexamethylene diisocyanates down at 50 ℃; Reacted 3 hours; When the isocyano-content of detection architecture remains unchanged, in system, add 0.5 weight part tetrahydrobenzene-3-methyl alcohol, and the DBTL (dibutyl tin dilaurate) of additional 0.1 weight part reacted 2 hours down at 50 ℃.When the isocyano-content of detection architecture remains unchanged once more, in system, add 0.3 weight part Peracetic Acid again, 50 ℃ of following catalyzed reactions 2 hours, when the epoxy equivalent (weight) of detection architecture remained unchanged, reaction finished.Obtain epoxide modified urethane A3.
Method according to embodiment 1 is tested, and obtaining the A3 epoxy equivalent (weight) is 850, and molecular weight is 1640, and MWD is 1.06, and obtaining its number of repeat unit is 3.(DSC, the DSC that plum Teller-Tuo benefit group produces) tests its glass transition temperature Tg through DSC
-A3It is 7 ℃.
2, preparation ultraviolet-curing paint
The preparation method of ultraviolet-curing paint is identical with embodiment 1, obtains ultraviolet-curing paint S3.
Embodiment 4
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
1, the epoxide modified urethane of preparation
In the 500ml there-necked flask, add 8 weight part polyoxyethylene glycol (molecular weight is 600) and 150ml N-Methyl pyrrolidone as reaction solvent; Treat that above-mentioned reactant dissolves the DBTL (dibutyl tin dilaurate) that the back adds 0.3 weight part fully; Drip 3 weight part hexamethylene diisocyanates down at 50 ℃, reacted 3 hours, when the hydroxy radical content of detection architecture remains unchanged; In system, add 0.8 weight part epoxy chloropropane and 0.3 weight part butyllithium again; 80 ℃ of following catalyzed reactions 2 hours, when the epoxy equivalent (weight) of detection architecture remained unchanged, reaction finished.Obtain epoxide modified urethane A4.
Method according to embodiment 1 is tested, and obtaining the A4 epoxy equivalent (weight) is 1500, and molecular weight is 3200, and MWD is 1.04, and obtaining its number of repeat unit is 3.(DSC, the DSC that plum Teller-Tuo benefit group produces) tests its glass transition temperature Tg through DSC
-A4Be-21 ℃.
2, preparation ultraviolet-curing paint
The preparation method of ultraviolet-curing paint is identical with embodiment 1, obtains ultraviolet-curing paint S4.
Embodiment 5
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
1, the epoxide modified urethane of preparation
In the 500ml there-necked flask, add 8 weight part polyoxyethylene glycol (molecular weight is 600) and 150ml N-Methyl pyrrolidone as reaction solvent; Treat that above-mentioned reactant dissolves the DBTL (dibutyl tin dilaurate) that the back adds 0.2 weight part fully; At 50 ℃ of following Dropwise 5 weight part hexamethylene diisocyanates; Reacted 3 hours; When the hydroxy radical content of detection architecture remains unchanged, in system, add 0.5 weight part tetrahydrobenzene-3-methyl alcohol again, and the DBTL (dibutyl tin dilaurate) of additional 0.1 weight part reacted 2 hours down at 50 ℃.When the isocyano-content of detection architecture remains unchanged once more, in system, add 0.3 weight part Peracetic Acid again, 50 ℃ of following catalyzed reactions 2 hours, when the epoxy equivalent (weight) of detection architecture remained unchanged, reaction finished.
Obtain epoxide modified urethane A5.
Method according to embodiment 1 is tested, and obtaining the A5 epoxy equivalent (weight) is 1150, and molecular weight is 2400, and MWD is 1.06, and obtaining its number of repeat unit is 3.(DSC, the DSC that plum Teller-Tuo benefit group produces) tests its glass transition temperature Tg through DSC
-A5Be-5 ℃.
2, preparation ultraviolet-curing paint
The preparation method of ultraviolet-curing paint is identical with embodiment 1, obtains ultraviolet-curing paint S5.
Embodiment 6
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
The preparation method of ultraviolet-curing paint is with embodiment 3, and wherein, different is: (organosilicon company of GE Toshiba produces, Tg with 57 weight part A3, the unmodified ZGK 5 of 16 weight parts
-wBe 7 ℃), 6 weight part light triggers (Switzerland vapour Bagong department produce Irgacure261) and 21 weight part hydroxy butyl vinyl ethers (BASF AG's production) mixing, stir.
Obtain ultraviolet-curing paint S6.
Embodiment 7
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
The preparation method of ultraviolet-curing paint is with embodiment 3, and wherein, different is: (organosilicon company of GE Toshiba produces, Tg with 32 weight part A3, the unmodified ZGK 5 of 12 weight parts
-wBe-12 ℃), (organosilicon company of GE Toshiba produces the epoxide modified ZGK 5 of 32 weight parts; Functionality is 6), 8 weight part light triggers (Switzerland vapour Bagong department produce Irgacure250) and 16 weight part triethylene glycol divinyl ethers (BASF AG's production) mixing, stir.
Obtain ultraviolet-curing paint S7.
Embodiment 8
Present embodiment is used to explain ultraviolet-curing paint disclosed by the invention and preparation method thereof.
The preparation method of ultraviolet-curing paint is with embodiment 3, and wherein, different is: (organosilicon company of GE Toshiba produces, Tg with 42 weight part A3, the unmodified ZGK 5 of 8 weight parts
-wBe-21 ℃), (organosilicon company of GE Toshiba produces the epoxide modified ZGK 5 of 21 weight parts; Functionality is 2), 8 weight part light triggers (Switzerland vapour Bagong department produce Irgacure250), 13 weight part N-caprolactams, 2 weight part BYK333,2 weight part AFCONA2022,2 weight part KH570,2 weight part Adherant1031 mix, stir.
Obtain ultraviolet-curing paint S8.
Comparative Examples 1
This Comparative Examples is used to explain ultraviolet-curing paint of the prior art.
With 4 gram light triggers (Darocurl173) and 5 gram thinner (toluene: butylacetate=1: 1) mix, be stirred to abundant dissolving, obtain containing the solution of light trigger;
With 40 grams, 10 functionality polyurethane acrylate resins (Japanese synthetic chemistry Zhu Shi commercial firm product; Model is 1700B; Viscosity in the time of 60 ℃ is 1500cP; Functionality is 10, and hardness is 8H) and 20 gram reactive thinners (DPHA) and 30 gram thinner (toluene: butylacetate=1: 1) mix, obtain containing the slurries of aforementioned body resin and reactive thinner;
The above-mentioned solution that contains light trigger, the slurries that contain aforementioned body resin and reactive thinner are mixed, obtain mixture; In resulting mixture, continue to add the flow agent (BYK333) of 2.0 grams; 2.0 the coupling agent (DOW CORNING Z-6040) of the skimmer (BYK354) of gram, 5.0 grams and 2.0 gram fluorine surfactants (Zonyl 8857A); Mix, then filter to remove residue, with remaining 5 gram thinner (toluene: butylacetate=1: 1) all add; Stir, obtain ultraviolet-curing paint D1 of the prior art.
Performance test
The ultraviolet-curing paint for preparing in embodiment 1-8 and the Comparative Examples 1 is sprayed on respectively on the plastic casing (60mm * 100mm black PC colour table), and wherein impact resistance detects model and requires to make model according to GB/T1732-1998; Snappiness detects model and requires to make model according to GB/T 1732-93; Irradiation 25s obtains the paint film that thickness is 12um at plastic casing under UV-light.
Resulting paint film is carried out following performance test:
1, sticking power
Method according to GB/T 9286-1998 is tested;
2, impact resistance
Method according to GB/T 1732-93 is tested;
3, snappiness
Method according to GB/T 1731-93 is tested;
4, erosion resistance
Method according to GB/T1771-91 is tested.
Test result is as shown in table 1.
Table 1
| Sample | Sticking power | Impact resistance | Snappiness/mm | Erosion resistance/h |
| S1 | 1 | Positive 45, anti-35 | 1 | 603 |
| S2 | 0 | Positive 50, anti-35 | 1 | 606 |
| S3 | 0 | Positive 50, anti-40 | 0.5 | 612 |
| S4 | 0 | Positive 50, anti-45 | 0.5 | 672 |
| S5 | 0 | Positive 50, anti-45 | 0.5 | 675 |
| S6 | 0 | Positive 50, anti-45 | 0.5 | 727 |
| S7 | 0 | Positive and negative 50 | 0.5 | 725 |
| S8 | 0 | Positive and negative 50 | 0.5 | 725 |
| D1 | 1 | Positive and negative 35 | 2 | 600 |
Test result through table 1 can find out that the sticking power of ultraviolet-curing paint disclosed by the invention, impact resistance and snappiness are significantly improved, and simultaneously, finds also that through the test contriver erosion resistance of solidifying the back coating also is significantly improved.
From another point of view, the unmodified ZGK 5 that interpolation the present invention limits in ultraviolet-curing paint is more favourable to improving coating performance.
Claims (14)
1. epoxide modified urethane, contain as shown in the formula 1 or formula 2 shown in structure:
Formula 1:
Wherein, n is the integer of 1-10;
R
1Contain following structural formula:
Wherein, Z
1Be selected from a kind of in hydrogen, methyl, ethyl, the halogen, i is the integer of 1-6;
R
2Be selected from
In one or more;
Formula 2:
Wherein, R
0Be alkyl, m is the integer of 1-10;
R
4Contain following structural formula:
R
3Be selected from
In one or more.
2. ultraviolet-curing paint; Comprise matrix resin, light trigger, thinner, said matrix resin contains epoxide modified urethane, and said light trigger is a cationic photoinitiator; Said epoxide modified urethane, contain as shown in the formula 1 or formula 2 shown in structure:
Formula 1:
Wherein, n is the integer of 1-10;
R
1Contain following structural formula:
R
2Be selected from
In one or more;
Formula 2:
Wherein, R
0Be alkyl, m is the integer of 1-10;
R
4Contain following structural formula:
R
3Be selected from
In one or more.
3. ultraviolet-curing paint according to claim 2; Wherein, Said epoxide modified urethane contains one or more in the urethane of epoxychloropropane modified urethane or alicyclic epoxy modification, and said epoxychloropropane modified urethane has the structure of formula 1 expression:
Formula 1:
Wherein, n is the integer of 1-10;
R
1Contain following structural formula:
Wherein, Z
1Be selected from a kind of in hydrogen, methyl, ethyl, the halogen, i is the integer of 1-6;
R
2Be selected from
In one or more.
4. ultraviolet-curing paint according to claim 3, wherein, the urethane of said alicyclic epoxy modification has the structure of formula 2 expressions:
Formula 2:
Wherein, R
0Be alkyl, m is the integer of 1-10;
R
4Contain following structural formula:
R
3Be selected from
In one or more.
5. according to any described ultraviolet-curing paint among the claim 2-4, wherein, the second-order transition temperature of said epoxide modified urethane is-40～40 ℃.
6. ultraviolet-curing paint according to claim 2, wherein, said cationic photoinitiator is selected from one or more in diazonium salt, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and the triaryl silica ether; Thinner is selected from one or more in (methyl) propenoate, N-vinyl pyrrolidone, N-caprolactam, vinylbenzene and verivate thereof, the vinyl ether.
7. ultraviolet-curing paint according to claim 2 wherein, is a benchmark with the ultraviolet-curing paint gross weight, and the content of said matrix resin is 20-80wt%, and the content of light trigger is 1-10wt%, and surplus is a thinner.
8. ultraviolet-curing paint according to claim 2 wherein, also contains unmodified ZGK 5 in the said matrix resin, the second-order transition temperature of said unmodified ZGK 5 is-30～10 ℃.
9. ultraviolet-curing paint according to claim 8 wherein, is a benchmark with the ultraviolet-curing paint gross weight, and the content of said unmodified ZGK 5 is 0-20wt%.
10. ultraviolet-curing paint according to claim 2 wherein, also contains epoxide modified ZGK 5 in the said matrix resin.
11. ultraviolet-curing paint according to claim 10, wherein, said epoxide modified ZGK 5 is the epoxide modified ZGK 5 of 1-4 functionality.
12. according to claim 10 or 11 described ultraviolet-curing paints, wherein, be benchmark with the ultraviolet-curing paint gross weight, the content of said epoxide modified ZGK 5 is 10-40wt%.
13. ultraviolet-curing paint according to claim 2 wherein, also contains auxiliary agent in the said ultraviolet-curing paint; With the ultraviolet-curing paint gross weight is benchmark, and the content of said auxiliary agent is 1-10wt%.
14. the preparation method of ultraviolet-curing paint according to claim 2 comprises the matrix resin that contains epoxide modified urethane, cationic photoinitiator, mixing diluents.
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| CN103013423B (en) * | 2012-12-20 | 2014-06-04 | 南通高盟新材料有限公司 | Preparation method for high temperature-resistant waterborne polyurethane adhesive |
| CN106832185B (en) * | 2017-01-04 | 2019-06-07 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
| CN118185431B (en) * | 2024-03-25 | 2024-08-23 | 湖北三雷德化工有限公司 | Environment-friendly paint for inner and outer walls of corrosion-resistant cast iron drain pipe, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093377A (en) * | 1994-01-11 | 1994-10-12 | 青岛化工学院 | The preparation method of the urethane-epoxy resin composite material of high strength, high tenacity and high-wearing feature |
| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| EP1916272A1 (en) * | 2006-10-24 | 2008-04-30 | Sika Technology AG | Heat curable epoxide compositions containing a blocked and an epoxyterminated polyurethane prepolymer. |
| WO2008049857A1 (en) * | 2006-10-24 | 2008-05-02 | Sika Technology Ag | Blocked polyurethane prepolymers and heat-curable epoxy resin compositions |
| CN101235148A (en) * | 2007-12-29 | 2008-08-06 | 华南理工大学 | Multiple crosslinking ultraviolet light solidifying water polyurethane dispersoid and its preparation method and application |
-
2009
- 2009-04-30 CN CN 200910107176 patent/CN101875715B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093377A (en) * | 1994-01-11 | 1994-10-12 | 青岛化工学院 | The preparation method of the urethane-epoxy resin composite material of high strength, high tenacity and high-wearing feature |
| EP1916272A1 (en) * | 2006-10-24 | 2008-04-30 | Sika Technology AG | Heat curable epoxide compositions containing a blocked and an epoxyterminated polyurethane prepolymer. |
| WO2008049857A1 (en) * | 2006-10-24 | 2008-05-02 | Sika Technology Ag | Blocked polyurethane prepolymers and heat-curable epoxy resin compositions |
| CN101003715A (en) * | 2007-01-05 | 2007-07-25 | 华南理工大学 | Method for preparing modified aqueous adhesion agent of polyurethane |
| CN101235148A (en) * | 2007-12-29 | 2008-08-06 | 华南理工大学 | Multiple crosslinking ultraviolet light solidifying water polyurethane dispersoid and its preparation method and application |
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