CN105440894B - For Metal surface anti-corrosion light solidifying paint composition - Google Patents
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Abstract
The invention discloses one kind to be used for Metal surface anti-corrosion light solidifying paint composition；Including 30~45 parts of Epocryl, 10~30 parts of polyurethane acrylate resin, 10~30 parts of polybutadiene-modified acrylate, 15~25 parts of acrylic ester monomer, 4~7 parts of photoinitiator, 1~5 part of adhesion promoter.The urethane acrylate is to adhere to preferable low degree of functionality resin to metal；Polybutadiene-modified acrylate is the lower low degree of functionality resin of polarity；Acrylic ester monomer is selected from trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane trimethacrylate etc..Metal base is widely used in decoration industry at present, but because its is oxidizable, chemicals-resistant is poor, it is therefore desirable in surface coat protective layer；Acid and alkali-resistance can be improved using composition of the invention very well, salt spray resistance, and in system it is solvent-free be truly realized it is environmentally friendly.
Description
Technical field
The invention belongs to ultraviolet-curing paint fields, and in particular to one kind is used for Metal surface anti-corrosion photocureable coating group
Close object.
Background technique
In today's society various industries, sheet metal such as aluminium foil is widely used in ornament materials.In order to improve gold
Belong to the decorative effect and anti-corrosion capability of plate, is usually coated with a coating as protective layer on surface.For traditional heat curing type
Coating, coating process are while coating, and plate is by high-temperature baking, thus make curing of coatings, but due to expanding with heat and contract with cold
Effect will lead to foil deformation, while high-temperature baking also results in the grid electricity fee cost of great number.
Ultraviolet-curing paint (UV is coating material solidified) is the low molecule prepolymer caused in coating using the energy of ultraviolet light
Or oligomer and as the polymerization and cross-linking reaction between the monomer molecule of reactive diluent, obtain a kind of painting of hardening paint film
Material, compared with traditional natural drying or heat curing coating, photocureable coating have capacity usage ratio is high, be applicable in heat-sensitive substrate material,
It is pollution-free, film forming speed is fast, film quality is high, be suitble to continuous mass production the features such as, be known as Environmentally friendly coatings.
By the retrieval discovery to existing literature, Chinese patent CN1014007650A discloses one on April 15th, 2009
Kind UV curing polyaniline anti-corrosive paint and preparation method thereof, which is made using polyaniline
Based on anti-corrosion material, oligomer, reactive diluent, polyaniline, filler, photoinitiator, auxiliary agent are blended according to the proportion,
Stirring, grinding, filtering etc. obtain UV curing polyaniline anti-corrosive paint, but the coating uses physical admixture, Bu Neng
Fine and close cross-linked network structure is formed on film, can not solve the alkaline-resisting bottleneck under film.CN102850899A is in January, 2013
A kind of photocuring alkali-resisting paint is disclosed within 2nd, improves the comprehensive anticorrosive performance of film by addition solid superpolymer, but it is high
The addition of polymers must be added to solvent to dissolve, and the embodiment photocuring of real meaning is not environmental-friendly.
Summary of the invention
It is an object of the invention to overcome above-mentioned the shortcomings of the prior art, provide a kind of for Metal surface anti-corrosion light
Cure coating compositions.
The purpose of the present invention is achieved through the following technical solutions:
The present invention relates to one kind to be used for metal surface light solidifying paint composition, each component including following parts by weight:
Preferably, the Epocryl is selected from bisphenol A-type acrylate, novolac epoxy resin, organic titanacycle
One or more of oxygen resin, glycerol epoxy acrylate, alicyclic epoxy acrylate.The epoxy acrylate
EB648, EB3701, EB9636 selected from Qing Te company, the U.S., the 623-100 of Changxing chemical company, 6234,6235, the U.S. are husky
One or more of CN117, CN159 of more Ma companies.
Preferably, the polyurethane acrylate resin is 3,4 degrees of functionality, to metal base (especially aluminium foil, Ma Kou
Iron) adhesive force be 5B polyurethane acrylate resin.The urethane acrylate be U.S. Qing Te company EB800,
EB830, EB264, EB270, EB1290, EB5129, U100, U400, U600 of Bayer A.G, Changxing chemical company
6145,6195,6113, DR-U150,6197, CN293, CN220 of Sartomer, the U.S., the BR-144 of Bo Ma company, the U.S.,
One or more of BR-446, BR-941.
In the present invention, polybutadiene-modified acrylate is voluntarily developed for my company, and synthetic route is as follows: being containing double first
Hydroxyl polybutadiene (being purchased from BASF, molecular weight ranges 500-800) is reacted with isophorone diisocyanate, is rubbed by adjusting
You are the oligomer of isocyanate groups than producible end, are reacted again with hydroxy-ethyl acrylate later, and final compound is synthesized.
Polybutadiene-modified acrylate obtained, resin backbone hetero atom is less, and polarity is very low.Inventors be surprised to learn that in this hair
In bright composition, polybutadiene-modified acrylate can play good hydrophobic effect, prevent from seeping under solution and decompose coating.
In addition it should be pointed out that be ingredient proportion by adjusting double hydroxyl polybutadiene and isophorone diisocyanate, Ke Yihe
At the oligomer of different hydrophobicities, be conducive to the tolerance of follow-up formula debugging.
Preferably, the acrylic ester monomer be selected from 1,6- hexanediyl ester, tripropylene glycol diacrylate,
Polyethyleneglycol diacrylate, trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, ethoxyquin three
Hydroxymethyl-propane triacrylate, the third oxidation trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythrite
Tetraacrylate, ethoxyquin pentaerythritol tetraacrylate, the third oxidation pentaerythritol tetraacrylate, six propylene of dipentaerythritol
One or more of acid esters.
Preferably, the photoinitiator is selected from benzophenone, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl-
One or more of -1 acetone of 1- phenyl, 2,4,6- trimethylbenzoy-dipheny phosphine oxides, isopropyl thioxanthone.
Preferably, the adhesion promoter is phosphoric acid ester list official's monomer.The adhesion promoter is selected from upper Haitai
PM-1, PM-2 of lattice Polymer Company, one or more of the G40 of RAHN company, Switzerland.
Compared with prior art, the present invention has the advantage that are as follows:
1, each component compatibility is good in this formula, and viscosity is low, can directly be coated with after heating, there is no need to add solvent, keeps away
The destruction that solvent volatilizees to environment in conventional coating is exempted from, has been truly realized pollution-free；
2, conventional thermosetting thermoplastic system is due to needing to be heating and curing, and required temperature reaches 200~400 DEG C, expends a large amount of
Electric energy, and mass energy is saved without this process in the present invention；
3, polybutadiene-modified acrylate is added in the present invention, when soda acid drop is behind surface, effectively prevents liquid
Excellent resistance to acid and alkali and salt fog resistance can be well realized in lower infiltration.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several modifications can also be made.These belong to protection of the invention
Range.
Examples 1 to 5
Examples 1 to 5 is related to a kind of for aluminium foil surface anti-corrosion light solidifying paint composition, including component shown in table 1
And parts by weight.
Using 100 microns of thick aluminium foils as substrate, impregnated 30 seconds using preceding with 5% sodium hydroxide solution, after warm water washing
It is dried for standby.Coating is poured into heating hopper, is heated up to 70 DEG C, is glued using 3 rollers, coating is coated on processed aluminium foil table
Face, control film thickness are 1.2 microns, are directly solidified after coating, energy 1000mJ/cm2。
Embodiment 6,7
Embodiment 6,7 is related to a kind of for tinplate surface anticorrosion light solidifying paint composition, the component indicated including table 1
And parts by weight.
Using 100 microns of thick tinplates as substrate, impregnated 30 seconds using preceding with 5% sodium hydroxide solution, warm water washing
After be dried for standby.Coating is poured into heating hopper, is heated up to 70 DEG C, is glued using 3 rollers, coating is coated on processed Ma Kou
Iron surface, control film thickness are 1.2 microns, are directly solidified after coating, energy 800mJ/cm2。
Comparative example 1
This comparative example is related to a kind of solvent type heat-curing anticorrosive paint composition, including component shown in table 2 and parts by weight
Number.
Coating is coated on processed aluminium foil (processing step is with embodiment 1) surface, coating dry measure control is micro- 1.2
Rice is dried 1 minute using 340 DEG C of baking ovens, takes out specimen page to room temperature.
Comparative example 2
This comparative example be related to it is a kind of for aluminium foil surface anti-corrosion light solidifying paint composition, including component shown in table 3 and
Parts by weight.
Coating is coated on processed aluminium foil (processing step is with embodiment 1) surface, control coating weight is 1.2 microns,
It places to dry for 40 seconds in 60 DEG C of baking ovens and removes solvent, later with ultraviolet light curing, energy 700mJ/cm2。
Comparative example 3
This comparative example is related to a kind of for tinplate surface anticorrosion light solidifying paint composition, including component shown in table 4
And parts by weight.
Coating is coated on processed tinplate (processing step is with embodiment 6) surface, control coating weight is 1.2 micro-
Rice is placed to dry for 40 seconds in 60 DEG C of baking ovens and removes solvent, later with ultraviolet light curing, energy 800mJ/cm2。
Comparative example 4
This comparative example be related to it is a kind of for aluminium foil surface anti-corrosion light solidifying paint composition, including component shown in table 5 and
Parts by weight.
Coating is coated on processed aluminium foil (processing step is with embodiment 1) surface, coating dry measure control is micro- 1.2
Rice, directly solidifies, energy 800mJ/cm after coating2。
Comparative example 5
This comparative example be related to it is a kind of for aluminium foil surface anti-corrosion light solidifying paint composition, including component shown in table 6 and
Parts by weight.
Coating is coated on processed aluminium foil (processing step is with embodiment 1) surface, coating dry measure control is micro- 1.2
Rice, directly solidifies, energy 800mJ/cm after coating2。
Comparative example 6
This comparative example be related to it is a kind of for aluminium foil surface anti-corrosion light solidifying paint composition, including component shown in table 7 and
Parts by weight.
Coating is coated on processed aluminium foil (processing step is with embodiment 1) surface, coating dry measure control is micro- 1.2
Rice, directly solidifies, energy 800mJ/cm after coating2。
Comparative example 7
This comparative example is related to a kind of for tinplate surface anticorrosion light solidifying paint composition, including component shown in table 8
And parts by weight.
Coating is coated on processed tinplate (processing step is with embodiment 6) surface, coating dry measure control is micro- 1.2
Rice, directly solidifies, energy 800mJ/cm after coating2。
Each component and its parts by weight in 1 embodiment of table
Each component and weight fraction in 2 comparative example 1 of table
| Raw material | Parts by weight |
| Chlorinated polyether resin (solid content 30%) | 40 |
| Petropols (solid content 30%) | 20 |
| Bisphenol A epoxide resin E51 | 9 |
| Zinc naphthenate | 3 |
| Toluene | 28 |
Each component and weight fraction in 3 comparative example 2 of table
Each component and weight fraction in 4 comparative example 3 of table
Each component and weight fraction in 5 comparative example 4 of table
| Raw material | Parts by weight |
| EB645 (cyanogen is special) | 35 |
| CN159 (Sartomer) | 10 |
| 6145 (Changxing) | 10 |
| Epoxy modification acrylate | 14 |
| Trimethylolpropane trimethacrylate | 5 |
| Pentaerythritol triacrylate | 5 |
| Third oxidation pentaerythritol tetraacrylate | 13 |
| 1- hydroxy-cyclohexyl-phenyl ketone | 5 |
| - 1 acetone of 2- hydroxy-2-methyl -1- phenyl | 2 |
| PM-2 | 1 |
Each component and weight fraction in 6 comparative example 5 of table
| Raw material | Parts by weight |
| EB645 (cyanogen is special) | 35 |
| CN159 (Sartomer) | 10 |
| 6145 (Changxing) | 10 |
| Organosilicon-modified acrylate | 14 |
| Trimethylolpropane trimethacrylate | 5 |
| Pentaerythritol triacrylate | 5 |
| Third oxidation pentaerythritol tetraacrylate | 13 |
| 1- hydroxy-cyclohexyl-phenyl ketone | 5 |
| - 1 acetone of 2- hydroxy-2-methyl -1- phenyl | 2 |
| PM-2 | 1 |
Each component and weight fraction in 7 comparative example 6 of table
| Raw material | Parts by weight |
| EB645 (cyanogen is special) | 35 |
| CN159 (Sartomer) | 10 |
| 6145 (Changxing) | 10 |
| Polybutadiene-modified acrylate | 15 |
| Trimethylolpropane trimethacrylate | 5 |
| Pentaerythritol triacrylate | 5 |
| Third oxidation pentaerythritol tetraacrylate | 13 |
| 1- hydroxy-cyclohexyl-phenyl ketone | 5 |
| - 1 acetone of 2- hydroxy-2-methyl -1- phenyl | 2 |
Each component and weight fraction in 8 comparative example 7 of table
| Raw material | Parts by weight |
| EB645 (cyanogen is special) | 10 |
| 623-100 (Changxing) | 20 |
| CN159 (Sartomer) | 10 |
| U100 (Bayer) | 15 |
| BR-144 (wave horse) | 6 |
| Polybutadiene-modified acrylate | 15 |
| Trimethylolpropane trimethacrylate | 8 |
| Third oxidation pentaerythritol tetraacrylate | 7 |
| Isopropyl thioxanthone | 2 |
| - 1 acetone of 2- hydroxy-2-methyl -1- phenyl | 3 |
Embodiment 8, performance detection
Performance detection is carried out to coating made from Examples 1 to 7 and comparative example 1~7 respectively, measures the attachment of coating
Power, acidproof, alkaline-resisting, salt spray resistance performance.
Specific performance detection project and corresponding method are as follows:
One, adhesive force
Using 3M610 adhesive tape, baige method tests specimen page adhesive force.
Appraisal procedure: 5B- scribing edge is smooth, at the edge and intersection of scribing line without peeling paint；
4B- has the peeling paint of small pieces in the intersection of scribing line, and the gross area that falls off is less than 5%；
3B- has the peeling paint of small pieces at the edge and intersection of scribing line, and falls off the gross area between 5-15%；
2B- has sheet of peeling paint at the edge and intersection of scribing line, and fall off the gross area 15-35% it
Between；
1B- has sheet of peeling paint at the edge and intersection of scribing line, and fall off the gross area 35-65% it
Between；
OB- has sheet of peeling paint at the edge and intersection of scribing line, and the gross area that falls off is greater than 65%.
Two, acid and alkali-resistance
The hydrochloric acid or sodium hydroxide solution for configuring 10% concentration, drop to coating surface 5 minutes, wash down drying with water, observation
Coating surface.
Appraisal procedure: observation treated coating is whether there is or not whitening, and whether there is or not bubblings.If there is above-mentioned bubbling phenomenon of whitening, comment
Valence is unqualified (NG), if unchanged qualified (OK)
Three, salt spray resistance
Specimen page is put on the table top of Shanghai sunset emblem C/YW-90 salt fog machine, configures 10% sodium chloride solution, it is continuous spraying
240 hours.
Appraisal procedure: whether observation coating, which damages, falls off, and it is otherwise unqualified (NG) that not damaged, which is qualified (OK),.
By the test result of Examples 1 to 7 and comparative example 1~7, including attachment, acid and alkali-resistance, salt spray resistance are summarized as follows table 9.
9 embodiment and comparative example test result of table
| Attachment | It is acidproof | It is alkaline-resisting | Salt spray resistance | |
| Embodiment 1 | 5B | OK | OK | OK |
| Embodiment 2 | 5B | OK | OK | OK |
| Embodiment 3 | 5B | OK | OK | OK |
| Embodiment 4 | 5B | OK | OK | OK |
| Embodiment 5 | 5B | OK | OK | OK |
| Embodiment 6 | 5B | OK | OK | OK |
| Embodiment 7 | 5B | OK | OK | OK |
| Comparative example 1 | 5B | NG | OK | OK |
| Comparative example 2 | 4B | OK | OK | NG |
| Comparative example 3 | 4B | NG | OK | NG |
| Comparative example 4 | 5B | NG | OK | NG |
| Comparative example 5 | 5B | OK | NG | NG |
| Comparative example 6 | 4B | NG | OK | OK |
| Comparative example 7 | 4B | NG | OK | OK |
As shown in Table 9, light solidifying paint composition of the invention has excellent adhesive force and acid and alkali-resistance, salt fog resistance
Energy；Comparative example 1 is solvent type heat-curing anticorrosive paint composition, and acid resistance is poor；Comparative example 2,3 is solvent-laden light
Cure coating compositions, solvent volatilization can bring pollution, meanwhile, there is a problem of that poor adhesive force, salt spray resistance are poor.This
Outside, inventors be surprised to learn that, in the present compositions, polybutadiene-modified acrylate can play good hydrophobic effect
Fruit prevents from seeping under solution and decomposes coating, and then excellent resistance to acid and alkali and salt fog resistance can be well realized.Comparative example 4,5
The difference from embodiment 1 is that epoxy modification acrylate, organosilicon-modified acrylate is respectively adopted to replace polybutadiene
Modification acrylate, by performance comparison it is found that the acid and alkali-resistance of embodiment 1, salt spray resistance are much better than comparative example 4,5.Meanwhile
Comparative example 4,5 and embodiment 1 all have good adhesive force, it is seen that adhesion promoter has played the good work for promoting attachment
With.By to the comparative example 6 and embodiment 1 for being added without adhesion promoter, the performance of comparative example 7 and embodiment 6 it was found that,
The adhesive force of comparative example 6,7 declines, however corresponding acid resistance is also declined, this illustrates in the present compositions,
Adhesion promoter is used in combination with polybutadiene-modified acrylate, also rises to the acid resistance of polybutadiene-modified acrylate
Collaboration facilitation is arrived.
It is the description carried out to specific embodiments of the present invention and comparative example above.It is to be appreciated that the present invention is not
It is confined to above-mentioned particular implementation, those skilled in the art can make various modifications within the scope of the claims, this is simultaneously
Substantive content of the invention is not influenced.
Claims (5)
1. one kind is used for Metal surface anti-corrosion light solidifying paint composition, which is characterized in that the composition includes following weight
The each component of number:
The polybutadiene-modified acrylate is by molecular weight ranges 500-800 containing double hydroxyl polybutadiene and isophorone
Di-isocyanate reaction, by adjust molar ratio generate end be isocyanate groups oligomer, later again with acrylic acid hydroxyl
Ethyl ester reaction, is synthesized into；
The adhesion promoter is phosphoric acid ester list official's monomer.
2. according to claim 1 be used for Metal surface anti-corrosion light solidifying paint composition, which is characterized in that the epoxy
Acrylate be selected from bisphenol A-type acrylate, novolac epoxy resin, organotitanium epoxy resin, glycerol epoxy acrylate,
One or more of alicyclic epoxy acrylate.
3. according to claim 1 be used for Metal surface anti-corrosion light solidifying paint composition, which is characterized in that the poly- ammonia
The polyurethane acrylate resin that ester acrylate is 3,4 degrees of functionality, is 5B to metal base adhesive force.
4. according to claim 1 be used for Metal surface anti-corrosion light solidifying paint composition, which is characterized in that the propylene
Esters of gallic acid monomer is selected from 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, polyethyleneglycol diacrylate, three hydroxyls
Propane tri, trimethylol-propane trimethacrylate, ethoxyquin trimethylolpropane trimethacrylate, third
Aoxidize trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxyquin Ji Wusi
One or more of alcohol tetraacrylate, the third oxidation pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.
5. according to claim 1 be used for Metal surface anti-corrosion light solidifying paint composition, which is characterized in that the light draws
It sends out agent and is selected from benzophenone, 1- hydroxy-cyclohexyl-phenyl ketone, -1 acetone of 2- hydroxy-2-methyl -1- phenyl, 2,4,6- front three
One or more of base benzoyl-diphenyl phosphine oxide, isopropyl thioxanthone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107236426A (en) * | 2017-06-28 | 2017-10-10 | 太仓市美航涂料有限公司 | A kind of high rigidity plated film UV finish paints |
| CN108641550A (en) * | 2018-05-25 | 2018-10-12 | 广州惠利电子材料有限公司 | A kind of curing insulation protection glue and its preparation method and application |
| CN109321125A (en) * | 2018-09-14 | 2019-02-12 | 依工特种材料（苏州）有限公司 | A kind of UV moisture dual cure three-proofing coating |
| CN111662632B (en) * | 2020-05-20 | 2022-03-08 | 中牟县美林包装有限责任公司 | Local reverse UV printing method for packaging box |
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| CN101392152A (en) * | 2008-09-28 | 2009-03-25 | 广东恒大新材料科技有限公司 | Photo-setting adhesive |
| CN101560370A (en) * | 2009-05-15 | 2009-10-21 | 烟台德邦科技有限公司 | Light-curable adhesive with shock absorption property |
| CN103059697A (en) * | 2012-12-28 | 2013-04-24 | 上海乘鹰新材料有限公司 | Ultraviolet curing coating composition for metallic yarn protective layer |
| CN103865470A (en) * | 2014-02-12 | 2014-06-18 | 惠晶显示科技（苏州）有限公司 | Light-curing edge sealing adhesive |
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|---|---|---|---|---|
| CN101392152A (en) * | 2008-09-28 | 2009-03-25 | 广东恒大新材料科技有限公司 | Photo-setting adhesive |
| CN101560370A (en) * | 2009-05-15 | 2009-10-21 | 烟台德邦科技有限公司 | Light-curable adhesive with shock absorption property |
| CN103059697A (en) * | 2012-12-28 | 2013-04-24 | 上海乘鹰新材料有限公司 | Ultraviolet curing coating composition for metallic yarn protective layer |
| CN103865470A (en) * | 2014-02-12 | 2014-06-18 | 惠晶显示科技（苏州）有限公司 | Light-curing edge sealing adhesive |
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Effective date of registration: 20200309 Address after: 201108 Shanghai city Minhang District Zhuan Hing Road No. 889 Building 1 Patentee after: Shanghai Zijiang new materials Polytron Technologies Inc Address before: 201111 Shanghai city Minhang District Kunyang Road No. 2055 Co-patentee before: Shanghai Chengying New Materials Co., Ltd. Patentee before: SHANGHAI WEIKAI OPTOELECTRONIC NEW MATERIALS CO., LTD. Co-patentee before: JIANGSU CHENGYING NEW MATERIALS CO., LTD. |