Curable composition, substrate and application
阅读说明：本技术 固化性组合物、基材及应用 (Curable composition, substrate and application ) 是由 钱彬 杨金梁 严春霞 于 2019-04-29 设计创作，主要内容包括：本发明提供了一种固化性组合物、基材及应用。该组合物包含如下组分：组分A、组分B、组分C以及组分D,组分A包含一种或多种化合物a,化合物a的结构中含有环氧环己基,组分B包含一种或多种化合物b,化合物b的结构中含有氧杂环丁基和环氧基,且化合物b的分子量≤500；组分C包含一种或多种化合物c,化合物c的结构中含有氧杂环丁烷基和苯基；组分D为光致酸产生剂。申请的固化性组合物为无溶剂添加型组合物,因而在进行涂装施工时,具有较低的环境成本,且无膨胀现象,表面附着力强,无需进行打磨或砂光即可重新施涂,尤其适宜在材料表面涂层的修补领域或厚涂领域进行推广应用。(The invention provides a curable composition, a substrate and application. The composition comprises the following components: the component A comprises one or more compounds a, the structure of the compound a contains epoxycyclohexyl, the component B comprises one or more compounds B, the structure of the compound B contains oxetanyl and epoxy, and the molecular weight of the compound B is less than or equal to 500; the component C comprises one or more compounds C, and the structure of the compound C contains an oxetanyl group and a phenyl group; component D is a photoacid generator. The curable composition is a solvent-free additive composition, so that the curable composition has low environmental cost, no expansion phenomenon and strong surface adhesion during coating construction, can be applied again without polishing or sanding, and is particularly suitable for popularization and application in the field of repairing or thick coating of material surface coatings.)
1. A curable composition, characterized in that it comprises the following components:
the component A comprises one or more compounds a, wherein the structure of the compound a contains epoxy cyclohexyl;
the component B comprises one or more compounds B, the structure of the compound B contains an oxetanyl group and an epoxy group, and the molecular weight of the compound B is less than or equal to 500;
a component C comprising one or more compounds C containing an oxetanyl group and a phenyl group in the structure; and
a component D, said component D being a photoacid generator.
2. The curable composition according to claim 1, wherein the compound a has 6 to 30 carbon atoms.
3. The curable composition according to claim 1, wherein the compound b has 5 to 25 carbon atoms.
4. The curable composition according to claim 1, wherein the compound c has 9 to 35 carbon atoms.
5. The curable composition according to claim 1 or 2, wherein the compound a is selected from any one of the following compounds:
6. The curable composition according to claim 1 or 3, wherein the compound b is selected from any one of the following compounds:
7. the curable composition according to claim 1 or 4, wherein the compound c is selected from compounds of the following structural formula I:
the R group is at least one of H, alkyl, substituted alkyl, phenyl or substituted phenyl.
8. The curable composition according to claim 7, wherein the structural formula (I) is one of the following compounds:
9. the curable composition according to claim 1, wherein the component D is: iodonium salts, sulfonium salts or arylferrocenium salts in which the negative ion can be replaced by Al [ OC (CF)3)3]4 -、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-Sulfonate ion, B (C)6X5)4 -Or [ (R)f)bPF6 -b]-Alternatively, wherein X is F or Cl, RfRepresents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, b represents an integer of 1 to 5, and b R' sfThe groups may be the same or different from each other.
10. Use of the curable composition of any one of claims 1 to 9 for refinishing the surface of a solid wood substrate, a metal substrate or a glass substrate.
11. A substrate having a photocurable film provided on a surface thereof, wherein the photocurable composition according to any one of claims 1 to 9 is cured to form the photocurable film.
12. The substrate of claim 11, wherein the substrate is a solid wood substrate, a metal substrate, or a glass substrate.
Technical Field
The invention relates to the field of photocuring compositions and application thereof, in particular to a curable composition, a substrate and application thereof.
Background
In recent years, researchers often form a plurality of layers on the surface of a substrate depending on the specific application of the cured product, and cure the cured product by using an active energy ray (ultraviolet ray, electron beam, visible light having a wavelength of 400nm to 500nm, or the like) at the time of forming each layer or at the time of patterning the transparent layer.
Disclosure of Invention
The invention mainly aims to provide a curable composition, a substrate and application, which solve the problem that the prior cured composition has high environmental pollution cost when in use.
In order to achieve the above object, according to one aspect of the present invention, there is provided a curable composition comprising the following components: the component A comprises one or more compounds a, the structure of the compound a contains epoxycyclohexyl, the component B comprises one or more compounds B, the structure of the compound B contains oxetanyl and epoxy, and the molecular weight of the compound B is less than or equal to 500; the component C comprises one or more compounds C, and the structure of the compound C contains an oxetanyl group and a phenyl group; component D is a photoacid generator.
Further, the compound a is a compound having 6 to 30 carbon atoms.
Further, the compound b is a compound having 5 to 25 carbon atoms.
Further, the compound c is a compound having 9 to 35 carbon atoms.
Further, the compound a is selected from any one of the following compounds:
further, compound b is selected from any one of the following compounds:
Further, compound c is selected from compounds of the following structural formula I:
the R group is at least one of H, alkyl, substituted alkyl, phenyl or substituted phenyl.
Further, structural formula (I) is a compound as follows:
further, the component D is: iodonium salt, sulfonium salt or arylferrocenium salt, wherein the anion in iodonium salt, sulfonium salt or arylferrocenium salt can be replaced by Al [ OC (CF)3)3]4 -、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-Sulfonate ion, B (C)6X5)4 -Or [ (R)f)bPF6 -b]-Alternatively, wherein X is F or Cl, RfRepresents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, b represents an integer of 1 to 5, and b R' sfThe groups may be the same or different from each other.
In order to achieve the above object, according to one aspect of the present invention, there is provided a use of any one of the above curable compositions for recoating a surface of a solid wood substrate, a metal substrate or a glass substrate.
According to another aspect of the present invention, there is provided a substrate having a photocurable film formed on a surface thereof, wherein the photocurable film is obtained by curing any one of the curable compositions.
Further, the substrate is a solid wood substrate, a metal substrate or a glass substrate.
The curable composition of the present invention is a solvent-free additive composition, and therefore, has a low environmental cost in coating work. In addition, the photocuring film formed by the combination of the monomers has no expansion phenomenon after being cured, has strong surface adhesion, can be applied again without polishing or sanding, and has better performances of a recoated curing product, so that the surface trace of the curing film caused in the prior construction polishing process can be avoided, the production cost is low, and the photocuring film is particularly suitable for being popularized and applied in the field of repairing or thick coating of material surface coatings.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As mentioned in the background section, the light-curable compositions of the prior art all suffer from the problem of high environmental pollution costs, and in order to improve this situation, the present application has conducted intensive research and analysis on the formulation of the existing curable compositions, and has proposed an improved curable composition comprising the following components: components A, B, C and D, wherein component A comprises one or more compounds a having epoxycyclohexyl groups in the structure; the component B comprises one or more compounds B, the structure of the compound B contains an oxetanyl group and an epoxy group, and the molecular weight of the compound B is less than or equal to 500; the component C comprises one or more compounds C, and the structure of the compound C contains an oxetanyl group and a phenyl group; component D is a photoacid generator.
The curable composition of the present invention is a solvent-free additive composition, and has a low environmental cost in coating work. In addition, the photocuring film formed by the combination of the monomers has no expansion phenomenon after being cured, has strong surface adhesion, can be applied again without polishing or sanding, and has better performances of a recoated curing product, so that the surface trace of the curing film caused in the prior construction polishing process can be avoided, the production cost is low, and the photocuring film is particularly suitable for being popularized and applied in the field of repairing or thick coating of material surface coatings.
In order to further increase the curing effect of the monomers in component A, in a preferred embodiment, compound a is a compound having 6 to 30 carbon atoms. Similarly, in a preferred embodiment, the compound b is a compound having 5 to 25 carbon atoms. In a preferred embodiment, the compound c is a compound having 9 to 35 carbon atoms.
In a more preferred embodiment of the present application, the compound a is selected from any one of the following compounds:
in a more preferred embodiment, compound b is selected from any one of the following compounds:
in a more preferred embodiment, compound c is selected from compounds of the following structural formula I:
the R group is at least one of H, alkyl, substituted alkyl, phenyl or substituted phenyl.
In a more preferred embodiment, the compound of formula (I) above may be any one of the following:
the compounds of components A, B and C are both photocurable monomers as curing monomers and are therefore curable to form polymers under the action of photoacid generators. The specific type of the specific photoacid generator can be reasonably selected according to different practical application scenes or requirements. Examples of such photoacid generators include onium salt compounds (e.g., sulfonium salts, iodonium salts) and arylferrocenium salts. Component D may be a cationic photoinitiator, and further a cationic photoacid generator disclosed in application No. 201710035435.3 may be selected, in consideration of the combination of cost and effect of co-use, such as photoinitiation efficiency, curing speed, etc.
In a preferred embodiment, component D is: iodonium salt, sulfonium salt or arylferrocenium salt, wherein the anion in the iodonium salt, sulfonium salt or arylferrocenium salt is coated with Al [ OC (CF)3)3]4 -、X-、ClO4 -、HSO4 -、CF3COO-、(BX4)-、(SbX6)-、(AsX6)-、(PX6)-Sulfonate ion, B (C)6X5)4 -Or [ (R)f)bPF6 -b]-Alternatively, wherein X is F or Cl, RfRepresents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, b represents an integer of 1 to 5, and b R' sfThe groups may be the same or different from each other.
Commercially available cationic photoinitiators of the same type of structure may also be used in component D of the present invention, examples include, but are not limited to: PAG20001, PAG20001s, PAG20002s, PAG30201, PAG30101, etc., manufactured by Tronly, and Irgacure250, manufactured by BASF, etc.
The curable composition may contain the above components in different proportions depending on the actual application. In a preferred embodiment, the proportion of the above components in the composition is as follows: and (2) component A: 10-30 wt%; and (B) component: 10-30 wt%; and (3) component C: 30-75 wt%; and (3) component D: 2-10 wt%. In another preferred embodiment of the present application, the content ratio of the above components is further optimized, specifically, the ratio of component a: 15-25 wt%; and (B) component: 15-25 wt%; and (3) component C: 40-60 wt%; and (3) component D: 3-7 wt%.
It should be noted that, the curable composition of the present application may further include some optional auxiliary monomers, such as monofunctional compounds and monofunctional epoxy compounds and/or multifunctional epoxy compounds, examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1, 2-epoxybutane, 1, 3-butadiene monoxide, 1, 2-epoxydodecane, epichlorohydrin, 1, 2-epoxydecane, styrene oxide, epoxycyclohexane, 3-methacryloyloxymethyl cyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene oxide, and the like.
Examples of the polyfunctional epoxy compound include bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol a diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol a diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4 '-epoxycyclohexylmethyl 3', 4 '-epoxycyclohexanecarboxylate, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl 3', 4 '-epoxy-6' -methylcyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3, 4-epoxycyclohexylmethyl) ether, ethylenebis (3, 4-epoxycyclohexanecarboxylate), dioctyl cyclohexylphthalate, di-2-ethylhexyl cyclohexylphthalate, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 13-tetradecane dioxide, limonene dioxide, 1,2,7, 8-diepoxyoctane and the like.
The content of the auxiliary monomer is 0 to 5% by weight, preferably 0 to 3% by weight, of the sum of the aforementioned components A, B and C.
The curable composition of the present invention may further comprise an auxiliary component E, and the auxiliary component E may be organic and/or inorganic auxiliary agents commonly used in the art, including but not limited to color materials, leveling agents, curing accelerators, light/heat acid generators, plasticizers, adhesion promoters, fillers, defoamers, surface conditioners, antioxidants, ultraviolet absorbers, dispersion aids, anti-agglomeration agents, catalysts, thickeners, sensitizers, coupling agents, crosslinking agents, and the like.
As the coloring material, for example, a pigment, a dye, a natural pigment, and the like can be used, and these coloring materials may be used alone or in combination of two or more.
As an illustrative example of the Blue Pigment or cyan Pigment, Pigment Blue (Pigment Blue)1, 2, 3, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60; examples of the Green Pigment include Pigment Green (Pigment Green)7, 26, 36, and 50.
Examples of the Red Pigment or magenta Pigment include Pigment Red (Pigment Red)1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 19, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:2, 58:4, 63:1, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, iron oxide, and the like; examples of the Violet Pigment include Pigment Violet (Pigment Violet)3, 19, 23, 29, 30, 37, 50, 88; examples of orange pigments include pigment orange (pigment orange)13, 16, 20, and 36.
Examples of the Yellow Pigment include Pigment Yellow (Pigment Yellow)1, 2, 3, 4, 5, 6, 7, 10, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193.
Examples of the Black Pigment include Pigment Black (Pigment Black)7, 28, and 26, furnace Black, lamp Black, acetylene Black, and channel Black; mitsubishi chemical products NO.2300, NO.900, MCF88, NO.33, NO.40, NO.45, NO.52, MA7, MA8 and MA 100; carbon blacks such as Regal 400R, Regal 300R, Regal 660R, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, and Monarch 1400 manufactured by Cabot Japan.
Examples of the White Pigment include Pigment White (Pigment White)6, 18, 21, and titanium oxide.
The content of the color material is 0 to 40% by weight, preferably 5 to 40% by weight, based on the total mass of the components a + B + C + D in the curable composition of the present invention. The average particle size of the color material is not particularly limited and may be appropriately selected depending on the intended use.
For the dispersion of the color materials, there are optional dispersion apparatuses such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint stirrer, a kneader, a stirrer, a henschel mixer, a colloid mill, an ultrasonic homogenizer, a bead mill, a wet jet mill, or the like.
In the present invention, in order to stably disperse the color material in the curable composition of the present invention, it is preferable to add a dispersing monomer and/or a dispersing aid. The content of the dispersing aid in the curable composition of the present invention is 1 to 80 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the color material. When the dispersion aid is set within the above range, the color material is not easily aggregated or precipitated when used in the composition, and the composition has excellent storage stability and suitable viscosity.
As the dispersing aid usable in the present invention, a polymer dispersant is preferable. As an illustrative example, the polymer dispersant may be mentioned DISPERBYK-101/102/103/106/111/161/162/163/164/166/167/168/170/171/174/182 manufactured by BYK Chemie, etc.; EFKA4010/4046/4080/5010/5207/5244/6745/6750/7414/7462/7500/7570/7575/7580 prepared from EFKA additive; DISPERSE AID 6/8/15/9100 manufactured by San Nopco Limited, and the like; SOLSPERSE dispersants made by Avecia such as: SOLSPERSE3000/5000/9000/12000/13240/13940/17000/22000/24000/26000/28000/32000/36000/39000/41000/71000, etc.; ADEKA PLURONIC L31/F38/L42/L44/L61/L64/F68/L72/P95/F77/P84/F87/P94/L101/P103/F108/L121 manufactured by Adeka corporation, and the like.
The dispersion monomer used when the color material is dispersed in the above composition is not particularly limited, and for example, a polymerizable compound having a low molecular weight, preferably a low-viscosity polymerizable compound, may be used as the dispersion monomer. When the dispersing monomer, the color material and the dispersing auxiliary agent are preferentially mixed, the sum of the weight fraction of the dispersing monomer and the weight fraction of the color material is 100 percent.
The sensitizer is used for the purpose of improving the sensitivity of the ink, and particularly when the radiation source is an LED, the sensitizer may be a pyrazoline compound, an acridine compound, an anthracene compound, a thioxanthone compound, a naphthalene compound, a coumarin compound, a tertiary amine compound, or the like. As the anthracene-based sensitizer compound, the sensitizer content is 0-0.5 wt%, preferably 0.01-0.5 wt%, based on the total mass of the aforementioned components A + B + C + D, and may be selected from the sensitizers disclosed in patent 2017100354353, preferably one or more combinations selected from the following compounds:
in order to obtain a coating effect excellent in smoothness, the curable composition of the present invention may contain a leveling agent in an amount of 0 to 0.5% by weight, preferably 0.01 to 0.5% by weight, based on the total of component a to component D.
In a second exemplary embodiment, a photocurable film is provided, which is formed by curing any one of the above-described curable compositions. The composition is a solvent-free additive composition, so that the environment cost is low when coating construction is carried out. The photocuring film formed by the combination of the monomers has no expansion phenomenon after being cured, has strong surface adhesion, can be applied again without polishing or sanding, and has better performances of a recoated curing product, so that the surface trace of the curing film caused in the prior construction polishing process can be avoided, the production cost is low, and the photocuring film is particularly suitable for popularization and application in the field of repairing or thick coating of material surface coatings.
In a third exemplary embodiment of the present application, there is provided a substrate having a photocurable film provided on a surface thereof, wherein the photocurable film is obtained by curing any one of the curable compositions. The photocurable film formed from the curable composition herein is a multilayer coating or multilayer printed matter formed on a substrate in accordance with the application properties.
The photocuring film formed after the composition is cured has no expansion phenomenon and strong surface adhesion, can be applied again without polishing or sanding, and has better performances of a recoating curing product, so that surface traces of the curing film caused in the existing construction polishing process can be avoided, the production cost is low, and the photocuring film is particularly suitable for popularization and application in the field of repairing or thick coating of material surface coatings.
The base material is not particularly limited, and may be appropriately selected depending on the purpose of use, and may be, for example: paper, paper laminated with plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), metal plate (e.g., aluminum, zinc, copper, etc.), plastic film (e.g., cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film laminated or vapor-deposited with the above metal, polyester film, polyolefin film, cycloolefin film, acrylic film, etc. The thickness of the base material may be appropriately selected depending on the intended use, and is generally 20 to 300. mu.m.
In a preferred embodiment, the substrate may be a solid wood substrate, a metal substrate or a glass substrate.
The curable composition of the present invention can be used for photocuring molding by stirring and mixing until uniform, and specifically can be stirred and mixed until uniform by using a stirrer, a disperser, a homogenizer, or the like. The specific coating method is appropriately selected depending on the purpose, and known methods such as coating methods using a bar, a wire bar, a blade, reverse roll coating, spray coating, microgravure, gravure, curtain, or spin coating can be used.
In the present application, a specific method for curing the above-mentioned curable composition is to apply the curable composition to a substrate and to cure the curable composition on the substrate by irradiation with active energy rays (for example, ultraviolet rays, electron beams, visible rays having a wavelength of 400nm to 500nm, and the like). Specifically, as the light source of ultraviolet rays and visible rays having a wavelength of 400nm to 500nm, an LED lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used.
The advantageous effects of the present application will be further described with reference to specific examples.
The starting materials used in the following examples are, unless otherwise indicated, all materials commonly used in the art and commercially available. The test methods used in the following examples and comparative examples are as follows:
Experimental preparation of colored composition and application
1.1. Preparation of pigment dispersions
The color materials, dispersion aids, and dispersion monomers were weighed according to the formulations shown in examples 1 to 5 in table 1 and were used. The dispersing monomers are firstly and uniformly mixed according to the sequence from top to bottom in the table, then the dispersing auxiliary agents are sequentially added into the dispersing monomers according to the sequence from top to bottom in the table, and a homogenizer is used for stirring until the dispersing monomers and the dispersing auxiliary agents are uniformly mixed. Adding the color material and the dispersing beads within 10min, pre-stirring for 1h at the speed of 800-. D of the pigment dispersion observed as measured by an Oumeck TopSizer laser particle size Analyzer90When the particle size was 1.500. mu.m or less, the stirring was stopped, and the dispersed beads were filtered off to obtain pigment dispersions 1 to 5. Wherein the dispersing beads are zirconia ceramic microspheres with the average grain diameter of 0.80 mm; the ratio of the total pigment dispersion (excluding the mass of the dispersion beads) to the amount of the dispersion beads (which have been ground and subsequently filtered) added, in terms of mass ratio, is 1: 1.
table 1:
in the formula, the pigment black is American cabot ME carbon black; the pigment white is DuPont titanium white R706; pigment Blue is CI.pigment Blue 15: 3; pigment Yellow is ci.pigment Yellow 74; pigment Red is ci.pigment Red 122.
DM1 is of the structural formulaDM2 is TTA21S with a structural formula of Jiangsu Tytel, DM3 is with a structural formula of
1.2. Formulation of colored compositions
A color strength of 40% k was prepared using the pigment dispersions obtained in examples 1 to 5. The color concentration k of the pigment dispersion is calculated by the formula: the amount of color material/(amount of color material + amount of dispersed monomer + amount of dispersion aid) × 100%.
According to the formula shown in the following table 2, the component A, B, C, D and the sensitizer are respectively and uniformly mixed in advance at 20-30 ℃, then the raw materials are sequentially added into a constant temperature and constant pressure reactor according to the components A, B, C, the sensitizer, the pigment dispersion, the leveling agent BYK 307 and the defoaming agent BYK055 and D, the raw materials are pre-stirred for 0.5h under the condition of a yellow light lamp (i.e. a safety lamp which can not trigger the reaction) at the rotating speed of 800 plus 1000rpm by using a stirrer, and then the raw materials are formally stirred under the rotating speed of 1500 plus 2000rpm, when the visual inspection mixed liquid is a uniform mixture (in the following embodiment, the visual inspection mixed liquid is uniformly mixed for 10-30min), and the colored composition of the embodiments 6-10 of the invention is obtained by filtering through a filter screen.
Table 2:
in Table 2, A1 isA2 is
B1 is
C1 is
C2 is
D1 is a compound of PAG20002 s; d2 is tag 20001s for yokou strong electrons;
ZGJ1 is
Storage stability tests were carried out on the compositions prepared in examples 6 to 10, in particular with reference to the method of the GB-T6753.3-1986 storage stability test. The method comprises the following steps: covering a cover on two cans of samples which are filled with the same composition and have the same weight, placing the two cans of samples in a constant-temperature drying oven at 50 ℃, taking out the samples after 7 days, measuring the viscosity of the composition after standing the mixture at room temperature for 24 hours to obtain the after-viscosity, and carrying out rating according to the ratio percentage of the after-viscosity to the initial viscosity (the ratio percentage of the two cans of samples which are the same is close to or the same and is in the following division range, otherwise, the ratio percentage is not considered) as follows: o: the viscosity change ratio is below 5%; very good: the viscosity change proportion is more than 5 percent and less than 10 percent; ●: the viscosity change ratio is more than 10%.
The results of the storage stability tests of the above examples 6 to 10 were all: and O.
1.3. Use of a coloured composition
1.3.1 solid Wood substrate surface coating and recoating
The following embodiment provides white paint for coating and recoating the surface of a solid wood substrate, has a simple construction process, can be directly recoated without polishing, and is implemented by the following technical scheme:
(1.3.1a) the white curable composition prepared in example 7 was dispersed at a high speed of 1000-1200r/min for 10min to control the fineness below 30 μm;
(1.3.1b) coating the composition obtained in the step (1.3.1a) on the surface of a solid wood substrate (provided by Xuzhou Laotai furniture) by using a 15-micron wire rod to form a film in a single time, and exposing the film to UVLED crawler-type light source with the wavelength of 385nm at the temperature of 25 ℃ and the relative humidity of 50% (the light intensity is 18W/cm)2270m/min track speed), curing, and standing for 24 hours at room temperature to obtain a white primary coating plate;
(1.3.1c) under the condition of not sanding the white primary coating plate, coating the composition obtained in the step (1.3.1a) on the surface of the white primary coating plate by a 15-micrometer wire rod for a second time to form a film, and exposing the coated film by a UV LED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and 50% of relative humidity (the light intensity is 18W/cm)2And the track speed is 270 m/min), and the white secondary coating plate is obtained after the curing and the standing for 24 hours at room temperature.
The white primary-coated board and the white secondary-coated board were each subjected to performance evaluation including the curability, boiling resistance, acid/alkali/salt resistance, and gasoline resistance of the cured layer.
Specifically, the evaluation of the curability described above employs: testing a completely cured film under the conditions of 23 ℃ and 50% relative humidity, manually cutting the cured film into hundreds of grids by adopting a QFH (quad Flat No-lead) paint film grid cutting instrument according to a paint film grid cutting test method specified in GB/T9286-1998, adhering a 3M transparent test adhesive tape to the marked hundreds of grids in different directions, applying force to firmly adhere the adhesive tape to the film surface and the grid cutting part, holding one end of the 3M adhesive tape within 2min, and stably tearing off the adhesive tape within 1s at an angle of 60 degrees, wherein the evaluation criteria are as follows: o: grade 0-1 ∈ x: grade 2-3, x: 4-5 grades.
The boiling resistance test is to immerse 2/3 areas of the white primary coating plate and the white secondary coating plate in boiling distilled water respectively and keep boiling for 1h, observe the coating condition, and adopt the test results as follows: evaluation was performed on three scales ≧ no change ≈ 20% area dropout and ≧ 20% area dropout.
The acid/alkali/salt resistance is measured by respectively using 5% (mass concentration) NaOH solution and 5% (mass concentration) H under the conditions of 20 ℃ and 50% relative humidity2SO4The solution, 5% (mass concentration) of distilled aqueous solution of sodium chloride was dropped on the surface of the above-mentioned coating plate, and observed after 24 hours, the test results were as follows: evaluation was performed on three scales of "o (no change)," o (wrinkled) "and" x (peeled off).
The gasoline resistance test is to test the coated plate by referring to the gasoline resistance test method of paint film specified in GB/T1734-93, and the test result is as follows: evaluation was performed on three scales of "o (no change)," o (wrinkled) "and" x (peeled off). The above evaluation results are summarized in the following Table 3.
Table 3:
testing
Curing Properties
Resistant poaching
Acid resistance
Alkali resistance
Salt tolerance
Gasoline resistant
White one-time coating plate
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White secondary coated plate
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As can be seen from table 3, when the curable composition of example 7 is used to coat and recoat the surface of a solid wood substrate (wood furniture, floor, cabinet, bathroom, etc.), the obtained cured film has good environmental protection performance, smooth surface and strong adhesion after curing, can be recoated or repaired without sanding, and is particularly suitable for recoating or repairing thicker films. The curable composition is used for recoating, preparing or repairing, the VOC emission is zero in the curing process, the environment friendliness of a cured film is better, the surface is smooth and has no polishing trace, the film surface is vivid and is rich in aesthetic feeling, the cured film is not easy to drop or crack in the later use process, the labor intensity of workers can be effectively reduced, the production efficiency is improved, the product quality is effectively guaranteed, and the curable composition is suitable for further large-scale popularization and application.
After the sensitizer is removed from the composition of the embodiment, the obtained cured film can achieve or exceed the technical effects of the above table 3 under the ultraviolet light source of the mercury lamp with the wavelength range of 200-450 nm and under the condition of the same light intensity or less, and the details are not repeated here.
1.3.2 surface coating and recoating of Metal substrates
The following embodiment of the invention provides the blue refinishing paint for coating the surface of the metal base material, the construction process is simple, and the refinishing can be directly carried out without polishing. The first class of embodiments is specifically practiced by the steps of:
(1.3.2a) the blue curable composition obtained in example 8 was dispersed at a high speed of 1000 and 1200r/min for 10 min;
(1.3.2b) coating the composition obtained in the step (1.3.2a) on the surface of a tinplate substrate (a tinplate sheet of a coating test grade) by a 15-micrometer wire rod for forming a film in a single time, and exposing the coated film to a UV LED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and the relative humidity of 50% (the light intensity is 18W/cm)2270m/min track speed), curing, and standing for 24 hours at room temperature to obtain a blue primary coating plate;
(1.3.2c) under the condition that the blue primary coating plate is not sanded, the composition obtained in the step (1.3.2a) is coated on the surface of the blue primary coating plate by a 15-micrometer wire rod to form a film once again, and the coated film is exposed by a UV LED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and 50% of relative humidity (the light intensity is 18W/cm) 2And the track speed is 270 m/min), and the blue secondary coating plate is obtained after the curing and the standing for 24 hours at room temperature.
The blue primary coated panel and the blue secondary coated panel were subjected to performance evaluation with reference to the aforementioned test methods, respectively, and the results are shown in table 4 below.
Table 4:
testing
Curing Properties
Resistant poaching
Acid resistance
Alkali resistance
Salt tolerance
Gasoline resistant
Blue once coated board
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Blue secondary coating plate
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As can be seen from Table 4, the curable composition of example 8 is applied and recoated on the surface of a metal substrate (the surface of a traffic sign), and the obtained cured film has good environmental protection performance, smooth surface and strong adhesive force after curing, can be recoated or repaired without sanding, and is particularly suitable for recoating or repairing thicker films. The curable composition is used for recoating, preparing or repairing, the VOC emission is zero in the curing process, the environment friendliness of a cured film is better, the surface is smooth and has no polishing trace, the film surface is vivid and is rich in aesthetic feeling, the cured film is not easy to drop or crack in the later use process, the labor intensity of workers can be effectively reduced, the production efficiency is improved, the product quality is effectively guaranteed, and the curable composition is suitable for further large-scale popularization and application.
A second class of embodiments of the surface coating and recoating of metal substrates of the present invention is as follows:
The compositions obtained in example 7 and example 9 were coated on the surface of the same tinplate substrate (coating test grade tinplate) by a single coating film forming process with a 10 μm wire rod, the film forming areas of the compositions obtained in example 7 and example 9 were 1/3 of the tinplate substrate, respectively, and the above coating films were exposed to UV LED crawler light source with a wavelength of 385nm (light intensity 18W/cm)2And the track speed is 280 m/min), and the white and yellow once-coated plate is obtained after the curing and the standing for 24 hours at room temperature.
The composition obtained in example 10 was coated on the surface of the white and yellow primary coated plate with a 10 μm wire bar in a single pass to form a film, the film-formed surface covered the entire surface of the primary coated plate, and the film was exposed to UV LED crawler light source having a wavelength of 385nm (light intensity 18W/cm)2And the track speed is 280 m/min), and the plate is placed for 24 hours at room temperature after being cured to obtain the red/white + yellow secondary coating plate.
The coated sheets were evaluated for their respective properties, and the results are shown in Table 5 below.
Table 5:
as can be seen from table 5, the curable composition in the above embodiments can be applied and recoated on the surface of a metal substrate (repair of a cured film on the surface of a metal substrate such as automobile paint repair and hub scratch), and can be laminated to form a printed pattern or applied on the surface of a metal (such as a metal tank, a metal barrel, a metal container, etc.) in different colors, the obtained cured film is formed without sanding or grinding, the cured film is environmentally friendly, the surface is smooth and has no grinding mark, the film surface is vivid and is rich in aesthetic feeling, and the cured film is not easy to drop or crack in the later use process, so that the labor intensity of workers can be effectively reduced, the production efficiency can be improved, the product quality can be effectively guaranteed, and the curable composition is suitable for large-scale.
After the sensitizer is removed from the composition of the embodiment, the obtained cured film can achieve or be superior to the technical effects of the table 4 or 5 under the ultraviolet light source of a mercury lamp with the wavelength range of 200-450 nm and under the condition of the same light intensity or less.
1.3.3 glass substrate surface coating and recoating
The following examples provide red repair coatings for glass substrate surface coating, which are simple in construction process and can be directly recoated without polishing. The method is implemented by the following technical scheme:
(1.3.3a) the curable composition obtained in example 10 was dispersed at a high speed of 1000-;
(1.3.3b) coating the composition obtained in the step (1.3.3a) on the surface of a glass substrate (common window glass sheet) by a 15-micron wire rod to form a film in a single time, and exposing the coated film to a UVLED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and the relative humidity of 50% (the light intensity is 18W/cm)2270m/min track speed), curing, and standing for 24 hours at room temperature to obtain a red primary coating plate;
(1.3.3c) under the condition that the red primary coating plate is not sanded, the composition obtained in the step (1.3.3a) is coated on the surface of the red primary coating plate by a 15-micrometer wire rod to form a film once again, and the coated film is exposed by a UV LED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and 50% of relative humidity (the light intensity is 18W/cm) 2And the track speed is 270 m/min), and the red secondary coating plate is obtained after the curing and the standing for 24 hours at room temperature.
The red-coated plates were each subjected to performance evaluation in accordance with the foregoing test method, and the results are shown in table 6 below.
Table 6:
testing
Curing Properties
Resistant poaching
Acid resistance
Alkali resistance
Salt tolerance
Gasoline resistant
Red one-time coated board
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Red secondary coating plate
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As can be seen from the above Table 6, the above curable composition can be applied and recoated on the surface of a glass substrate (surface of a glass substrate is coated and repaired, and the surface of a glass bottle is coated and repaired, and the like), the obtained cured film is formed under the sanding-free process condition, the cured film has good environmental protection property, smooth surface, no polishing trace, vivid film surface and good aesthetic feeling, is not easy to drop or crack in the later use process, can effectively reduce the labor intensity of workers, improve the production efficiency, effectively ensure the product quality, and is suitable for large-scale popularization and application.
After the sensitizer is removed from the composition of the embodiment, the obtained cured film can achieve or be superior to the technical effects of the following table 6 under the conditions of the ultraviolet light source of the mercury lamp with the wavelength range of 200-450 nm and the same light intensity or less.
1.3.4 surface coating and recoating of Plastic substrates
The compositions obtained in examples 6 and 9 were coated with a 10 μm wire rod to form a film on the surface of a PET substrate (available from Dongguan plastics) in a single pass, the film-forming areas of the compositions obtained in examples 6 and 9 were 1/3 of the PET substrate, respectively, and the film was exposed to UV LED crawler light source with a wavelength of 385nm (light intensity 18W/cm)2And the track speed is 280 m/min), and the plate is placed at room temperature for 24 hours after being cured to obtain the black and yellow once-coated plate.
The compositions obtained in example 7 and example 8 were coated on the surface of the black and yellow primary coating plate with a 10 μm wire rod to form a film in a single pass, the film-forming surface covered the entire surface of the black and yellow primary coating plate, and the film was exposed to UV LED crawler light source with a wavelength of 385nm (light intensity 18W/cm) at 25 ℃ and a relative humidity of 50%2And the crawler speed is 280 m/min), and the white/(black + yellow) secondary coating plate and the blue/(black + yellow) secondary coating plate are obtained after the curing and the placement for 24 hours at room temperature.
The following were performance evaluations of the black + yellow primary coated panel, the white/(black + yellow) secondary coated panel and the blue/(black + yellow) secondary coated panel, respectively, with reference to the foregoing test methods, and the results are shown in table 7 below.
Table 7:
testing
Curing Properties
Resistant poaching
Acid resistance
Alkali resistance
Salt tolerance
Gasoline resistant
Black and yellow once coated plate
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White/black + yellow secondary coating plate
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Blue/black + yellow secondary coating plate
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As can be seen from Table 7, the curable composition in the above examples can be used for color layer lamination, colorless color lamination to form printed patterns or coating (such as plastic surface pattern printing, surface packaging of living goods (such as surface pattern layer lamination of sign pen and protective layer lamination), and is suitable for further popularization and application in the laminating field.
After the sensitizer is removed from the composition of the embodiment, the obtained cured film can achieve or be superior to the technical effects of the following table 7 under the conditions of an ultraviolet light source of a mercury lamp with the wavelength range of 200-450 nm and the same light intensity or less.
Preparation and application of experiment colorless composition
2.1 preparation of colorless compositions
According to the formula shown in Table 8, the polymerizable compound A, B, C, D and the sensitizer are respectively and uniformly mixed in advance at 20-30 ℃, then the raw materials are added into a constant temperature and pressure reactor according to the sequence of A, B, C, the sensitizer, the leveling agent BYK 307, the defoaming agent BYK 055 and D, the mixture is stirred at the rotation speed of 1500-2000rpm under the condition of a yellow light lamp (i.e. a safety lamp which does not trigger the reaction), and when the mixture is uniform by visual inspection (in the following examples, the mixture is uniformly mixed from stirring to visual inspection for 10-30min), the composition of the embodiment 11-15 is obtained by filtering through a filter screen.
TABLE 8
In Table 8, A3 is
A4 is
B3 isB4 is
C3 is
C4 is
C9 isn-1, 2, 3, wherein n-1 accounts for 80%, n-2 accounts for 10%, and n-3 accounts for 10%;
d3 is PAG30201 for Changzhou strong electron;
ZGJ3 isA compound of structural formula (la);
ZGJ4 is
The compositions prepared in examples 11-15 were tested for storage stability using the methods described above and all results were: and O.
2.2 use of colorless compositions
The following examples provide colorless priming layers for coating the surfaces of the metal substrate, the solid wood substrate, the glass substrate and the plastic substrate, the construction process is simple, the colorless priming layers can be directly recoated without polishing, and the implementation scheme is as follows:
(2.2a) the curable compositions obtained in examples 11 to 15 were dispersed at a high speed of 1000 and 1200r/min for 10 min;
(2.2b) coating the composition obtained in the step (2.2a) on the surface of a tinplate substrate (a tinplate sheet of a coating test grade), a solid wood substrate (provided by Xuzhou old four-piece furniture), a glass substrate (provided by glass sheets for ordinary windows) and a PET substrate (provided by Dongguan Dong plastics) by using 15 mu m wire rods to form a film in a single time, and exposing the coated film to a UV LED crawler-type light source with the wavelength of 385nm (the light intensity is 18W/cm) under the conditions of 25 ℃ and the relative humidity of 50 percent (the light intensity is 18W/cm) 2270m/min track speed), curing, and standing for 24 hours at room temperature to obtain a primary coated plate; wherein examples 11 and 12 are for plastic substrates, example 13 is for solid wood substrates, example 14 is for glass substrates, example 15 is for metal substrates;
(2.2c) coating the primary coating composition on the original substrate on the surface of the primary coating plate by using a 15-micrometer wire rod to form a film on the primary coating plate in a single time under the condition that the primary coating plate is not sanded, and exposing the coated film by using a UV LED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and the relative humidity of 50 percent (the light intensity is 18W/cm)2And the track speed of 270 m/min), and standing for 24 hours at room temperature after curing to obtain the secondary coated plate.
The performance evaluation was performed with respect to the above-described primary coated board and secondary coated board, respectively, with reference to the aforementioned test methods, and the results are shown in table 9 below.
Table 9:
as can be seen from Table 9, the colorless curable composition can be coated or recoated on the surface of different substrates, and the surface of the cured film is also smooth and has strong adhesion, so that recoating or repairing can be carried out without polishing.
Replacement of C4 by C5 in example 15The remainder was unchanged, thus resulting in example 16, which was applied to the above application and all of the above properties tested were equally good.
The formulation of example 16 was selected and designedExamples 17 and 18 and comparative example 1, examples 17 and 18 and comparative examples 1 and 16 differ in their composition: in example 17, C5 in example 16 is replaced by C6
The curable compositions obtained in examples 17 and 18 and comparative example 1 were dispersed at a high speed of 1000-; coating the composition on the surface of a tinplate substrate (coating test grade tinplate) by a 15-micrometer wire rod to form a film once, and exposing the coated film by a UV LED crawler-type light source with the wavelength of 385nm (the light intensity is 18W/cm)2270m/min track speed) and left at room temperature for 24 hours after curing to give the primary coated panels of examples 17, 18 and comparative example 1.
Under the condition that the primary coating plates are not sanded, the surfaces of the primary coating plates of the working examples 17 and 18 and the comparative example 1 are coated with films by a 15-micrometer wire rod for one time, and the coated films are exposed by a UVLED crawler-type light source with the wavelength of 385nm under the conditions of 25 ℃ and 50% of relative humidity (the light intensity is 18W/cm)2And the track speed of 270 m/min), and standing for 24 hours at room temperature after curing to obtain respective secondary coated plates.
The performance evaluation was performed with respect to the above-described test methods for the primary coated sheet and the secondary coated sheet of examples 17 and 18 and comparative example 1, respectively, and the results are shown in table 10 below.
Table 10:
from the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the curable composition is a solvent-free composition, has lower environmental cost or production cost when being used for coating construction, has no expansion phenomenon after curing, has strong adhesive force, can be applied again without polishing or sanding, has better curability, boiling resistance, acid/alkali/salt resistance and gasoline resistance of recoated cured products, can avoid surface marks of a cured film caused in the construction polishing process, has lower environmental cost or production cost, is beneficial to improving the fullness and the attractiveness of the cured pattern film on the surface of a material, is also beneficial to improving the construction efficiency and reducing the labor intensity of workers, and is suitable for popularization and application in the repair field or the thick coating field of the surface coating of the material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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