CN111117495A - Bio-based material radiation curing composition and application thereof - Google Patents
Bio-based material radiation curing composition and application thereof Download PDFInfo
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- CN111117495A CN111117495A CN201911350295.4A CN201911350295A CN111117495A CN 111117495 A CN111117495 A CN 111117495A CN 201911350295 A CN201911350295 A CN 201911350295A CN 111117495 A CN111117495 A CN 111117495A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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Abstract
The invention discloses a radiation curing composition of a bio-based material and application thereof, wherein the composition is mainly prepared from the following components in parts by weight: 25-50 parts of bio-based polyether amine type benzoxazine resin, 5-15 parts of bio-based hydrogenated coumarin toughened epoxy resin, 5-20 parts of polyacrylate, 8-15 parts of methyl etherified melamine formaldehyde resin, 20-30 parts of pentaerythritol triacrylate, 1-3 parts of a polyurethane dispersant, 3.5-6.5 parts of a photoinitiator and 1-3 parts of propoxylated neopentyl glycol diacrylate. The bio-based radiation curing material provided by the invention adopts a natural base material, is natural and environment-friendly, and has good adhesive force, flexibility, weather resistance, impact resistance, external force scratch resistance, bending resistance and flexibility.
Description
Technical Field
The invention belongs to the field of curing materials, and particularly relates to a radiation curing composition of a bio-based material.
Background
The bio-based polymer is a polymer synthesized by taking bio-renewable resources as raw materials through biological or chemical processes. Plastics, rubbers, fibers, adhesives, and paints obtained by using a bio-based polymer as a matrix resin are collectively referred to as bio-based polymer materials. The bio-based polymer material avoids the dependence of petrochemical resources, has the advantages of low carbon and environmental protection, and has the potential of replacing petrochemical polymer materials, but the use amount of the bio-based polymer material is less than 1% of that of the polymer material at present. Therefore, bio-based polymer materials will be one of the important directions for future development of polymer field.
Radiation curing technology has entered the print publishing industry on a large scale late, approximately 90 s in the last century. Radiation curing covers almost all printing processes including dry offset printing, wet lithographic printing, screen printing, flexographic printing, letterpress printing, gravure printing and the like. Besides paper, printed materials also comprise plastics, metals, paint films and the like.
In fact, the application of radiation curing in the manufacturing industry of printed circuit boards, large-scale integrated circuits, digital cameras, compact disks (CD-ROMs, DVDs), mobile phones, liquid crystal displays, plasma displays, and the like is an irreplaceable technology that can perform various tasks such as coating, printing, painting, and adhesion in the manufacturing process of products. Radiation curing is breaking through the automobile and building materials industries. It is not surprising that radiation curing has entered the everyday lives of millions of households and the general public, although not everyone is directly aware of this.
Disclosure of Invention
The invention aims to provide a bio-based radiation curing material based on the prior art, which has higher adhesion, high temperature resistance, scratch resistance, chemical resistance and weather resistance, and can meet the requirement of environmental protection to the greatest extent due to the adoption of a natural substrate.
It is another object of the present invention to provide a use of a natural based radiation curable material in a film coating adhesive.
The object of the invention can be achieved by the following measures:
a radiation curing composition of bio-based materials is mainly prepared from the following components in parts by weight: 25-50 parts of bio-based polyether amine type benzoxazine resin, 5-15 parts of bio-based hydrogenated coumarin toughened epoxy resin, 5-20 parts of polyacrylate, 8-15 parts of methyl etherified melamine formaldehyde resin, 20-30 parts of pentaerythritol triacrylate, 1-3 parts of a polyurethane dispersant, 3.5-6.5 parts of a photoinitiator and 1-3 parts of propoxylated neopentyl glycol diacrylate.
The preferable weight part of the bio-based polyether amine type benzoxazine resin in the invention is 30-40 parts.
The preferable weight part of the bio-based hydrogenated coumarin toughened epoxy resin is 7-12 parts.
The preferable weight part of the polyacrylate in the invention is 8-15 parts.
The preferred weight part of the methylated melamine formaldehyde resin in the invention is 9-12 parts.
The preferable weight part of the pentaerythritol triacrylate in the invention is 22-25 parts.
The polyurethane dispersant in the present invention is preferably BYK 163.
The photoinitiator is oxime ester photoinitiator, preferably one or more of carbazole ketoxime lipid photoinitiator, coumarin oxime ester photoinitiator, thiophene ring dioxime photoinitiator or oxyacyl oxime ester photoinitiator.
The preparation method of the radiation curing composition of the bio-based material comprises the step of uniformly stirring all the components at the temperature of 30-40 ℃.
The invention mainly adopts the interaction of four components of bio-based polyether amine type benzoxazine resin, bio-based hydrogenated coumarin toughened epoxy resin, polyacrylate and methylated melamine formaldehyde resin to play a better role in curing and cementing. The bio-based polyether amine type benzoxazine resin is prepared by taking biomass raw materials, namely methyl diphenolate and bisphenol A, as phenol sources and polyether amine as an amine source and performing Mannich reaction with paraformaldehyde, and has better thermal stability and mechanical property (the specific preparation method can refer to the preparation and performance research of bio-based polyether amine type benzoxazine resin of Zhang, et al (J. Nanjing university Proc., Nature science, 2019,55(05):832 (839)). The bio-based hydrogenated coumarin toughened epoxy resin is prepared by alternately copolymerizing a bio-based raw material hydrogenated coumarin (DHC) and epoxy ether substances under the concerted catalysis of a chromium (III) complex and an ammonium chloride complex to obtain a three-dimensional network polymer; and then the epoxy resin (EP) monomer and the epoxy resin (EP) monomer construct a double-network structure in the curing process, and the epoxy resin toughening and reinforcing effect is achieved (the specific preparation method can refer to the preparation and the performance of the bio-based hydrogenated coumarin toughened epoxy resin of Kotao et al, chemical reports of higher schools, 2019,40(05): 1043-. Experiments show that the four components have good hardness, flexibility and adhesive force after being radiated through reasonable proportion and mutual synergistic effect of the four components; under the coordination of other conditions, the colloid has good adhesive force, cohesive force, high temperature resistance, wear resistance, weather resistance, external force scratch resistance, impact resistance, bending resistance and flexibility, and is particularly suitable for the surface of a metal substrate.
The bio-based material radiation curing composition of the present invention is applicable in film coating adhesives, especially in UV radiation curing.
The bio-based radiation curing material has no or less solvent, low VOC volatile matter and no pollution to the ambient air, the components of the adhesive are less limited or forbidden in environmental regulations, and meanwhile, the adhesive has low flammability and is environment-friendly and safe because of no solvent; the curing is fast, the reaction is controllable, the energy is saved, the efficiency is high, and the method is suitable for automatic operation; high gloss, high hardness, excellent weather resistance and no yellowing; the optical performance is excellent, and the glue solution is colorless and transparent and has no whitening; the product has good platability, good release property, scratch resistance, stretching, wide bonding material, high bonding strength, structural bonding and wide application range.
The bio-based radiation curing material provided by the invention adopts a natural base material, is natural and environment-friendly, has good adhesive force, flexibility, weather resistance, impact resistance, external force scratch resistance, bending resistance and flexibility, does not crack when being bent to a certain degree, has smooth hand feeling, and is particularly suitable for the surface of a metal base material.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1:
a radiation curing composition of bio-based materials is prepared from the following components in parts by weight: 30 parts of bio-based polyether amine type benzoxazine resin, 8 parts of bio-based hydrogenated coumarin toughened epoxy resin, 15 parts of polyacrylate, 12 parts of methyl etherified melamine formaldehyde resin, 22 parts of pentaerythritol triacrylate, 1.5 parts of BYK163 polyurethane dispersant, 3.5 parts of carbazole ketoxime lipid photoinitiator and 2.4 parts of propoxylated neopentyl glycol diacrylate. And (3) uniformly stirring the components at the temperature of 30-40 ℃.
Example 2:
a radiation curing composition of bio-based materials is prepared from the following components in parts by weight: 35 parts of bio-based polyether amine type benzoxazine resin, 12 parts of bio-based hydrogenated coumarin toughened epoxy resin, 13 parts of polyacrylate, 9 parts of methyl etherified melamine formaldehyde resin, 25 parts of pentaerythritol triacrylate, 1.5 parts of BYK163 polyurethane dispersant, 3.5 parts of carbazole ketoxime lipid photoinitiator and 1.9 parts of propoxylated neopentyl glycol diacrylate. And (3) uniformly stirring the components at the temperature of 30-40 ℃.
Example 3:
a radiation curing composition of bio-based materials is prepared from the following components in parts by weight: 40 parts of bio-based polyether amine type benzoxazine resin, 9 parts of bio-based hydrogenated coumarin toughened epoxy resin, 11 parts of polyacrylate, 10 parts of methyl-etherified melamine formaldehyde resin, 23 parts of pentaerythritol triacrylate, 1.5 parts of BYK163 polyurethane dispersant, 5.5 parts of carbazole ketoxime lipid photoinitiator and 1.7 parts of propoxylated neopentyl glycol diacrylate. And (3) uniformly stirring the components at the temperature of 30-40 ℃.
Example 4:
a radiation curing composition of bio-based materials is prepared from the following components in parts by weight: 35 parts of bio-based polyether amine type benzoxazine resin, 10 parts of bio-based hydrogenated coumarin toughened epoxy resin, 9 parts of polyacrylate, 9 parts of methyl-etherified melamine formaldehyde resin, 24 parts of pentaerythritol triacrylate, 2 parts of BYK163 polyurethane dispersant, 5.5 parts of carbazole ketoxime lipid photoinitiator and 1.5 parts of propoxylated neopentyl glycol diacrylate. And (3) uniformly stirring the components at the temperature of 30-40 ℃.
Comparative example 1:
in example 1, the bio-based polyether amine type benzoxazine resin was changed to 38 parts, and the bio-based hydrogenated coumarin toughened epoxy resin was removed, otherwise the same as in example 1.
Comparative example 2:
in example 2, 47 parts of bio-based hydrogenated coumarin toughened epoxy resin was changed, and the bio-based polyetheramine benzoxazine resin was removed, otherwise the same as in example 2.
Comparative example 3:
in example 3, the bio-based hydrogenated coumarin toughened epoxy resin was changed to 20 parts and the polyacrylate was removed, otherwise the same as in example 3.
Comparative example 4:
in example 4, the polyacrylate was changed to 18 parts and the methylated melamine formaldehyde resin was removed, otherwise the same as in example 4.
Example 5
The compositions prepared in examples 1 to 4 and comparative examples 1 to 4 were applied to the surface of a metal substrate, the film thickness was 100 μm, curing was performed for 18 seconds using a UV lamp, and the adhesive film was tested after curing, with the test results shown in table 1.
TABLE 1 relevant Performance test data
The test method and requirements are as follows:
adhesion force: and (3) marking the coating film on the substrate according to the national standard GB9286-88 to prepare a sample, wherein the marking number is 5 multiplied by 5, and the side length of each grid is 2 mm. After cutting, the film is brushed with a soft hairbrush in a reciprocating manner for 5 times along the direction of two diagonal lines of the lattice array, and the adhesion of the film to the base material is represented in a grading manner by observing the number of the remaining film grids on the surface of the base material, wherein the best grade is 0 grade, the worst grade is 5 grade, and the three grades of 0, 1 and 2 can meet the requirements of common purposes.
RCA wear resistance: abrasion resistance tester, load 175 g.
Cold and heat shock resistance: setting the high-low temperature test chamber to be placed at 60 +/-5 ℃ for 2 hours and at-25 +/-2 ℃ for 2 hours, wherein the cycle is a test after the cycle is performed; the ink coating surface of the glass does not fall off and crack, and the color of the glass is not obviously different from that of a standard sample; the specified glue, the adhesive tape and the foaming material part are stuck on the back of the coating, and the color change phenomenon can not occur when the glass is observed from the front side.
Boiling in water: decocting in water at 100 deg.C. The method comprises the following steps: the surface of the coating does not fall off or is incomplete.
Alkali resistance: soaking with 0.1M NaOH at 55 deg.C. The method comprises the following steps: the ink coating surface has no pinhole bubble, no expansion, no peeling, no shedding phenomenon and no color change phenomenon on the front surface.
Acid resistance: at 20 ℃ with H at a concentration of 0.05M2SO4And (5) soaking. The method comprises the following steps: the ink coating surface has no pinhole bubble, no expansion, no peeling, no shedding phenomenon and no color change phenomenon on the front surface.
Alcohol resistance: the test head was wrapped with cotton cloth, dipped in a qualified alcohol (concentration > 99.5%), and rubbed back and forth with 500g of pressure. The method comprises the following steps: the surface of the coating does not fall off.
Claims (9)
1. The radiation curing composition of the biobased material is characterized by being mainly prepared from the following components in parts by weight: 25-50 parts of bio-based polyether amine type benzoxazine resin, 5-15 parts of bio-based hydrogenated coumarin toughened epoxy resin, 5-20 parts of polyacrylate, 8-15 parts of methyl etherified melamine formaldehyde resin, 20-30 parts of pentaerythritol triacrylate, 1-3 parts of a polyurethane dispersant, 3.5-6.5 parts of a photoinitiator and 1-3 parts of propoxylated neopentyl glycol diacrylate.
2. The bio-based material radiation curable composition according to claim 1, wherein the bio-based polyetheramine type benzoxazine resin is 30 to 40 parts by weight.
3. The bio-based material radiation curing composition according to claim 1, wherein the bio-based hydrogenated coumarin toughened epoxy resin is present in an amount of 7 to 12 parts by weight.
4. The radiation curable biobased material composition according to claim 1, wherein the polyacrylate is present in an amount of 8 to 15 parts by weight.
5. The radiation curable biobased material composition according to claim 1, wherein the methylated melamine formaldehyde resin is present in an amount of 9 to 12 parts by weight.
6. The radiation curable biobased material composition according to claim 1, wherein the pentaerythritol triacrylate is present in an amount of 22 to 25 parts by weight.
7. The radiation curable biobased material composition of claim 1 wherein the polyurethane dispersant is BYK 163; the photoinitiator is oxime ester photoinitiator, preferably one or more of carbazole ketoxime lipid photoinitiator, coumarin oxime ester photoinitiator, thiophene ring dioxime photoinitiator or oxyacyl oxime ester photoinitiator.
8. The radiation curable biobased material composition according to claim 1, wherein the preparation method comprises the step of uniformly stirring the components at 30-40 ℃.
9. Use of the bio-based material radiation curable composition of claim 1 for film coating adhesives.
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| CN201911350295.4A CN111117495A (en) | 2019-12-24 | 2019-12-24 | Bio-based material radiation curing composition and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944121A (en) * | 2020-08-26 | 2020-11-17 | 山西生物质新材料产业研究院有限公司 | Hyperbranched polyether modified lignin epoxy resin and carbon fiber composite prepreg thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181611A (en) * | 2018-09-05 | 2019-01-11 | 滁州金桥德克新材料有限公司 | A kind of natural base radiation curing material and its application in film coating UV adhesive |
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2019
- 2019-12-24 CN CN201911350295.4A patent/CN111117495A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109181611A (en) * | 2018-09-05 | 2019-01-11 | 滁州金桥德克新材料有限公司 | A kind of natural base radiation curing material and its application in film coating UV adhesive |
Non-Patent Citations (2)
| Title |
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| 张勋等: "生物基聚醚胺型苯并噁嗪树脂的制备与性能研究", 《南京大学学报（自然科学版）》 * |
| 韩涛等: "生物基氢化香豆素增韧环氧树脂的制备及性能", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944121A (en) * | 2020-08-26 | 2020-11-17 | 山西生物质新材料产业研究院有限公司 | Hyperbranched polyether modified lignin epoxy resin and carbon fiber composite prepreg thereof |
| CN111944121B (en) * | 2020-08-26 | 2022-11-08 | 山西生物质新材料产业研究院有限公司 | Hyperbranched polyether modified lignin epoxy resin and carbon fiber composite prepreg thereof |
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