CN113136133A - Hybrid UV (ultraviolet) curing composition and preparation method and application thereof - Google Patents
Hybrid UV (ultraviolet) curing composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN113136133A CN113136133A CN202110498123.2A CN202110498123A CN113136133A CN 113136133 A CN113136133 A CN 113136133A CN 202110498123 A CN202110498123 A CN 202110498123A CN 113136133 A CN113136133 A CN 113136133A
- Authority
- CN
- China
- Prior art keywords
- hybrid
- curable composition
- epoxy resin
- composition according
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 25
- 150000003254 radicals Chemical class 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 229920001225 polyester resin Polymers 0.000 claims description 13
- 239000004645 polyester resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 9
- -1 hexafluorophosphate Chemical compound 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims 2
- 238000001723 curing Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000000016 photochemical curing Methods 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000012949 free radical photoinitiator Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- VALXVSHDOMUUIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical group OP(O)(O)=O.CC(=C)C(O)=O VALXVSHDOMUUIC-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical group C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a hybrid UV curing composition and a preparation method and application thereof. The invention discloses a hybrid UV cured material, which adopts a UV photocuring drying mode, almost has no VOC in the production process, and has the advantages of high solid content (100%), fast curing, low energy consumption, low investment, excellent coating performance and the like compared with the traditional baking type composition; compared with the traditional free radical light-curing type, the material has the advantages of small shrinkage, good adhesion, no oxygen inhibition, no small molecule migration and the like.
Description
Technical Field
The invention belongs to the technology of resin compositions, and particularly relates to a hybrid UV curing composition, and a preparation method and application thereof.
Background
The ultraviolet light curing (UV curing) composition is used after mixing the main resin and the light curing agent, so that the uniformity of mixing directly affects the quality of the product. The prior art discloses a UV curing composition and a glue film containing the composition, wherein the UV curing composition is a UV curing composition catalyzed by photobase, and comprises (1) acrylic polymers and/or ethylene vinyl acetate copolymers; (2) a curable composition comprising a multifunctional thiol and a multifunctional epoxy resin; (3) a photobase generator; the composition can be coated into an adhesive tape or an adhesive film, the adhesive tape or the adhesive film has initial viscosity when not subjected to UV curing, and can reach the strength of semi-structural adhesive or structural adhesive after UV curing. Although the traditional free radical photo-curing composition overcomes the defects of high volatilization of baking organic solvents, high energy consumption, high noise, large occupied area and the like, the defects of large influence of oxygen inhibition, high shrinkage rate, large smell, high mobility and the like cannot be overcome.
Disclosure of Invention
The invention discloses a hybrid UV cured material, which adopts a UV photocuring drying mode, almost has no VOC in the production process, and has the advantages of high solid content (100%), fast curing, low energy consumption, low investment, excellent coating performance and the like compared with the traditional baking type composition; compared with the traditional free radical light-curing type, the material has the advantages of small shrinkage, good adhesion, no oxygen inhibition, no small molecule migration and the like.
The invention adopts the following technical scheme:
a hybrid UV-curable composition comprises epoxy resin, polyester acrylate, a reactive monomer, polyester resin, a cationic initiator and a free radical initiator; preferably, the hybrid UV curing composition consists of epoxy resin, polyester acrylate, a reactive monomer, polyester resin, a cationic initiator and a free radical initiator; more preferably, the sum of the weight of the epoxy resin, the polyester acrylate, the active monomer and the polyester resin is 100%, wherein the epoxy resin accounts for 55-65%, the polyester acrylate accounts for 15-25%, the active monomer accounts for 5-15%, and the balance is the polyester resin; 1.5-4% of cationic initiator and 0.5-2% of free radical initiator.
In the present invention, the epoxy resin is an alicyclic epoxy resin, and more preferably an alicyclic epoxy resin in which an epoxy group is directly grafted to a six-membered ring structure, and the cured composition used in the present invention has excellent transparency, low viscosity, low shrinkage and high hardness.
In the invention, the active monomer is a monofunctional monomer or a bifunctional monomer, further, the carbon number of the carbon-carbon main chain of the active monomer is more than or equal to 6, for example, an acrylic monomer is used together with polyester acrylate, so that the UV curing composition has excellent flexibility and adhesiveness, and the UV curing composition is endowed with excellent adhesive force and toughness.
In the present invention, the polyester resin is a carboxyl group-containing polyester resin, and is used together with a polyester acrylate to impart better adhesion and water resistance to the UV curable composition.
In the invention, the cationic initiator is sulfur-containing hexafluorophosphate; the radical initiator is an acylphosphine oxide, preferably an acylphosphine oxide having 3 or more oxygen atoms. The selection of the initiator gives the UV composition excellent curing rate and low migration.
According to the invention, epoxy resin and linear polyester acrylate are used as main resin for the first time, active monomer and a small amount of polyester are added to obtain the hybrid UV curing composition, which is a hybrid network interpenetrating technical principle, namely, after a cationic photoinitiator and a free radical photoinitiator are irradiated by light, strong protonic acid and free radical are generated, the strong protonic acid initiates epoxy group fracture-polymerization curing, and the free radical initiates double bond fracture polymerization curing to form a network interpenetrating structure. The coating is coated on the surface of the metal decorating plate, and has good adhesive force, T bending performance, excellent mechanical performance and chemical resistance.
The invention discloses a preparation method of the hybrid UV curing composition, which comprises the steps of firstly stirring and mixing epoxy resin, active monomer, cationic initiator and free radical initiator, then adding polyester acrylate and polyester resin, and stirring and mixing again to obtain the hybrid UV curing composition.
In the technical scheme, the rotation speed of the first stirring is 400-800 rpm, and the time is 20-50 min; the rotating speed of the secondary stirring is 1000-1500 rpm, and the time is 20-50 min.
According to the invention, the initiator is selected and matched with the resin, so that the micromolecule mobility of the UV curing composition is adjusted, and the food safety of deep-processed products is improved; the carboxyl-containing linear polyester prepolymer is selected to adjust the toughness and the adhesiveness of the UV curing composition with epoxy resin, so that the adhesion and the impact resistance of a UV curing composition coating are improved; the curing shrinkage and mechanical property of the UV curing composition are reduced by adjusting the proportion of the added alicyclic epoxy resin and matching with polyester and polyester acrylate; the curing speed and the application performance of the UV curing composition are improved by the matching of the reactive monomer and the resin.
Detailed Description
The raw materials of the invention are the existing products, and the specific operation method and the test method are the prior art.
A1. Alicyclic epoxy resin: 3,4-Epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate (3,4-Epoxycyclohexylmethyl 3, 4-epoxycyclohexylamine Carboxylate, TTA21P, Jiangsutatel New materials science and technology Co., Ltd.);
A2. polyester acrylate oligomer: aliphatic polyester Acrylate (Aliphatic Urethane Acrylate, DR-E524, Changxing materials industries, Ltd.);
B1. acrylic acid monomer: cyclic Trimethylolpropane Formal Acrylate (Cyclic trimethyolpropane Formal Acrylate, EM212, changxing materials industries, ltd.);
B2. acrylic acid monomer: pentaerythritol Triacrylate (Pentaerythritol triacylate, lucire 865, luo chemicals, inc., guangzhou);
C1. cationic polymerization initiator: 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate & Bis (4- (diphenylsulfonium) phenyl) sulfide-Bis hexafluorophosphate (Diphenyl [4- (phenylthio) phenyl ] sulfonium hexafluorophosphate & Bis (4- (diphenylthio) phenyl) sulfate Bis (hexafluoro phosphate), TTA UV-692, gotu kol new materials co.);
C2. free radical photoinitiator: bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (819, King titanium (Shanghai) chemical science and technology, Inc.);
D. auxiliary resin: polyester Resin (Polyester Resin, LTH, winning specialty Chemicals (Shanghai) Co., Ltd.).
Examples
The formulations of examples 1 to 9 are shown in table 1, while comparative examples 1 to 7 are set.
Table 1 examples and comparative formulations, g
Remarking: in comparative example 3, resin D was replaced with methacrylic acid phosphate (Unicryl R9107, yoto chemical materials ltd, guangzhou); in comparative example 4, initiator C1 was replaced with 4-isobutylphenyl-4' -methylphenyliodilium hexafluorophosphate (VL-3025, Nanjing Waals chemical technology Co., Ltd.); in comparative example 5, initiator C2 was replaced with 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO, hunbei solidly technologies ltd.); in comparative example 6, resin A2 was replaced with an aliphatic urethane acrylate (DR-U299, Changxing materials industries, Ltd.); in comparative example 7, resin A1 was replaced with 3, 4-epoxycyclohexylmethylmethacrylate (TTA15, Jiangsuttler New materials science and technology Co., Ltd.).
The preparation method of the embodiment and the comparative example comprises the steps of adding the epoxy resin A1 into a white rust steel stirring barrel, adding the active monomer B1, the initiator C1 and the initiator C2 under the stirring of 600rpm, and then stirring for 30min at 800 rpm; then, resin D and polyester acrylate oligomer A2 were added, followed by stirring at 1200rpm for 30min to obtain a hybrid type UV curable composition.
If the formulation contains reactive monomer B2, it is added with reactive monomer B1; if a component is omitted from the formulation, that component is not added.
The above composition was applied to a tin plate (tin plate with tin plated on both sides, cold rolled low carbon steel sheet) with a thickness of 20 μm and a light intensity of 100mW/cm in the same light source (UV mercury lamp)2) The cured layer was obtained by exposure to light at the same irradiation height (150mm) for the same time (20 seconds).
The examples and comparative examples were tested:
and (3) wear resistance test: in order to compare the abrasion resistance of the hybrid UV curing composition, a paint film abrasion tester (model: JM-V, Shanghai modern environmental engineering service Co., Ltd.) was used. The abrasion resistance of the coating is tested according to ISO 7784-2:1997 (rotating rubber grinding wheel method for determining abrasion resistance of paints and varnishes), the number of times of abrasion is more than or equal to 1000 times and the coating is evaluated as √; the number of rubbing was less than 1000 times but not less than 500 times and was evaluated as O without breakage; the number of abrasion was less than 500 times, and the breakage was evaluated as X.
And (3) testing the adhesive force: in order to compare the adhesion of the hybrid UV-curable composition to the substrate, the adhesion rating of the subbing layer (thickness: 20 μm) on the metal substrate was measured according to ISO2409-2013 paint and varnish cross-cut test, and an adhesion rating of 1 or less was rated as √; the adhesion rating of more than 1 grade but 3 or less was rated as O; an adhesion rating of greater than 3 was rated as x.
Migration resistance test: in order to compare the migration resistance of the hybrid UV curing composition, the migration condition of small molecules of the UV curing composition is measured according to a detection method of migration quantity of 7 photoinitiators in SN/T4317-; the amount of migration was larger than 0.5. mu.g/kg but 1. mu.g/kg or less was rated as O; a migration amount of more than 1. mu.g/kg was rated as X.
TABLE 2 examples, comparative examples and commercial UV coatings test results
The product of example 9 was tested by conventional methods for 1200 rubs without breakage, adhesion rating 0, and migration 0.38 μ g/kg. The UV curing composition disclosed by the invention is good in adhesive force, wear resistance and fluidity, and the alicyclic epoxy resin and the polyester acrylate are used as main body resins to endow the UV curing composition with better mechanical properties.
Claims (10)
1. A hybrid UV curing composition is characterized by comprising epoxy resin, polyester acrylate, a reactive monomer, polyester resin, a cationic initiator and a free radical initiator.
2. The hybrid UV-curable composition according to claim 1, wherein the hybrid UV-curable composition consists of epoxy resin, polyester acrylate, reactive monomer, polyester resin, cationic initiator, and radical initiator.
3. The hybrid UV-curable composition according to claim 1, wherein the epoxy resin is a cycloaliphatic epoxy resin; the reactive monomer is a monofunctional or difunctional monomer.
4. The hybrid UV-curable composition according to claim 3, wherein the epoxy resin is a cycloaliphatic epoxy resin in which epoxy groups are directly grafted to a six-membered ring structure; the carbon number of the carbon-carbon main chain of the active monomer is more than or equal to 6.
5. The hybrid UV-curable composition according to claim 1, wherein the polyester resin is a carboxyl group-containing polyester type resin.
6. The hybrid UV-curable composition according to claim 1, wherein the cationic initiator is a sulfur-containing hexafluorophosphate; the free radical initiator is an acylphosphine oxide.
7. The hybrid UV-curable composition according to claim 6, wherein the oxygen atom number of the acylphosphorus oxide is 3 or more.
8. The method for preparing the hybrid UV-curable composition according to claim 1, wherein the hybrid UV-curable composition is obtained by first stirring and mixing the epoxy resin, the reactive monomer, the cationic initiator and the radical initiator, adding the polyester acrylate and the polyester resin, and stirring and mixing again.
9. Use of the hybrid UV-curable composition according to claim 1 for the preparation of coatings.
10. Use according to claim 9, wherein the coating is a metallic surface coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110498123.2A CN113136133A (en) | 2021-05-08 | 2021-05-08 | Hybrid UV (ultraviolet) curing composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110498123.2A CN113136133A (en) | 2021-05-08 | 2021-05-08 | Hybrid UV (ultraviolet) curing composition and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113136133A true CN113136133A (en) | 2021-07-20 |
Family
ID=76816982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110498123.2A Pending CN113136133A (en) | 2021-05-08 | 2021-05-08 | Hybrid UV (ultraviolet) curing composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113136133A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709196A (en) * | 2009-11-27 | 2010-05-19 | 深圳职业技术学院 | Light mixing cured coating composition and preparation method thereof |
| CN106478899A (en) * | 2016-07-20 | 2017-03-08 | 杭州乐新材料科技有限公司 | A kind of modification light curing resin composition and preparation method thereof |
| CN108329657A (en) * | 2018-03-09 | 2018-07-27 | 北京瑞达科博技术有限公司 | Free radical-Cationic Hybrid curing glass fiber reinforcement plastic feed composition |
| CN111205733A (en) * | 2020-02-28 | 2020-05-29 | 上海超彩油墨有限公司 | Cationic/free radical dual-curing UV gloss oil for tin printing ink and preparation method thereof |
| CN111234662A (en) * | 2020-03-20 | 2020-06-05 | 宁波野山羊新材料科技有限公司 | Photocurable composition, photocured product and preparation method of substrate coating |
| US20200347180A1 (en) * | 2018-01-24 | 2020-11-05 | Daicel Corporation | Resin composition for forming hard coating layer |
-
2021
- 2021-05-08 CN CN202110498123.2A patent/CN113136133A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709196A (en) * | 2009-11-27 | 2010-05-19 | 深圳职业技术学院 | Light mixing cured coating composition and preparation method thereof |
| CN106478899A (en) * | 2016-07-20 | 2017-03-08 | 杭州乐新材料科技有限公司 | A kind of modification light curing resin composition and preparation method thereof |
| US20200347180A1 (en) * | 2018-01-24 | 2020-11-05 | Daicel Corporation | Resin composition for forming hard coating layer |
| CN108329657A (en) * | 2018-03-09 | 2018-07-27 | 北京瑞达科博技术有限公司 | Free radical-Cationic Hybrid curing glass fiber reinforcement plastic feed composition |
| CN111205733A (en) * | 2020-02-28 | 2020-05-29 | 上海超彩油墨有限公司 | Cationic/free radical dual-curing UV gloss oil for tin printing ink and preparation method thereof |
| CN111234662A (en) * | 2020-03-20 | 2020-06-05 | 宁波野山羊新材料科技有限公司 | Photocurable composition, photocured product and preparation method of substrate coating |
Non-Patent Citations (2)
| Title |
|---|
| 凌云星等: "《油墨技术手册（上）》", 31 May 2009, 印刷工业出版社 * |
| 张国瑞: "《印刷应用UV固化技术问答》", 31 December 2001, 印刷工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102850899B (en) | A kind of photocuring alkali-resisting paint | |
| KR20140080929A (en) | Composition for coating of graphene, manufacturing method thereof and graphene coated steel sheet | |
| WO2019223026A1 (en) | Coil coating based on eb-curing | |
| US8642673B2 (en) | Radiation-curable formulations | |
| CN113861808B (en) | Roller-coated UV white primer with excellent UV ink wettability and preparation method thereof | |
| CN111471375A (en) | Anti-scratch photocuring odorless matte white finish | |
| CN105567063A (en) | Ultraviolet curable coating for low energy curing and preparation method of ultraviolet curable coating | |
| CN111253837B (en) | Water-based one-coating UV (ultraviolet) curing epoxy acrylate coating and preparation method thereof | |
| CN115353803A (en) | Preparation method of non-thickening water-based UV (ultraviolet) curing coating | |
| CN113234376B (en) | Solvent-free UV tin printing coating and preparation method and application thereof | |
| CN113136133A (en) | Hybrid UV (ultraviolet) curing composition and preparation method and application thereof | |
| JP2011256378A (en) | Active energy ray-curable coating composition for pre-coated metal and method for manufacturing pre-coated metal using the composition | |
| CN114874694B (en) | Anti-oxidation polymerization-inhibition UVLED paint | |
| CN1261471C (en) | Radiation curable hot melt composition and process for application thereof | |
| KR20070104458A (en) | Radiation curable putty compositions and methods for refinishing a substrate using such compositions | |
| JPS6152169B2 (en) | ||
| JPH11302562A (en) | Photocurable coating composition | |
| CN113755077A (en) | Hydrophobic anti-fouling ultraviolet curing coating and preparation method thereof | |
| CN111004567A (en) | UV (ultraviolet) glazing oil and preparation method thereof | |
| CN110016144A (en) | A kind of water solubility polyfunctional group resin and preparation method thereof | |
| CN110903741A (en) | Ultraviolet curing coating | |
| CN115558402B (en) | UV (ultraviolet) photocuring coating for tin printing and preparation process thereof | |
| EP4050038A1 (en) | Preparation process for solid acrylic resin suitable for uv photocuring system | |
| JP2008063434A (en) | Visible ray-curable coating for woodworking coating use and coating method | |
| JP3358445B2 (en) | Curable liquid resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |