CN116218268A - UV (ultraviolet) curing PP (Polypropylene) primer - Google Patents
UV (ultraviolet) curing PP (Polypropylene) primer Download PDFInfo
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- CN116218268A CN116218268A CN202310173757.XA CN202310173757A CN116218268A CN 116218268 A CN116218268 A CN 116218268A CN 202310173757 A CN202310173757 A CN 202310173757A CN 116218268 A CN116218268 A CN 116218268A
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- iboa
- primer
- aibn
- acrylic resin
- mass
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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
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—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 C09D159/00 - C09D187/00
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to the technical field of coatings, in particular to a UV (ultraviolet) curing PP (polypropylene) primer. The adhesion of the printing ink on the surface of the PP substrate is difficult to be poor. Aiming at the problems, the invention provides the UV curing PP primer, modified acrylic resin is added in the formula of the primer, IBOA is adopted as an A chain segment, acrylic acid is adopted as a B chain segment, the structure of the chain segment is strictly controlled through active controllable polymerization, the modified acrylic resin similar to the AAAAAAABBBAAAAAAA molecular structure is obtained, meanwhile, the molecular weight distribution range of the obtained modified acrylic resin is narrower, the structure is more regular, and the adhesive force between a paint film and a PP substrate is improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a UV (ultraviolet) curing PP (polypropylene) primer.
Background
Polypropylene (PP) is a semi-crystalline thermoplastic. Has high impact resistance, strong mechanical property and resistance to corrosion of various organic solvents and acid and alkali. Many are used in cosmetic packaging bottles for their excellent performance advantages and cheaper prices.
However, polypropylene (PP) plastics have low surface energy, low polarity, poor wettability and certain crystallinity, and are not easy to directly adhere to materials such as paints containing polar functional groups or polar components. The PP molecules are nonpolar, the adhesion between the inside of the plastic and the external objects belongs to the worst, the polarity treatment of the lower surface is needed before printing, a layer of PP treatment water is sprayed on the surface of PP materials, and then printing ink is printed on the PP treatment water, so that the adhesion of the coating is very stable, but the cost waste and the energy consumption caused by spraying the PP treatment water and the emission of a large amount of VOC (volatile organic compounds) are caused, the environmental pollution is caused, and the solvents generally contained in the PP treatment water are toluene and dimethylbenzene, so that the human body is greatly damaged.
In view of the above problems, chinese patent No. 108690449a discloses a PVD primer for ultraviolet photo-curing PP treatment-free water and a method for preparing the same, which mainly uses full-chain acrylic modified polybutadiene resin as an adhesion resin, and provides adhesion of a coating, however, the method is not high enough for PVD, and if a PP substrate with high crystallinity is encountered, the method is limited because the regularity of the formed coating is not high enough, and according to similar compatibility, the more regular the structure of the coating is similar to the PP substrate, the better the permeability is, and the better the adhesion to the PP substrate is, and the solution still needs a solvent for dissolution assistance, although toluene and xylene are not used, and the method is still not environment-friendly.
For this, this patent has designed a UV solidification PP primer, add modified acrylic resin in its formula, modified acrylic resin adopts IBOA as the A chain segment, acrylic acid is the B chain segment, but the structure of the strictly controlled chain segment through the controllable polymerization of activity is AAAAABBBAAAAAAA's structure, the molecular weight is 40000 alkene acid ester that distributes narrowly, the formation of structure can't be controlled to common polymerization method, molecular weight distribution is wide simultaneously, thereby can't reach regular effect, the reason of preferential IBOA is that it has certain erosion effect to PP itself, after the macromolecular ization, form regular structure, isobornyl ester cyclic structure can firmly lie prone to the PP substrate as the side chain, the introduction of B fragment can improve the compatibility of acrylic ester.
Disclosure of Invention
The problems in the prior art are: the adhesion of the printing ink on the surface of the PP substrate is difficult to be poor. Aiming at the problems, the invention provides a UV curing PP primer, which comprises the following components in parts by weight:
specifically, the preparation method of the modified acrylic resin comprises the following steps:
(1) Adding IBOA, initiator AIBN and chain transfer agent DDMAT into a 1, 4-dioxygen solvent, wherein the volume of the 1, 4-dioxygen hexacyclic solvent is 3 times that of the IBOA, the addition amount of the initiator AIBN is 1% of the mass of the IBOA, the addition amount of the chain transfer agent DDMAT is 0.8% of the mass of the IBOA, and stirring and reacting for 6 hours at 70 ℃ under nitrogen protection to obtain a reaction liquid I;
(2) After the temperature of the reaction liquid I in the step (1) is reduced to room temperature, starting to add MA and AIBN, wherein the molar ratio of MA to IBOA in the step (1) is 1:3, the adding amount of AIBN is 0.8% of the mass of MA, and the reaction liquid II is obtained by nitrogen protection and stirring reaction for 6 hours at 70 ℃;
(3) After the temperature of the reaction solution II in the step (2) is reduced to room temperature, adding IBOA and AIBN, wherein the molar ratio of the IBOA to the IBOA in the step (1) is 1:1, the addition amount of AIBN is 1 percent of the mass of IBOA in the step (1), nitrogen is used for protection, the mixture is stirred and reacts for 6 hours at 70 ℃, and the solvent is removed by rotary evaporation, so that the modified acrylic resin is obtained.
Specifically, the acrylic monomer includes at least one of HDDA, THFA, CTFA, TMPTA, PETA, DPHA.
Specifically, the photoinitiator is a free radical photoinitiator.
Specifically, the photoinitiator specifically comprises at least one of TPO, 819, 1173, 184, ITX, 907.
Specifically, the fumed silica is cabot LM150.
Advantageous effects
(1) According to the UV curing PP primer disclosed by the invention, the modified acrylic resin is added, IBOA is adopted as an A chain segment, acrylic acid is adopted as a B chain segment, the structure of the chain segment is strictly controlled through active controllable polymerization, so that the modified acrylic resin similar to the AAAAAAABBBAAAAAAA molecular structure is obtained, meanwhile, the weight average molecular weight of the obtained modified acrylic resin is 40000, the molecular weight distribution range is smaller, the polydispersity index PDI is 0.98, the structure is more regular, and the adhesive force between a paint film and a PP substrate is improved;
(2) The modified acrylic resin is preferably selected from IBOA as the A chain segment, because the IBOA has a certain erosion swelling effect on PP, can accelerate the infiltration of the primer on the PP substrate, forms a regular structure after macromolecular formation, enables the side chain of the isobornyl ester ring structure to firmly lie on the PP substrate, and is very beneficial to further improving the adhesive force between a paint film and the PP substrate due to the compatibility of the B segment with acrylic monomers in a primer material system.
Detailed Description
The modified acrylic resins in the following examples of the present invention were prepared as follows:
(1) Adding IBOA, initiator AIBN and chain transfer agent DDMAT into a 1, 4-dioxygen solvent, wherein the volume of the 1, 4-dioxygen hexacyclic solvent is 3 times that of the IBOA, the addition amount of the initiator AIBN is 1% of the mass of the IBOA, the addition amount of the chain transfer agent DDMAT is 0.8% of the mass of the IBOA, and stirring and reacting for 6 hours at 70 ℃ under nitrogen protection to obtain a reaction liquid I;
(2) After the temperature of the reaction liquid I in the step (1) is reduced to room temperature, starting to add MA and AIBN, wherein the molar ratio of MA to IBOA in the step (1) is 1:3, the adding amount of AIBN is 0.8% of the mass of MA, and the reaction liquid II is obtained by nitrogen protection and stirring reaction for 6 hours at 70 ℃;
(3) After the temperature of the reaction solution II in the step (2) is reduced to room temperature, adding IBOA and AIBN, wherein the molar ratio of the IBOA to the IBOA in the step (1) is 1:1, the addition amount of AIBN is 1 percent of the mass of IBOA in the step (1), nitrogen is used for protection, the mixture is stirred and reacts for 6 hours at 70 ℃, and the solvent is removed by rotary evaporation, so that the modified acrylic resin is obtained.
The fumed silica used in the following examples of the present invention is cabot LM150.
Example 1
The UV curing PP primer comprises the following components in parts by weight:
example 2
The UV curing PP primer comprises the following components in parts by weight:
example 3
The UV curing PP primer comprises the following components in parts by weight:
example 4
The UV curing PP primer comprises the following components in parts by weight:
example 5
The UV curing PP primer comprises the following components in parts by weight:
comparative example 1 the same as example 1 except that the modified acrylic resin (random copolymerization structure) in comparative example 1 was prepared according to the following procedure:
(1) Adding IBOA, MA, an initiator AIBN and a chain transfer agent DDMAT into a 1, 4-dioxygen solvent, wherein the volume of the 1, 4-dioxygen hexacyclic solvent is 3 times that of the IBOA, the adding amount of the initiator AIBN is 1% of the mass of the IBOA, the adding amount of the chain transfer agent DDMAT is 0.8% of the mass of the IBOA, the molar ratio of the IBOA to the MA is 1:1, stirring and reacting for 6 hours at 70 ℃ under nitrogen protection to obtain a reaction liquid I, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
Comparative example 2 the same as example 1, except that the modified acrylic resin (containing no B segment) in comparative example 2 was prepared as follows:
adding IBOA, initiator AIBN and chain transfer agent DDMAT into a 1, 4-dioxygen solvent, wherein the volume of the 1, 4-dioxygen hexacyclic solvent is 3 times that of IBOA, the addition amount of the initiator AIBN is 1% of the mass of IBOA, the addition amount of the chain transfer agent DDMAT is 0.8% of the mass of IBOA, and stirring and reacting for 6 hours at 70 ℃ under nitrogen protection to obtain a reaction solution I, and removing the solvent by rotary evaporation to obtain the modified acrylic resin.
Comparative example 3 the same as example 1 was conducted except that comparative example 3 uses a common commercially available epoxy acrylic resin as a substitute for the modified acrylic resin in example 1 at 620-100 a.
Comparative example 4 the same as example 1 was different in that a was replaced with other monomer C having a cyclic structure in the preparation of the modified acrylic resin of comparative example 4, and the specific preparation process was as follows:
(1) Adding DCPA, initiator AIBN and chain transfer agent DDMAT into a 1, 4-dioxygen solvent, wherein the volume of the 1, 4-dioxygen hexacyclic solvent is 3 times that of the DCPA, the adding amount of the initiator AIBN is 1% of the mass of the DCPA, the adding amount of the chain transfer agent DDMAT is 0.8% of the mass of the DCPA, and stirring and reacting for 6 hours at 70 ℃ under nitrogen protection to obtain a reaction liquid I;
(2) After the temperature of the reaction liquid I in the step (1) is reduced to room temperature, starting to add MA and AIBN, wherein the molar ratio of MA to DCPA in the step (1) is 1:3, the adding amount of AIBN is 0.8% of the mass of MA, and stirring and reacting for 6 hours at 70 ℃ under the protection of nitrogen to obtain a reaction liquid II;
(3) After the temperature of the reaction solution II in the step (2) is reduced to room temperature, starting to add DCPA and AIBN, wherein the molar ratio of DCPA to DCPA in the step (1) is 1:1, the addition amount of AIBN is 1 percent of the mass of DCPA in the step (1), nitrogen is protected, the mixture is stirred and reacts for 6 hours at 70 ℃, and the solvent is removed by rotary evaporation, so that the modified acrylic resin is obtained.
Performance testing
According to the formula amount, the raw materials of the examples 1-5 and the comparative examples 1-3 are respectively and uniformly stirred and mixed to obtain the UV curing PP primer, the UV curing PP primers obtained in the examples 1-5 and the comparative examples 1-3 are respectively coated on the surface of a PP substrate, and are subjected to photo-curing under an ultraviolet lamp to obtain a paint film, wherein the thickness of the paint film is 20 mu m, and then the paint film is subjected to related performance test, and the test results are shown in the table 1.
Adhesion force: the test was carried out in accordance with GB/T9286-1998.
Boiling in water: boiling in water at 100deg.C for 2 hr, without foaming and whitening.
Violence test: the paint film is buckled by nails to see whether the paint film is buckled.
TABLE 1
| Test item | Adhesion force | Water boiling | Violence test |
| Example 1 | 0 | By passing through | By passing through |
| Example 2 | 0 | By passing through | By passing through |
| Example 3 | 0 | By passing through | By passing through |
| Example 4 | 0 | By passing through | By passing through |
| Example 5 | 0 | By passing through | By passing through |
| Comparative example 1 | 0 | Not pass through | Easy-to-buckle movement |
| Comparative example 2 | ---- | ---- | ---- |
| Comparative example 3 | 2 | Not pass through | Movement of the clasp |
| Comparative example 4 | 2 | Not pass through | Movement of the clasp |
The modified acrylic resin obtained in comparative example 2 in Table 1 was not compatible with the acrylic monomer because it did not contain the B segment, and could not form a coating system.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. The UV curing PP primer is characterized by comprising the following components in parts by weight:
2. the UV-cured PP primer of claim 1 wherein the modified acrylic resin is prepared by:
(1) Adding IBOA, initiator AIBN and chain transfer agent DDMAT into a 1, 4-dioxygen solvent, wherein the volume of the 1, 4-dioxygen hexacyclic solvent is 3 times that of the IBOA, the addition amount of the initiator AIBN is 1% of the mass of the IBOA, the addition amount of the chain transfer agent DDMAT is 0.8% of the mass of the IBOA, and stirring and reacting for 6 hours at 70 ℃ under nitrogen protection to obtain a reaction liquid I;
(2) After the temperature of the reaction liquid I in the step (1) is reduced to room temperature, starting to add MA and AIBN, wherein the molar ratio of MA to IBOA in the step (1) is 1:3, the adding amount of AIBN is 0.8% of the mass of MA, and the reaction liquid II is obtained by nitrogen protection and stirring reaction for 6 hours at 70 ℃;
(3) After the temperature of the reaction solution II in the step (2) is reduced to room temperature, adding IBOA and AIBN, wherein the molar ratio of the IBOA to the IBOA in the step (1) is 1:1, the addition amount of AIBN is 1 percent of the mass of IBOA in the step (1), nitrogen is used for protection, the mixture is stirred and reacts for 6 hours at 70 ℃, and the solvent is removed by rotary evaporation, so that the modified acrylic resin is obtained.
3. The UV-cured PP primer of claim 1 wherein the acrylic monomer comprises at least one of HDDA, THFA, CTFA, TMPTA, PETA, DPHA.
4. The UV-cured PP primer of claim 1 wherein the photoinitiator is a free radical photoinitiator.
5. The UV-cured PP primer of claim 4 wherein said photoinitiator comprises at least one of TPO, 819, 1173, 184, ITX, 907.
6. The UV-cured PP primer of claim 1 wherein the fumed silica is cabot LM150.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310173757.XA CN116218268A (en) | 2023-02-28 | 2023-02-28 | UV (ultraviolet) curing PP (Polypropylene) primer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310173757.XA CN116218268A (en) | 2023-02-28 | 2023-02-28 | UV (ultraviolet) curing PP (Polypropylene) primer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116218268A true CN116218268A (en) | 2023-06-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310173757.XA Pending CN116218268A (en) | 2023-02-28 | 2023-02-28 | UV (ultraviolet) curing PP (Polypropylene) primer |
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| CN (1) | CN116218268A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602917A (en) * | 2009-07-10 | 2009-12-16 | 中国乐凯胶片集团公司 | A kind of ultraviolet-curing paint |
| WO2018016407A1 (en) * | 2016-07-21 | 2018-01-25 | 大塚化学株式会社 | Block copolymer, composition, and film |
-
2023
- 2023-02-28 CN CN202310173757.XA patent/CN116218268A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602917A (en) * | 2009-07-10 | 2009-12-16 | 中国乐凯胶片集团公司 | A kind of ultraviolet-curing paint |
| WO2018016407A1 (en) * | 2016-07-21 | 2018-01-25 | 大塚化学株式会社 | Block copolymer, composition, and film |
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