CN112011256A - UV thermosetting adhesive and preparation method thereof - Google Patents
UV thermosetting adhesive and preparation method thereof Download PDFInfo
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- CN112011256A CN112011256A CN202010924810.1A CN202010924810A CN112011256A CN 112011256 A CN112011256 A CN 112011256A CN 202010924810 A CN202010924810 A CN 202010924810A CN 112011256 A CN112011256 A CN 112011256A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/04—Printing inks based on proteins
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/06—Printing inks based on fatty oils
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- 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
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- Oil, Petroleum & Natural Gas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a UV thermosetting adhesive and a preparation method thereof, wherein the UV thermosetting adhesive comprises the following raw materials in parts by weight: 20-70 parts of epoxy acrylic acid with a structural formula 1, 20-50 parts of epoxy resin, 10-50 parts of acrylic resin, 0.1-5 parts of gas silicon, 0.1-5 parts of filler, 0.05-5 parts of photoinitiator, 0.05-5 parts of coupling agent, 10-50 parts of mercaptan and 0.05-2 parts of curing agent. The UV thermosetting adhesive of the invention abandons common low-temperature latent epoxy curing agents, solves the problem of addition of small molecular monomers, and realizes normal-temperature storage.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, and particularly relates to a UV (ultraviolet) thermosetting adhesive and a preparation method thereof.
Background
The UV thermosetting dual-curing glue used in the market at present generally adopts an epoxy resin-acrylic resin and epoxy resin-acrylic resin-mercaptan system, the first step of acrylic acid or epoxy acrylic acid reaction is initiated by UV, and the second step of heating is carried out to polymerize epoxy, so that the effect of UV + low-temperature thermosetting dual curing is realized.
However, the UV thermosetting adhesive currently on the market, although many factories repeatedly designed and developed, still has the following problems:
1. the selectable range of the commercial resin raw materials is narrow, and the performance requirements of the UV thermosetting adhesive cannot be completely matched;
2. common epoxy low-temperature latent curing agents need to be stored at low temperature, so that products also need to be stored at low temperature, and the storage period is short;
3. the epoxy low-temperature latent curing agent is not resistant to corrosion of small molecular monomers, so that latent failure is easily caused, and the application of a large number of monomers in UV thermosetting adhesive is limited.
Therefore, how to solve the above technical problems is a matter that those skilled in the art have been dedicated to solve.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a UV thermosetting adhesive.
In order to achieve the purpose, the invention adopts the technical scheme that: the UV thermosetting adhesive comprises the following raw materials in parts by weight: 20-70 parts of epoxy acrylic acid with a structural formula 1, 20-50 parts of epoxy resin, 10-50 parts of acrylic resin, 0.1-5 parts of gas silicon, 0.1-5 parts of filler, 0.05-5 parts of photoinitiator, 0.05-5 parts of coupling agent, 10-50 parts of mercaptan and 0.05-2 parts of curing agent, wherein the structural formula of the epoxy acrylic acid is as follows:
wherein R is1、R2、R3、R4Represents any one of methyl, alkyl, ether bond, aldehyde group, carbonyl and aromatic ring.
Preferably, the epoxy acrylic acid is prepared by mixing and reacting an acrylate monomer or epoxy resin with isocyanate groups having a structural formula 2 with a modified monomer or resin having a structural formula 3, wherein the structural formula 2:
structural formula 3:
preferably, the epoxy acrylic acid is prepared as follows: calculating the adding proportion of the acrylate monomer or epoxy resin with isocyanate groups in the structural formula 2 and the modified monomer or resin in the structural formula 3 according to the molecular weight and the functional groups, then putting the two into a reaction kettle, premixing at the temperature of 0-50 ℃, uniformly mixing, heating to 50-100 ℃, stirring for reaction for 0.5-4h, and confirming that the reaction is complete when the NCO content is detected to be 0 to obtain the epoxy acrylic acid in the structural formula 1.
Preferably, the photoinitiator employs at least one of a radical photoinitiator and a cationic photoinitiator.
In a specific embodiment, the photoinitiator is prepared from a free radical photoinitiator and a cationic photoinitiator according to a mass ratio of 1 (0-3).
Preferably, the curing agent is a thermal acid curing agent.
In a specific embodiment, the thermal acid curing agent is at least one selected from diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxaneoxide curing agents.
The invention also aims to provide a preparation method of the UV thermosetting adhesive, which comprises the following steps:
1) weighing the raw materials in parts by weight, and then putting all the raw materials into a stirring kettle or a homogenizer for full mixing;
2) adding a curing agent into the mixture obtained in the step 1), stirring and reacting for 0.5-3h at the temperature of 25-65 ℃, fully and uniformly mixing, and discharging to obtain the required UV thermosetting adhesive.
Preferably, the raw materials are fully mixed in the step 1), and then are added into a three-roll grinder for grinding until the fineness is not more than 10 microns.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, by adopting an acrylate monomer or epoxy resin with isocyanate groups, isocyanate on the monomer reacts with hydroxyl or other active hydrogen on a modified monomer or resin to prepare polymers containing epoxy groups and acrylate double bonds and having different functionalities, molecular weights and structures, so as to match different requirements of UV thermosetting adhesive; meanwhile, in the UV curing process, a free radical initiator is adopted to initiate double bond reaction, and a thermal acid curing agent is adopted to cure an epoxy group in the thermal curing process, so that a common low-temperature latent epoxy curing agent is abandoned, the problem of addition of small molecular monomers is solved, and normal-temperature storage is realized.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
The UV thermosetting adhesive comprises the following raw materials in parts by weight: 20-70 parts of epoxy acrylic acid with a structural formula 1, 20-50 parts of epoxy resin, 10-50 parts of acrylic resin, 0.1-5 parts of gas silicon, 0.1-5 parts of filler, 0.05-5 parts of photoinitiator, 0.05-5 parts of coupling agent, 10-50 parts of mercaptan and 0.05-2 parts of curing agent, wherein the structural formula of the epoxy acrylic acid is as follows:
wherein R is1、R2、R3、R4Represents any one of methyl, alkyl, ether bond, aldehyde group, carbonyl and aromatic ring.
The epoxy acrylic acid is prepared by mixing and reacting acrylate monomer or epoxy resin with isocyanate group with structural formula 2 and modified monomer or resin with structural formula 3, wherein,
structural formula 2:
structural formula 3:
the preparation process of the epoxy acrylic acid is as follows: calculating the adding proportion of the acrylate monomer or epoxy resin with isocyanate groups in the structural formula 2 and the modified monomer or resin in the structural formula 3 according to the molecular weight and the functional groups, then putting the two into a reaction kettle, premixing at the temperature of 0-50 ℃, uniformly mixing, heating to 50-100 ℃, stirring for reaction for 0.5-4h, and confirming that the reaction is complete when the NCO content is detected to be 0 to obtain the epoxy acrylic acid in the structural formula 1.
The photoinitiator is at least one of a free radical photoinitiator and a cationic photoinitiator, and is specifically configured by the free radical photoinitiator and the cationic photoinitiator according to the mass ratio of 1 (0-3).
Here, as the curing agent, a thermal acid curing agent is used, and specifically, the thermal acid curing agent is at least one selected from diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxan-based curing agents.
The preparation method of the UV thermosetting adhesive comprises the following steps:
1) weighing the raw materials according to the parts by weight, putting all the raw materials into a stirring kettle or a homogenizer, fully mixing, adding into a three-roll grinder for grinding until the fineness is not more than 10 microns;
2) adding a curing agent into the mixture obtained in the step 1), stirring and reacting for 0.5-3h at the temperature of 25-65 ℃, fully and uniformly mixing, and discharging to obtain the required UV thermosetting adhesive.
Examples 1 to 5 and comparative example 1 are given below, and specific formulations thereof are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Epoxy acrylic acid | 20 | 35 | 50 | 70 | 45 | 50 |
| Epoxy resin | 40 | 20 | 28 | 32 | 50 | 0 |
| Acrylic resin | 20 | 30 | 50 | 40 | 30 | 0 |
| Gas silicon | 2 | 0.1 | 3 | 5 | 0.5 | 0 |
| Filler material | 3 | 5 | 0.5 | 0.1 | 2 | 2 |
| Free radical photoinitiators | 3 | 1 | 0.05 | 2 | 0.1 | 0 |
| Cationic photoinitiators | 0 | 3 | 0 | 3 | 0.2 | 0.5 |
| Coupling agent | 0.05 | 2 | 4 | 3 | 5 | 6 |
| Thermal acid curing agent | 10 | 30 | 50 | 38 | 45 | 0 |
| Epoxy latent curing agent | 0 | 0 | 0 | 0 | 0 | 50 |
| Modified thiols | 0.05 | 1 | 2 | 1.5 | 0.8 | 5 |
The performance tests were performed for examples 1 to 5 and comparative example 1, as follows:
shear strength test
According to the test standard of tensile shear strength of ISO-4587 adhesive, glue is coated on a PI plate (the size is 20mm x 100mm x 4mm), first-step curing is carried out in 395nm LED-UV and the like, then the PI plate is placed into an oven at 80 ℃ for heat curing for 30min and then taken out, and after a sample is cooled, a universal material testing machine is adopted for carrying out shear test in a normal temperature environment.
Storage & Long term storage at Room temperature test
The glue was placed in the dark at ambient temperature and the change in viscosity of the glue was measured using a Brookfield viscometer (CP51@10rpm,25 ℃), and the shelf life was defined as the time when the viscosity rose by more than 20%.
Depth of cure & speed of heat cure
The glue is cured by light and heat, and the curing depth and the heat curing speed of the glue are evaluated in a mode of searching an exothermic peak through hardness & DSC temperature scanning.
The results of the property comparison are shown in Table 2.
TABLE 2
As can be seen from Table 2, when the UV thermosetting adhesive prepared by the raw materials of the invention is adopted, the normal-temperature long-term storage performance of the adhesive is substantially improved, the adhesive strength is excellent, and the overall comprehensive performance is good.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The UV thermosetting adhesive is characterized by comprising the following raw materials in parts by weight: 20-70 parts of epoxy acrylic acid with a structural formula 1, 20-50 parts of epoxy resin, 10-50 parts of acrylic resin, 0.1-5 parts of gas silicon, 0.1-5 parts of filler, 0.05-5 parts of photoinitiator, 0.05-5 parts of coupling agent, 10-50 parts of mercaptan and 0.05-2 parts of curing agent, wherein the structural formula of the epoxy acrylic acid is as follows:
wherein R is1、R2、R3、R4Represents any one of methyl, alkyl, ether bond, aldehyde group, carbonyl and aromatic ring.
2. The UV thermosetting adhesive according to claim 1, wherein the epoxy acrylic acid is prepared by mixing and reacting an acrylate monomer or epoxy resin with isocyanate group of formula 2 with a modified monomer or resin of formula 3,
structural formula 2:
structural formula 3:
3. the UV thermosetting adhesive according to claim 2, wherein the epoxy acrylic acid is prepared by the following steps: calculating the adding proportion of the acrylate monomer or epoxy resin with isocyanate groups in the structural formula 2 and the modified monomer or resin in the structural formula 3 according to the molecular weight and the functional groups, then putting the two into a reaction kettle, premixing at the temperature of 0-50 ℃, uniformly mixing, heating to 50-100 ℃, stirring for reaction for 0.5-4h, and confirming that the reaction is complete when the NCO content is detected to be 0 to obtain the epoxy acrylic acid in the structural formula 1.
4. The UV thermosetting adhesive according to claim 1, wherein the photoinitiator is at least one of a radical photoinitiator and a cationic photoinitiator.
5. The UV thermosetting adhesive according to claim 4, wherein the photoinitiator is prepared from a free radical photoinitiator and a cationic photoinitiator according to a mass ratio of 1 (0-3).
6. The UV thermosetting adhesive according to claim 1, wherein a thermal acid curing agent is used as the curing agent.
7. The UV thermosetting adhesive according to claim 6, wherein the thermal acid curing agent is at least one selected from diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxaneoxide curing agents.
8. A method for preparing the UV thermosetting adhesive according to any one of claims 1 to 7, comprising the following steps:
1) weighing the raw materials in parts by weight, and then putting all the raw materials into a stirring kettle or a homogenizer for full mixing;
2) adding a curing agent into the mixture obtained in the step 1), stirring and reacting for 0.5-3h at the temperature of 25-65 ℃, fully and uniformly mixing, and discharging to obtain the required UV thermosetting adhesive.
9. The preparation method of the UV thermosetting adhesive according to claim 8, wherein the raw materials are fully mixed in the step 1), and then are added into a three-roll grinder for grinding until the fineness is not more than 10 microns.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010924810.1A CN112011256A (en) | 2020-09-05 | 2020-09-05 | UV thermosetting adhesive and preparation method thereof |
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| CN202010924810.1A CN112011256A (en) | 2020-09-05 | 2020-09-05 | UV thermosetting adhesive and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852113A (en) * | 2021-01-15 | 2021-05-28 | 珠海格力新材料有限公司 | SLA (SLA-molded photosensitive resin) and preparation method and application thereof |
| CN114716954A (en) * | 2022-04-22 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Low-temperature fast-curing UV thermosetting adhesive and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101397363A (en) * | 2008-08-19 | 2009-04-01 | 东莞市佳景印刷材料有限公司 | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof |
| CN103965821A (en) * | 2014-04-30 | 2014-08-06 | 京东方科技集团股份有限公司 | Frame sealant composition and display device |
-
2020
- 2020-09-05 CN CN202010924810.1A patent/CN112011256A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397363A (en) * | 2008-08-19 | 2009-04-01 | 东莞市佳景印刷材料有限公司 | Water ultraviolet light curing epoxy acrylic ester grafted polyurethane and preparation method thereof |
| CN103965821A (en) * | 2014-04-30 | 2014-08-06 | 京东方科技集团股份有限公司 | Frame sealant composition and display device |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852113A (en) * | 2021-01-15 | 2021-05-28 | 珠海格力新材料有限公司 | SLA (SLA-molded photosensitive resin) and preparation method and application thereof |
| CN114716954A (en) * | 2022-04-22 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Low-temperature fast-curing UV thermosetting adhesive and preparation method thereof |
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Application publication date: 20201201 |