CN111944472B - Photo-curing adhesive and preparation method and application thereof - Google Patents
Photo-curing adhesive and preparation method and application thereof Download PDFInfo
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- CN111944472B CN111944472B CN202010807907.4A CN202010807907A CN111944472B CN 111944472 B CN111944472 B CN 111944472B CN 202010807907 A CN202010807907 A CN 202010807907A CN 111944472 B CN111944472 B CN 111944472B
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a photocuring adhesive and a preparation method and application thereof, belonging to the technical field of adhesives, and comprising 30-70 parts of urethane acrylate, 25-65 parts of acrylate monomer, 0.5-5 parts of photoinitiator and 0.5-5 parts of mercaptan; the total weight portion of the polyurethane acrylate, the acrylate monomer, the photoinitiator and the mercaptan is 100 portions. Dispersing the components at a high speed for 1-2 minutes and 2-5 times at the rotation speed of 900 plus 1800 rpm; vacuumizing and defoaming for 2-5 minutes to obtain the photocuring adhesive. The adhesive can be rapidly cured by ultraviolet irradiation, and the cured adhesive has excellent adhesive strength, corrosion resistance, heat resistance and water resistance. Meanwhile, the adhesive provides very high elongation at break and suitable hardness, and can greatly enhance the bending resistance of the FPC.
Description
Technical Field
The invention belongs to the technical field of adhesives, particularly relates to a photocuring adhesive and a preparation method and application thereof, and particularly relates to a photocuring adhesive applied to a flexible circuit board and a preparation method thereof.
Background
A Flexible Printed Circuit (FPC), also called a Flexible Printed Circuit (FPC) or a Flexible Printed Circuit (FPC), is a printed circuit with high reliability and excellent flexibility, which is made of a polyester film or polyimide as a base material, and a large number of precision components are stacked and embedded in a narrow and limited space by embedding a circuit design on a bendable light and thin plastic sheet, thereby forming a bendable flexible circuit. Flexible circuit boards are preferred for their excellent characteristics such as light weight, thin thickness, and free flexibility and folding. With the rapid development of electronic products, the demand of FPCs has also increased significantly.
In the electronic device, the circuit board is easily corroded by external environment such as moisture, mold, vibration, etc. in the prior art, an adhesive is generally applied to protect the surface of the circuit board. The adhesive for circuit boards is required to have good corrosion resistance, adhesive strength, heat resistance, water resistance, and the like. However, in practical application, the FPC flexible flat cable is easy to break or the bonding part of the FPC is not resistant to folding, and the problem is not solved by an adhesive product at present.
The Chinese patent with publication number CN110607126A provides an electronic coating adhesive for protecting an electronic circuit board and a preparation method thereof, the electronic coating adhesive comprises components such as urethane acrylate, a UV monomer, nano silicon dioxide, a leveling aid, a defoaming agent, a wetting agent, a fluorescent agent and the like, the prepared UV coating adhesive is transparent in color, hard in texture, and remarkably improved in chemical corrosion resistance, wear resistance, strength, elongation and toughness, but the bending resistance of an FPC is not improved. Therefore, there is a need to develop an adhesive composition for FPC protection, which has good corrosion resistance, adhesive strength, heat resistance and water resistance after curing, and can greatly enhance the bending resistance of FPC.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a photocuring adhesive and a preparation method and application thereof. The adhesive can be rapidly cured by ultraviolet irradiation, and the cured adhesive has excellent adhesive strength, corrosion resistance, heat resistance and water resistance. Meanwhile, the adhesive has low water absorption, high elongation and high reliability, provides very high elongation at break and proper hardness, and can greatly enhance the bending resistance of the FPC.
The purpose of the invention is realized by the following technical scheme: the photo-curing adhesive comprises the following components in parts by weight:
preferably, the total weight parts of the urethane acrylate, the acrylate monomer, the photoinitiator and the mercaptan is 100 parts. Preferably, the light-cured adhesive further comprises additives, and the additives comprise one or more of organic/inorganic fillers, stabilizers and pigments.
Preferably, the synthetic raw materials of the polyurethane acrylate comprise a hydroxyl-terminated prepolymer and isocyanate; the hydroxyl-terminated prepolymer comprises one or more of polyethers, polyesters, polycarbonates or organic silicon; the isocyanate includes an aliphatic isocyanate or an aromatic isocyanate.
Preferably, the urethane acrylate comprises one or more of CN8881NS, CN8887NS, CN8888NS, CN9021NS, BR-7432GB of Dyma Dymax, BRC-843S, UA-1138P, U-200PA of New Memura chemical.
Preferably, the acrylate monomer comprises one or more of a monofunctional acrylate or a multifunctional acrylate.
Preferably, the acrylate monomer comprises one or more of isobornyl acrylate (IBOA), ethoxy acrylate, 3, 5-trimethylcyclohexane acrylate (TMCHA), trimethylolpropane formal acrylate (CTFA), tetrahydrofuran acrylate (THFA), lauryl acrylate, isodecyl acrylate, tricyclodecane dimethanol diacrylate, 1, 6-hexanediol diacrylate (HDDA), 2-ethoxy-1, 6-hexanediol diacrylate.
Preferably, the photoinitiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone (184), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzoin dimethyl ether (651), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819).
Preferably, the thiols comprise one or more of trimethylolpropane tris (3-mercaptopropionate) (TMTP), pentaerythritol tetrakis (3-mercaptobutanoate), pentaerythritol tetrakis (3-mercaptopropionate) (PETMP).
A preparation method of a light-cured adhesive comprises the following steps: heating and dissolving the photoinitiator, and dispersing the components at a high speed for 1-2 minutes and 2-5 times at the rotating speed of 900-1800 rpm; vacuumizing and defoaming for 2-5 minutes to obtain the photocuring adhesive.
The application of the photocuring adhesive is characterized in that the photocuring adhesive is coated on the surface of a flexible printed circuit board to protect the FPC from being corroded by external environments such as moisture, mould, vibration and the like, and the problem that the FPC flexible flat cable is easy to break or the bonding part of the FPC is not resistant to breaking is solved.
The hardness of the photo-cured adhesive after curing is more than A75, the water absorption is less than or equal to 0.51%, the peel strength is greater than or equal to 0.50MPa, the bending resistance times are greater than or equal to 45, the elongation is greater than or equal to 350%, and the tensile modulus at 25 ℃ is greater than or equal to 20 MPa.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a UV light curing mode, the curing speed is high, and the bending resistance of the FPC flexible flat cable part is greatly improved;
(2) the adhesive cured by the invention has good corrosion resistance, bonding strength, heat resistance and waterproofness.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values are to be considered as specifically disclosed herein, the invention is described in detail below with reference to specific examples:
example 1
A light-cured adhesive is prepared by the following components in proportion:
the preparation method comprises the following steps: heating IBOA and TPO on a magnetic stirrer at 50-60 ℃ in advance, stirring until the IBOA and the TPO are completely dissolved, and cooling to room temperature; the components are sequentially added into a small black tank matched with a high-speed dispersion machine and are dispersed for 1-2 minutes at a high speed for 2-5 times at the rotating speed of 900 plus 1800 rpm. And then the defoaming function of a dispersion machine is used for vacuumizing and defoaming for 2-5 minutes to obtain the light-curable adhesive. The obtained photocurable adhesive was subjected to various performance tests, and the results are shown in table 1.
Example 2
A light-cured adhesive is prepared by the following components in proportion:
the preparation method comprises the following steps: the components are sequentially added into a small black tank matched with a high-speed dispersion machine and are dispersed for 1-2 minutes at a high speed for 2-5 times at the rotating speed of 900 plus 1800 rpm. Then, the defoaming function of the dispersion machine is used, the vacuum pumping and defoaming are carried out for 2-5 minutes to obtain the photo-curable adhesive, and various performance tests are carried out on the obtained photo-curable adhesive in example 2, and the obtained results are shown in table 1.
Example 3
A light-cured adhesive is prepared by the following components in proportion:
the preparation method is the same as that of example 1, a light-curable adhesive is obtained, and various performance tests are performed on the obtained light-curable adhesive in example 3, and the obtained results are shown in table 1.
Example 4
A light-cured adhesive is prepared by the following components in proportion:
the preparation method was the same as in example 2 to obtain a photocurable adhesive, and various performance tests were performed on the obtained photocurable adhesive in example 4 to obtain results shown in table 1.
Example 5
A light-cured adhesive is prepared by the following components in proportion:
the preparation method was the same as in example 2 to obtain a photocurable adhesive, and various performance tests were performed on the obtained photocurable adhesive in example 5 to obtain results shown in table 1.
Example 6
A light-cured adhesive is prepared by the following components in proportion:
the preparation method was the same as in example 1 to obtain a photocurable adhesive, and various performance tests were performed on the obtained photocurable adhesive in example 6, and the results are shown in table 1.
Example 7
A light-cured adhesive is prepared by the following components in proportion:
the preparation method was the same as in example 2 to obtain a photocurable adhesive, and various performance tests were performed on the obtained photocurable adhesive in example 7 to obtain results shown in table 1.
Comparative example 1
A light-cured adhesive is prepared by the following components in proportion:
35 parts of polyurethane acrylate polyester acrylate;
60 parts of acrylate monomer isobornyl acrylate (IBOA);
5 parts of photoinitiator 1-hydroxycyclohexyl phenyl ketone (184);
the preparation method was the same as in example 2, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Comparative example 2
A light-cured adhesive is prepared by the following components in proportion:
the preparation method was the same as in example 2, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Comparative example 3
A light-cured adhesive is a variation of example 1, and is prepared according to the following composition ratio:
the preparation method was the same as in example 1, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Comparative example 4
A light-cured adhesive is a variation of the embodiment 2, and is prepared according to the following composition ratio:
the preparation method was the same as in example 2, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Comparative example 5
A photo-curable adhesive is a variation of example 3, and is prepared according to the following composition ratio:
the preparation method was the same as in example 3, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Comparative example 6
A photo-curable adhesive is a variation of example 4, and is prepared according to the following composition ratio:
the preparation method was the same as in example 4, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Comparative example 7
A photo-curable adhesive is a variation of example 3, and is prepared according to the following composition ratio:
the preparation method was the same as in example 3, and various performance tests were carried out on the obtained photocurable adhesive, and the results are shown in table 1.
Performance testing
The examples and comparative examples were tested for curable adhesives.
1. Hardness of
And (3) hardness testing: the hardness of each adhesive after curing was tested according to national standard GBT2411-2008 "hardness of plastic and hard rubber by indenter hardness (Shore hardness)".
2. Water absorption rate
Water absorption test: the adhesives of the examples and comparative examples were prepared into a disk having a diameter of 20mm and a thickness of 2mm, and boiled in boiling water for two hours. And weighing the mass before and after water boiling, and calculating the water absorption rate.
3. Peel strength
And (3) testing the peel strength: the flexibility of the flexible material is tested according to the national standard GB/T2791-1995 method for testing the T peel strength of the adhesive.
4. High temperature and high humidity
And (3) taking the FPC device, dispensing the adhesive on the device by using a dispenser, and curing by using an LED curing machine. The glued device was placed at 85 ℃ and 85% humidity for 500 hours. And taking out the colloid to observe the appearance, and if the colloid does not crack or fall off, determining that the colloid passes the test.
5. Number of times of bending
And (3) taking the FPC device, dispensing the adhesive on the device by using a dispenser, and curing by using an LED curing machine. And (3) bending the device at a constant speed, defining 0 degree/90 degree/180 degree/0 degree as one-time bending, and observing whether the device is broken or not under a microscope after each 5-time bending. The number of times the device began to break was recorded.
6. Elongation percentage
And (3) elongation testing: using standard ISO 527-3: 2018 determination of tensile Properties of plastics part 3: test conditions for films and sheets
7. Tensile modulus
Tensile modulus: testing with DMA instruments
TABLE 1 various Properties of Photocurable Adhesives
As can be seen from Table 1, the photocurable adhesive of the present invention has good peel strength, resistance to moist heat and water, suitable hardness, and high elongation at break and tensile modulus, so that the bending resistance of FPC is greatly improved.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (5)
1. The photo-curing adhesive is characterized by comprising the following components in parts by weight:
the total weight parts of the polyurethane acrylate, the acrylate monomer, the photoinitiator and the mercaptan are 100 parts;
the polyurethane acrylate is CN8888 NS;
the acrylate monomer is isoborneol acrylate and ethoxy acrylate.
2. The photocurable adhesive of claim 1 wherein the photoinitiator comprises one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, benzoin dimethyl ether, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyl oxime), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
3. The light-curable adhesive of claim 1 wherein the thiol comprises one or more of trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanoate), pentaerythritol tetrakis (3-mercaptopropionate).
4. A method for preparing a light-curable adhesive according to any one of claims 1 to 3, comprising the steps of: dispersing each component for 1-2 minutes at high speed for 2-5 times at the rotating speed of 900-1800 revolutions per minute; and vacuumizing and defoaming for 2-5 minutes to obtain the photocuring adhesive.
5. The use of the light-curable adhesive according to any one of claims 1 to 3, wherein the light-curable adhesive is coated on the surface of a flexible printed circuit board to protect the FPC from being corroded by the external environment and solve the problem that the FPC flexible flat cable is easy to break or the bonding part of the FPC is not resistant to breaking; the external environment is moisture, mould and vibration;
the hardness of the photo-cured adhesive after curing is more than A75, the water absorption is less than or equal to 0.51%, the peel strength is greater than or equal to 0.50MPa, the bending resistance times are greater than or equal to 45, the elongation is greater than or equal to 350%, and the tensile modulus at 25 ℃ is greater than or equal to 20 MPa.
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| CN202010807907.4A CN111944472B (en) | 2020-08-12 | 2020-08-12 | Photo-curing adhesive and preparation method and application thereof |
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| CN111944472B true CN111944472B (en) | 2022-05-06 |
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| CN116410657A (en) * | 2021-12-31 | 2023-07-11 | 宁波激智创新材料研究院有限公司 | Elastic polyurethane layer and reworkable foam adhesive tape |
| CN115124970A (en) * | 2022-07-29 | 2022-09-30 | 浙江国能科技有限公司 | Polyurethane three-proofing adhesive and preparation method and application thereof |
| CN115322735A (en) * | 2022-09-13 | 2022-11-11 | 珠海格力电器股份有限公司 | High-temperature-resistant ultraviolet-curing three-proofing adhesive, and preparation method and application thereof |
| CN115433537B (en) * | 2022-09-15 | 2023-06-23 | 江苏矽时代材料科技有限公司 | High-cohesiveness ultraviolet light curing adhesive and preparation method and application thereof |
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| CN103305178B (en) * | 2012-03-06 | 2014-11-26 | 上海佑威新材料科技有限公司 | Low-modulus optical adhesive composition |
| CN104356995A (en) * | 2014-10-22 | 2015-02-18 | 重庆市旭星化工有限公司 | Ultraviolet light curing adhesive |
| CN108949091A (en) * | 2018-06-26 | 2018-12-07 | 深圳市宝力新材料有限公司 | A kind of ultraviolet-curing adhesive composition and manufacture craft |
| CN108865045A (en) * | 2018-07-30 | 2018-11-23 | 江苏科琪高分子材料研究院有限公司 | Physical blowing light-cured acrylic adhesive and application thereof |
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