CN113621339B - Photochromic solder joint protective adhesive and preparation method and application thereof - Google Patents
Photochromic solder joint protective adhesive and preparation method and application thereof Download PDFInfo
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- CN113621339B CN113621339B CN202110895546.8A CN202110895546A CN113621339B CN 113621339 B CN113621339 B CN 113621339B CN 202110895546 A CN202110895546 A CN 202110895546A CN 113621339 B CN113621339 B CN 113621339B
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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
Abstract
The invention provides a photochromic welding spot protection adhesive and a preparation method and application thereof, wherein the preparation raw materials of the welding spot protection adhesive comprise a combination of a monofunctional acrylate monomer, a polyurethane acrylate oligomer, a photoinitiator, epoxy resin and UV (ultraviolet) color-changing powder in a specific part; the welding spot protection adhesive is prepared by selecting a combination of a difunctional polyurethane acrylate oligomer and a multifunctional polyurethane acrylate oligomer as an oligomer, regulating and controlling the addition amount of each component and adding a specific part of UV color-changing powder, has moderate hardness, has excellent curing depth, has obvious color change before and after UV illumination and has easy repair performance, and has important research value.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a photochromic welding spot protection adhesive, a preparation method and application thereof.
Background
The welding spots on the precision module are also called PINs, english called PIN, namely the connection wires with peripheral circuits are led out from the internal circuits of an integrated circuit (chip), the tail ends of the lead wires are connected to a printed board (usually an FPC soft board) through soft soldering, in some fine manufacturing industries, such as module assembly, glue is often required to be used for protecting the welding places of the PINs, and meanwhile, the strength of the glue is also enhanced, and the glue is called PIN glue or welding spot protection glue, and UV cured glue is usually used.
With the continuous development and progress of integrated circuits, conventional UV-curable adhesives have failed to meet the requirements, and thus, research into glues used in integrated circuit packages is also being conducted. CN108707447a discloses a strong bonding high conductive welding glue, the formula comprises, by mass, 5-15% of tin, 10-20% of bismuth, 5-15% of naphthalene epoxy, 10-20% of modified acrylic resin, 1-3% of phenolic resin, 0.5-1.5% of calcined silica, 0.5-1.5% of adipic acid, 0.1-0.5% of silane coupling agent, 5-15% of hardener and the balance of epoxy resin; the welding adhesive provided by the invention not only has better cohesiveness, but also has excellent conductivity, can avoid the problem of short circuit caused by cracking under the conditions of high temperature and high humidity, and is very suitable for electronic products with limited space. CN111826105a discloses a packaging adhesive for an LED, a use method and application thereof, the packaging adhesive for an LED comprises a component a and a component B, wherein the component a comprises an epoxy resin and an antioxidant, and optionally a color paste; the component B comprises a curing agent, a hydroxyl terminated polyurethane prepolymer, a polyol and an accelerator, and optionally an ultraviolet absorber; the LED packaging adhesive has good cold and hot impact resistance and wet heat resistance.
However, as for the solder joint protective paste for precision manufacturing, since the amount of devices to be handled per day is very large in an assembly factory, and further, the solder joint protective paste may go into the next process without UV curing, and at this time, it is necessary to provide means for preventing errors, and it is common practice to attach a color-changing label to a part tray, which changes color when UV-irradiated, and determine whether the whole tray of parts is UV-cured by the color change of the label. However, in the method, the condition of each part cannot be tracked, an additional process of manually sticking labels is needed, the cost is increased, the phenomenon of missing sticking can occur, and the method is not beneficial to use in the mass production process.
Therefore, developing a photochromic solder joint protective adhesive with moderate hardness, excellent curing depth is an urgent technical problem in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a photochromic welding spot protective adhesive and a preparation method and application thereof; the preparation raw materials of the welding spot protective adhesive comprise a combination of a monofunctional acrylic monomer, a polyurethane acrylic oligomer photoinitiator, epoxy resin and UV color-changing powder in a specific part; the combination of the difunctional polyurethane acrylate oligomer and the multifunctional polyurethane acrylate oligomer is selected as the polyurethane acrylate oligomer, and the components are matched with each other, so that the obtained welding spot protective adhesive has the characteristics of moderate hardness, excellent curing depth, obvious color change before and after UV illumination and easy repair, and is suitable for mass production of devices.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a photochromic solder joint protective adhesive, which comprises the following raw materials in parts by weight: 25-45 parts of monofunctional acrylate monomer, 50-65 parts of polyurethane acrylate oligomer, 1-5 parts of photoinitiator, 1-4 parts of epoxy resin and 2-5 parts of UV color-changing powder.
The urethane acrylate oligomer includes a difunctional urethane acrylate oligomer and a multifunctional urethane acrylate oligomer.
The monofunctional acrylate monomer may be 27 parts by weight, 29 parts by weight, 31 parts by weight, 33 parts by weight, 35 parts by weight, 37 parts by weight, 39 parts by weight, 41 parts by weight, 43 parts by weight, or the like.
The urethane acrylate oligomer may be 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, or the like.
The photoinitiator may be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or the like.
The epoxy resin may be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, or the like.
The UV color-changing powder may be 2.3 parts by weight, 2.6 parts by weight, 2.9 parts by weight, 3 parts by weight, 3.3 parts by weight, 3.6 parts by weight, 3.9 parts by weight, 4 parts by weight, 4.3 parts by weight, 4.6 parts by weight, 4.9 parts by weight, or the like.
On one hand, the UV color-changing powder is introduced into the preparation raw materials of the welding spot protective adhesive, so that the welding spot protective adhesive can be changed in color while being cured, thus the color-changing label does not need to be additionally and manually posted, and whether each part is subjected to UV curing can be intuitively observed from the color of the welding spot protective adhesive, thereby overcoming the defects of the welding spot protective adhesive in the prior art.
On the other hand, the welding spot protective adhesive needs to have moderate hardness (D40-D60) so as to resist certain deformation in actual use, and is not too soft so as not to provide better strength; the thickness of the glue in the partial area is larger, so that the solder joint protective glue with a certain curing depth is needed to avoid the bottom from being unable to be cured; the repair performance is also required, so that the parts can be repaired and reused when assembled incorrectly. The UV color-changing powder is directly added into the welding spot protective adhesive to greatly influence the curing depth of the welding spot protective adhesive, and meanwhile, the repairing performance of the welding spot protective adhesive is also deteriorated; according to the invention, the combination of the difunctional polyurethane acrylate oligomer and the multifunctional polyurethane acrylate oligomer is selected, and the total addition amount of the polyurethane acrylate oligomer is controlled to be 50-65 parts by weight of a specific part, so that the obtained welding spot protection adhesive has good curing depth and good repairing performance.
In summary, the photochromic welding spot protection adhesive provided by the invention selects a specific part of difunctional polyurethane acrylate oligomer and multifunctional polyurethane acrylate oligomer, the difunctional polyurethane acrylate oligomer and the multifunctional polyurethane acrylate oligomer are cooperated, the total addition amount of the difunctional polyurethane acrylate oligomer and the multifunctional polyurethane acrylate oligomer is controlled to be 50-65 parts by weight, and the specific part of UV color-changing powder is added, so that the performance of the welding spot protection adhesive is not affected; the obtained photochromic solder joint protective adhesive has moderate hardness and excellent curing depth, can avoid the problem that the bottom cannot be completely cured, has repairing performance, has obvious color change before and after UV illumination, can be repaired in time when parts are assembled incorrectly, is suitable for being used in the production of a large number of devices, and has important research significance.
Preferably, the monofunctional acrylate monomer comprises any one or a combination of at least two of isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, tetrahydrofuranacrylate, tetrahydrofuranmethacrylate, dodecyl acrylate, dodecyl methacrylate, isodecyl acrylate, N-vinylcaprolactam or N-vinylpyrrolidone.
Preferably, the difunctional urethane acrylate oligomer comprises a difunctional aliphatic urethane acrylate oligomer and/or a difunctional aromatic urethane acrylate oligomer.
Preferably, the content of the difunctional urethane acrylate oligomer in the preparation raw material of the solder joint protective adhesive is 30 to 50 parts by weight, for example, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight or the like.
Preferably, the difunctional aliphatic polyurethane acrylate oligomer may be selected from one or more of the following commercial products, for example, may be selected from the group consisting of sandomax CN8003, CN8010, CN8881, CN8883, CN8887, CN8888, CN9004, CN9007, CN9014, CN9023, CN9028, CN965, CN969, CN980, CN981, and CN996.
Preferably, the difunctional aromatic polyurethane acrylate oligomer may be selected from one or more of the following commercial products; for example, sandomax CN9167, CN978, CN9782, CN9783, or CN992 may be selected.
Preferably, the multifunctional urethane acrylate oligomer comprises a multifunctional aliphatic urethane acrylate oligomer and/or a multifunctional aromatic urethane acrylate oligomer.
Preferably, the multifunctional urethane acrylate oligomer comprises a 6 to 9 (e.g., 7 or 8) functionality urethane acrylate oligomer.
Preferably, the content of the difunctional urethane acrylate oligomer in the preparation raw material of the solder joint protective adhesive is 10 to 25 parts by weight, for example, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight or the like.
Preferably, the multifunctional aliphatic urethane acrylate oligomer may be selected from one or more of the following commercial products; for example, it is possible to select a sand-gama CN8000, CN8011, CN8885, CN9006, CN9010, CN9013, CN9026, CN9110, or the like.
Preferably, the multifunctional aromatic urethane acrylate oligomer may be selected from the group consisting of sabomacn 9165.
Preferably, the photoinitiator comprises any one or a combination of at least two of 1-hydroxycyclohexylphenyl ketone, 2,4,6- (trimethylbenzoyl) diphenyl phosphate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylphenyl) butanone, methyl benzoylformate, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-isopropylthioxanthone, benzoin dimethyl ether, dimethylbenzoyl ketal or benzophenone, further preferably a combination of 1-hydroxycyclohexylphenyl ketone and phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Preferably, the epoxy resin comprises bisphenol a epoxy resin or bisphenol F epoxy resin.
Preferably, the UV color-changing powder comprises a photochromic material, for example, the series of light-changing powder products in Shenzhen city and chemical industry can be selected.
In the invention, the UV color-changing powder is an ultraviolet sensitive material, the initial color is semitransparent milky white, the color can be changed into red or other various colors after ultraviolet light is absorbed, the color depth deepens along with the increase of the ultraviolet irradiation time, and the color change is irreversible change.
Preferably, the raw materials for preparing the welding spot protection glue further comprise any one or a combination of at least two of an antioxidant, a dispersing agent and a filler.
Preferably, the antioxidant is contained in the raw material for preparing the solder joint protective paste in an amount of 0 to 1 part by weight and not equal to 0, for example, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, or the like.
Preferably, the content of the dispersant in the raw material for preparing the solder joint protective paste is 0 to 2 parts by weight and is not equal to 0, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, or the like.
Preferably, the filler is contained in the raw material for preparing the solder joint protective paste in an amount of 0 to 5 parts by weight and equal to 0, for example, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or the like.
In a second aspect, the present invention provides a method for preparing the solder joint protective paste according to the first aspect, the method comprising the steps of:
(1) Mixing monofunctional acrylate mono-functional polyurethane acrylate oligomer, difunctional polyurethane acrylate oligomer and multifunctional polyurethane acrylate oligomer to obtain a transparent mixture;
(2) Mixing the transparent mixture obtained in the step (1), a photoinitiator and epoxy resin to obtain a uniform mixture;
(3) Mixing the uniform mixture obtained in the step (2), UV color-changing powder, optional antioxidant, optional dispersing agent and optional filler to obtain the solder joint protective adhesive.
Preferably, the mixing of step (1) is carried out under stirring conditions, preferably at a rotational speed of 100 to 4000rpm (e.g. 500rpm, 1000rpm, 1500rpm, 2000rpm, 2500rpm, 3000rpm or 3500 rpm).
Preferably, the temperature of the mixing in step (1) is 10 to 40 ℃, e.g. 13 ℃, 16 ℃, 19 ℃, 23 ℃, 26 ℃, 29 ℃, 33 ℃, 36 ℃, 39 ℃, etc.
Preferably, the mixing time in step (1) is 10-60 min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, etc.
Preferably, the mixing in step (2) is performed under stirring conditions, preferably at a rotational speed of 1000 to 3000rpm (e.g. 1200rpm, 1400rpm, 1600rpm, 1800rpm, 2000rpm, 2200rpm, 2400rpm, 2600rpm or 2800rpm, etc.).
Preferably, the temperature of the mixing in step (2) is 20 to 40 ℃, e.g. 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, etc.
Preferably, the mixing time in step (2) is 15-40 min, for example 17min, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min or 38min, etc.
In a third aspect, the present invention provides a use of the photochromic solder joint protective paste according to the first aspect in module assembly.
Preferably, the application comprises a pin paste for use in module assembly.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation raw materials of the photochromic solder joint protective adhesive provided by the invention comprise the combination of a specific part of monofunctional acrylate monomer, difunctional polyurethane acrylate oligomer, multifunctional polyurethane acrylate oligomer, a photoinitiator, epoxy resin and UV (ultraviolet) color-changing powder; the welding spot protective adhesive has moderate hardness, excellent curing depth and easy repair performance by limiting the dosage of each component and adding the specific part of UV color-changing powder, and has obvious color change before and after UV illumination, thus being suitable for devices in mass production.
(2) Specifically, the hardness of the welding spot protective adhesive is in the range of D40-D60, the curing depth exceeds 1mm, the repairing performance can reach 1 level, and the color change can be identified by naked eyes.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 25 parts by weight of isobornyl methacrylate, 45 parts by weight of difunctional urethane acrylate oligomer (sartomer, CN 9167), 20 parts by weight of multifunctional urethane acrylate oligomer (sartomer, CN 8000), 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 3 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 5 parts by weight of UV color-changing powder (Shenzhen City edge and chemical industry);
the preparation method of the photochromic solder joint protective adhesive provided by the embodiment comprises the following steps:
(1) Mixing isobornyl methacrylate, a difunctional urethane acrylate oligomer and a multifunctional urethane acrylate oligomer for 50min at a temperature of 30 ℃ and a rotating speed of 2000rpm to obtain a transparent mixture;
(2) Mixing the transparent mixture obtained in the step (1), 1-hydroxycyclohexyl phenyl ketone and epoxy resin for 20min at a rotating speed of 1500rpm to obtain a uniform mixture;
(3) And (3) mixing the uniform mixture obtained in the step (2) with UV color-changing powder, and stopping mixing until the fineness of the scraping plate is below 50 mu m to obtain the welding spot protection adhesive.
Example 2
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 45 parts by weight of isobornyl acrylate, 30 parts by weight of a difunctional urethane acrylate oligomer (saruma includes, CN 9167), 20 parts by weight of a multifunctional urethane acrylate oligomer (saruma, CN 8000), 1 part by weight of 2,4,6- (trimethylbenzoyl) diphenyl phosphorus oxide, 1 part by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 3 parts by weight of UV discoloration powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Example 3
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 31 parts by weight of hydroxyethyl methacrylate, 50 parts by weight of a difunctional urethane acrylate oligomer (saruma, CN 9167), 10 parts by weight of a multifunctional urethane acrylate oligomer (saruma, CN 8000), 5 parts by weight of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 2 parts by weight of UV discoloration powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Example 4
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 32 parts by weight of isobornyl methacrylate, 35 parts by weight of difunctional urethane acrylate oligomer (sartomer, CN 9167), 25 parts by weight of multifunctional urethane acrylate oligomer (sartomer, CN 8000), 1 part by weight of 1-hydroxycyclohexyl phenyl ketone, 3 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 4 parts by weight of UV color-changing powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Example 5
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 37 parts by weight of isobornyl methacrylate, 40 parts by weight of difunctional urethane acrylate oligomer (sartomer, CN 9167), 16 parts by weight of multifunctional urethane acrylate oligomer (sartomer, CN 8000), 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1 part by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 3 parts by weight of UV color-changing powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Example 6
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 40 parts by weight of isobornyl methacrylate, 32 parts by weight of difunctional urethane acrylate oligomer (sartomer, CN 9167), 18 parts by weight of multifunctional urethane acrylate oligomer (sartomer, CN 8000), 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 4 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 2 parts by weight of UV color-changing powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Comparative example 1
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 53 parts by weight of isobornyl methacrylate, 25 parts by weight of a difunctional urethane acrylate oligomer (sartomer, CN 9167), 15 parts by weight of a multifunctional urethane acrylate oligomer (sartomer, CN 8000), 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 2 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 3 parts by weight of UV color-changing powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Comparative example 2
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: isobornyl methacrylate 20 parts by weight, difunctional urethane acrylate oligomer (sartomer, CN 9167) 55 parts by weight, multifunctional urethane acrylate oligomer (sartomer, CN 8000) 20 parts by weight, 1-hydroxycyclohexyl phenyl ketone 2 parts by weight, bisphenol a epoxy resin (CAS: 25085-99-8) 1 part by weight and UV color changing powder (Shenzhen market edge and chemical industry) 2 parts by weight;
the preparation method is the same as in example 1.
Comparative example 3
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 25.8 parts by weight of isobornyl methacrylate, 46.5 parts by weight of difunctional urethane acrylate oligomer (sartomer, CN 9167), 20.7 parts by weight of multifunctional urethane acrylate oligomer (sartomer, CN 8000), 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 5 parts by weight of UV color-changing powder (Shenzhen city edge and chemical industry);
the preparation method is the same as in example 1.
Comparative example 4
The photochromic solder joint protective adhesive comprises the following raw materials in parts by weight: 30 parts by weight of isobornyl methacrylate, 35 parts by weight of difunctional urethane acrylate oligomer (sartomer, CN 9167), 20 parts by weight of multifunctional urethane acrylate oligomer (sartomer, CN 8000), 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 4 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8) and 6 parts by weight of UV color-changing powder (Shenzhen City edge and chemical industry);
the preparation method is the same as in example 1.
Comparative example 5
The photochromic solder joint protective adhesive is different from the embodiment 1 in that the preparation raw materials of the solder joint protective adhesive comprise the following components in parts by weight: 25 parts by weight of isobornyl methacrylate, 45 parts by weight of a difunctional urethane acrylate oligomer (sartomer, CN 9167), 20 parts by weight of a multifunctional urethane acrylate oligomer (sartomer, CN 8000), 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 3 parts by weight of bisphenol A epoxy resin (CAS: 25085-99-8);
the preparation method is the same as in example 1.
Comparative example 6
A photochromic solder joint protective paste was different from example 1 in that a bifunctional urethane acrylate oligomer was not added, the polyfunctional urethane acrylate oligomer was added in an amount of 65 parts by weight, and other components, amounts and preparation methods were the same as those of example 1.
Comparative example 7
A photochromic solder joint protective paste was different from example 1 in that a multifunctional urethane acrylate oligomer was not added, the amount of the difunctional urethane acrylate oligomer added was 65 parts by weight, and other components, amounts and preparation methods were the same as in example 1.
Performance test:
(1) Shore hardness: 2g of solder joint protective adhesive is taken and put into a mould to prepare a wafer with the diameter of 3cm, and a UV-LED ultraviolet lamp, such as XC210 with the wavelength of 365nm, is used for 5000mJ/cm 2 The front and back sides of the UV energy of the film are respectively cured once, and after standing for 24 hours, the hardness of the cured film is detected by using a digital Shore hardness tester;
(2) Depth of cure: using a UV-LED lamp (IGE XC210, wavelength 365 nm) at 500mW/cm 2 Curing the solder resist under the light intensity of 10s with total energy of 5000mJ/cm 2 Testing the thickness of the completely cured welding spot protective adhesive to obtain the curing depth;
(3) Reworkable performance: coating a PIN foot with a welding spot protective adhesive, fully curing by UV, and then placing in an oven at 80 ℃ for baking for 10min; after the PIN is taken out, the adhesive tape is lifted up by tweezers, whether the PIN can be completely peeled off or not is observed, whether residual adhesive exists on the PIN is rated, 1 represents that the PIN is completely free of residual adhesive, and 5 represents that the PIN cannot be peeled off after being completely adhered;
(4) Color change after UV cure: coating a welding spot protective adhesive on the PIN foot, observing color change before and after UV curing, wherein the color change cannot be obviously distinguished and is counted as 5; the color change is measured as 3 when the UV front and rear glues are placed together and aligned in parallel; the color change can be perceived as 2 without placing the UV front and back glue together; the difference of front and back colors is huge, and the visual recognition is very obvious as 1.
The solder joint protective adhesives provided in examples 1 to 6 and comparative examples 1 to 7 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
| Shore hardness of | Depth of cure (mm) | Reworking performance | Color change | |
| Example 1 | D45 | 1.35 | 1 | 1 |
| Example 2 | D60 | 1.15 | 1 | 2 |
| Example 3 | D40 | 1.45 | 1 | 2 |
| Example 4 | D54 | 1.25 | 1 | 1 |
| Example 5 | D51 | 1.3 | 1 | 2 |
| Example 6 | D57 | 1.25 | 1 | 2 |
| Comparative example 1 | D61 | 0.75 | 1 | 1 |
| Comparative example 2 | D34 | 1.6 | 3 | 2 |
| Comparative example 3 | D46 | 1.35 | 4 | 1 |
| Comparative example 4 | D50 | 0.85 | 2 | 1 |
| Comparative example 5 | D50 | 2.05 | 1 | 5 |
| Comparative example 6 | D64 | 1.05 | 3 | 1 |
| Comparative example 7 | D30 | 2.4 | 3 | 1 |
From the data in table 1, it can be seen that: when the addition amount of each component in the preparation raw materials is within the specific range set by the invention, the obtained solder joint protective adhesive has excellent comprehensive performance and can be used as UV color-changing pin adhesive; specifically, the hardness of the solder joint protective glue obtained in examples 1 to 6 is in the range of D40 to D60, the curing depth exceeds 1mm, the repairing performance can reach 1 level, and the color change can be identified by naked eyes.
As can be seen from comparative examples 1 and comparative examples 1 to 2, when the amount of urethane acrylate oligomer added is small and the amount of acrylate monomer added is large (comparative example 1), the obtained solder joint protective adhesive has poor curing depth, and when the amount of urethane acrylate oligomer added is large and the amount of acrylate monomer added is small (comparative example 2), the obtained solder joint protective adhesive has low hardness, and is easily broken and remains on the PIN foot due to the soft adhesive tape during repair; as can be seen from comparative examples 1 and 3, the solder joint protective paste obtained without adding epoxy resin has poor repairing performance and serious residual paste phenomenon, and greatly influences repairing effect; further comparing example 1 with comparative examples 4 to 5, it was found that when the addition amount of the UV color change material was too large (comparative example 4), the obtained solder joint protective paste had poor curing depth and the reworking performance was also affected to some extent, whereas when the raw material for preparation was not added with the UV color change material, the obtained solder joint protective paste (comparative example 5) had no color change; finally, as can be seen from comparative examples 1 and 6 to 7, when all the oligomers added in the preparation raw materials are multifunctional urethane acrylate oligomers (comparative example 6), the hardness of the obtained solder joint protective adhesive is relatively high, the adhesive tape is relatively hard and easily broken during repair, so that the adhesive residue is caused, and when all the oligomers are difunctional urethane acrylate oligomers (comparative example 7), the hardness of the solder joint protective adhesive is relatively low, and the adhesive tape is relatively soft during repair, and is easily broken and remains on the PIN; and in both cases, the reworking performance is poor.
The applicant states that the present invention is described by way of the above examples as a photochromic solder joint protective paste, and a method of preparing and using the same, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (23)
1. The photochromic solder joint protective adhesive is characterized by comprising the following raw materials in parts by weight: 25-45 parts of monofunctional acrylate monomer, 30-50 parts of difunctional polyurethane acrylate oligomer, 10-25 parts of multifunctional polyurethane acrylate oligomer, 1-5 parts of photoinitiator, 1-4 parts of epoxy resin and 2-5 parts of UV color-changing powder;
the UV color-changing powder is an ultraviolet sensitive material, the initial color is semitransparent and milky white, the color becomes other colors after absorbing ultraviolet rays, and the color depth deepens along with the increase of the ultraviolet irradiation time.
2. The solder joint protective paste of claim 1, wherein the monofunctional acrylate monomer comprises any one or a combination of at least two of isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, tetrahydrofuranacrylate, tetrahydrofuranmethacrylate, dodecyl acrylate, dodecyl methacrylate, or isodecyl acrylate.
3. Solder joint protective glue according to claim 1, characterized in that the difunctional urethane acrylate oligomer comprises a difunctional aliphatic urethane acrylate oligomer and/or a difunctional aromatic urethane acrylate oligomer.
4. The solder joint protective paste of claim 1, wherein the multifunctional urethane acrylate oligomer comprises a 6-9 functionality urethane acrylate oligomer.
5. The solder joint protective paste of claim 1, wherein the multifunctional urethane acrylate oligomer comprises a multifunctional aliphatic urethane acrylate oligomer and/or a multifunctional aromatic urethane acrylate oligomer.
6. The solder joint protective paste of claim 1, wherein the photoinitiator comprises any one or a combination of at least two of 1-hydroxycyclohexylphenyl ketone, 2,4,6- (trimethylbenzoyl) diphenyl phosphate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-phenylbenzyl-2-dimethyl-amine-1- (4-morpholinylphenyl) butanone, methyl benzoate, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-isopropylthioxanthone, benzoin dimethyl ether, dimethylbenzoyl ketal, or benzophenone.
7. The paste as claimed in claim 6, wherein the photoinitiator is a combination of 1-hydroxycyclohexyl phenyl ketone and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
8. The solder joint protective paste of claim 1, wherein the epoxy resin comprises bisphenol a epoxy resin or bisphenol F epoxy resin.
9. The welding spot protection glue according to claim 1, wherein the raw materials for preparing the welding spot protection glue further comprise any one or a combination of at least two of an antioxidant, a dispersing agent and a filler.
10. The welding spot protection glue according to claim 9, wherein the content of the antioxidant in the preparation raw material of the welding spot protection glue is 0-1 weight part and is not equal to 0.
11. The welding spot protection glue according to claim 9, wherein the content of the dispersing agent in the preparation raw material of the welding spot protection glue is 0-2 parts by weight and is not equal to 0.
12. The welding point protection glue according to claim 9, wherein the filler content in the raw material for preparing the welding point protection glue is 0-5 parts by weight and is not equal to 0.
13. A method for preparing the solder joint protective paste according to any one of claims 1 to 12, comprising the steps of:
(1) Mixing a monofunctional acrylate monomer, a difunctional urethane acrylate oligomer and a multifunctional urethane acrylate oligomer to obtain a transparent mixture;
(2) Mixing the transparent mixture obtained in the step (1), a photoinitiator and epoxy resin to obtain a uniform mixture;
(3) Mixing the uniform mixture obtained in the step (2), UV color-changing powder, optional antioxidant, optional dispersing agent and optional filler to obtain the solder joint protective adhesive.
14. The method of claim 13, wherein the mixing of step (1) is performed under stirring.
15. The method according to claim 14, wherein the mixing in the step (1) is performed under stirring at a rotation speed of 100 to 4000 rpm.
16. The method of claim 13, wherein the temperature of the mixing in step (1) is 10 to 40 ℃.
17. The method of claim 13, wherein the mixing in step (1) is for a period of 10 to 60 minutes.
18. The method of claim 13, wherein the mixing of step (2) is performed under stirring.
19. The method according to claim 18, wherein the mixing in the step (2) is performed under stirring at a rotation speed of 1000 to 3000 rpm.
20. The method of claim 13, wherein the temperature of the mixing in step (2) is 20 to 40 ℃.
21. The method of claim 13, wherein the mixing in step (2) is for 15 to 40 minutes.
22. Use of a photochromic solder joint protective paste according to any one of claims 1 to 12 in module assembly.
23. The use of claim 22, wherein the use comprises a pin paste for use in module assembly.
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