CN113814575A

CN113814575A - Laser cutting protection liquid and preparation method and application thereof

Info

Publication number: CN113814575A
Application number: CN202111091744.5A
Authority: CN
Inventors: 易玉玺; 黄明起; 夏建文; 刘彬灿; 叶振文; 刘献伟
Original assignee: Shenzhen Samcien Semiconductor Materials Co ltd
Current assignee: Shenzhen Samcien Semiconductor Materials Co ltd
Priority date: 2021-09-17
Filing date: 2021-09-17
Publication date: 2021-12-21

Abstract

The invention provides a laser cutting protection solution and a preparation method and application thereof, wherein the laser cutting protection solution comprises a combination of water-soluble resin, an azeotropic solvent, polyhydric alcohol, a water-soluble ultraviolet absorbent, a water-soluble antioxidant, a pH regulator and an anticorrosive agent; the azeotropic solvent consists of water and a high-boiling-point solvent with the boiling point higher than 145 ℃, and the mass ratio of the water to the high-boiling-point solvent is (3-11): 1; the laser cutting protection solution solves the problem that the existing cutting protection solution is serious in carbonization residue after use by using an azeotropic solvent, adding polyhydric alcohol, a water-soluble ultraviolet absorbent and a water-soluble antioxidant and utilizing the mutual synergistic effect of the components, and is beneficial to improving the photoelectric performance of a chip.

Description

Laser cutting protection liquid and preparation method and application thereof

Technical Field

The invention belongs to the technical field of laser cutting, and particularly relates to a laser cutting protection solution, and a preparation method and application thereof.

Background

With the continuous expansion of the high-brightness LED market, the improvement of the productivity, efficiency and yield of products becomes the current primary problem; in the process of a plurality of small chips, a diamond scribing knife is generally adopted, and a high-speed rotating cutter is utilized to rotate so as to drive a blade arranged on the cutter to cut the cut chip, so that the separation action is realized; when some high-hardness chips are cut, the chips must be cut and grooved by laser in advance, and the laser ablation processing has the balance of efficiency, qualification rate and cost; however, as the feature size of semiconductor integrated circuits is continuously reduced, during the separation process, the chip surface is likely to remain with impurities such as wax layer, dirt, and circuit oxidation residue, and the remaining impurities contain active oxidation components, which adhere to the chip surface for a long time, and thus some substances on the chip surface are likely to be oxidized, and even the edge of the chip is likely to be driven to be cracked under the gravity action of the dirt impurities.

Therefore, in order to avoid the problem of damage to the substrate silicon wafer caused by laser cutting and improve the yield of semiconductor products and the cutting efficiency, a protective film needs to be formed by coating a protective solution on the surface of the substrate before laser processing, so that other areas of the chip can be well protected in the processing process to inhibit the adhesion of fragments on the surface of the LED chip, and the requirements of narrow cutting path and chip miniaturization can be realized as far as possible in addition to meeting the cutting protection of sapphire, gallium arsenide, silicon carbide, semiconductor wafers and the like.

In the prior art, a lot of protective liquid and research and reports are provided for chip laser cutting. CN109207272A chip laser cutting protective solution, which comprises a surfactant, an organic cleaning agent, an organic solvent, a corrosion inhibitor and a coupling agent. When the laser cutting chip is used, the laser cutting protection liquid is scattered on the surface of the chip and uniformly diffused to the whole surface of the chip. The surfactant component and the organic solvent can decompose substances remained on the surface of the chip into tiny particles or chemical reaction, and the tiny particles or the chemical reaction are dissolved in the organic cleaning agent solution to achieve the cleaning capability of the surface of the chip. Meanwhile, the laser cutting protection liquid is diffused on the surface of the chip to form an organic protection film, so that the edge breakage phenomenon of the chip caused by cutting at high temperature is prevented. The corrosion inhibitor can prevent the metal circuit on the surface of the chip from being oxidized at high temperature to prevent the metal circuit from being oxidized by an oxide. CN107118825A discloses a cutting protection solution and a cutting method for a light-emitting diode, belonging to the technical field of photoelectrons. The cutting protection liquid comprises a nonionic surfactant, propylene glycol and water, wherein the mass fraction of the nonionic surfactant is 3-30%, the mass fraction of the propylene glycol is 5-35%, the mass fraction of the water is 35-92%, the cutting protection liquid and deionized water are mixed and used in the process of cutting the light-emitting diode, the deionized water can cool and clean a cutter wheel and a wafer, overheating of the cutter wheel or the wafer is avoided, scraps are timely removed, the nonionic surfactant and the propylene glycol can lubricate the cutter wheel and the wafer in the cutting process, abrasion of the cutter wheel is reduced, meanwhile, the edge crack condition of a single LED can be reduced, and therefore the yield of products is improved. CN112831261A discloses a protective liquid film composition for laser-induced supercritical fluid ablation processing and a laser cutting process, belonging to the technical field of chemical reagents and processing processes for semiconductor processing. The composition mainly comprises a matrix mixture capable of generating supercritical liquid through laser induction, a cooling agent, a wetting agent, a defoaming agent and water, wherein the protective liquid film composition is spin-coated on the processed surface of a material when in use, laser penetrates through a liquid film to irradiate the surface of the material and induces the composition to generate the supercritical liquid, and debris generated by laser ablation, and melt and crater height accumulated around an action area can be effectively removed.

However, the conventional protective solution for laser dicing causes a problem that a large amount of dicing street residues are carbonized and left on the surface of the substrate, and the substrate material is contaminated seriously, which affects the use thereof.

Therefore, the development of a laser cutting protection solution with low carbon residue is an urgent technical problem to be solved by those skilled in the art.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a laser cutting protective solution and a preparation method and application thereof, and the laser cutting protective solution solves the problem that the surface of a chip is seriously carbonized and remained after the existing cutting protective solution is used, and is beneficial to improving the photoelectric performance of the chip.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a laser cutting protection solution, which comprises a combination of a water-soluble resin, an azeotropic solvent, a polyol, a water-soluble ultraviolet absorber, a water-soluble antioxidant, a pH adjuster, and an anticorrosive agent.

The azeotropic solvent is composed of water and a high-boiling solvent having a boiling point higher than 145 ℃ (for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or 195 ℃ and the like), and the mass ratio of the water to the high-boiling solvent is (3-11) to 1 (for example, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1 and the like).

The azeotropic solvent is formed by blending a high-boiling-point solvent with a boiling point of over 145 ℃ and water, and the azeotropic solvent consisting of water and the high-boiling-point solvent with the boiling point of over 145 ℃ in a mass ratio of (3-11): 1 is added into a laser cutting protection solution, so that on the one hand, the boiling point of the obtained azeotropic solvent can be reduced, and the azeotropic solvent can begin to absorb heat at a low temperature; in a second aspect, the azeotropic solvent can be matched with the polyol in the laser cutting protection solution, so that the heat absorption capacity of the laser cutting protection solution is further improved, and the carbonization residue of the chip when the chip is cut is reduced: in a third aspect, the azeotropic solvent and the polyhydric alcohol are matched to improve the uniformity of the laser cutting protective solution during spin coating.

Besides, the water-soluble resin is selected to mainly form a protective film layer for blocking and adhering debris generated in the laser processing process; the added polyalcohol can not only generate a coordination effect with azeotropy, but also interact with water to provide a large amount of hydrogen bonds, and on one hand, a large amount of hydrogen bond groups can absorb a large amount of heat to prevent excessive carbonization of the film layer; on the other hand, the water-soluble resin has the functions of moisturizing the spin-coated protective film, preventing the film from drying, particularly for water-soluble resin, keeping the solvent of the water-soluble resin nonvolatile, and being beneficial to cleaning.

And finally, a water-soluble ultraviolet absorbent, a water-soluble antioxidant, a pH regulator and an anticorrosive agent are added to be matched with one another, so that the protection effect of the laser cutting protection solution on the substrate material after film formation is promoted, and the generation of carbonization is reduced.

Preferably, the mass percentage of the water-soluble resin in the laser cutting protection solution is 1-20%, for example, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, and the like, and preferably 2-8%.

Preferably, the water-soluble resin includes any one of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone-acetic acid homopolymer, polyethylene oxide, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, or a block copolymer of polyvinyl alcohol-polyacrylic acid, or a combination of at least two thereof.

Preferably, the water-soluble resin has a molecular weight of 150000-1500000 g/mol, such as 350000g/mol, 550000g/mol, 750000g/mol, 850000g/mol, 950000g/mol, 1050000g/mol, 1250000g/mol or 1450000 g/mol.

In the present invention, one kind of water-soluble resin may be used alone, or two or more kinds of water-soluble resins may be used in combination; the molecular weight of the water-soluble resin is selected to be 150000-1500000 g/mol as much as possible, and is recommended to be selected from K60-K90 in the case of polyvinylpyrrolidone. Although the water solubility of the low molecular weight water is better, the cleaning is more convenient, but the heat resistance is insufficient, on the contrary, the heat resistance of the high molecular weight is good, but the water solubility is poor, so that the water-soluble resin can be ensured to have better water-washing effect by adding the polyalcohol into the formula.

Preferably, the mass percentage of the high-boiling-point solvent in the laser cutting protection solution is 5-30%, for example, 7%, 9%, 13%, 16%, 19%, 23%, 26%, or 29%.

Preferably, the solvent comprises any one of diacetone alcohol, n-heptanol, resorcinol diethyl ether, phenyl acetate, ethylene glycol monophenyl ether, diacetone alcohol, ethylene glycol butyl ether, ethylene glycol tertiary butyl ether, diethylene glycol ethyl ether or diethylene glycol butyl ether, or a combination of at least two thereof.

Preferably, the mass percentage of the polyhydric alcohol in the laser cutting protection solution is 0.5-5%, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%, and preferably 0.5-2%.

Preferably, the mass ratio of the azeotropic solvent to the polyhydric alcohol is (85-100): 1, for example, 87:1, 89:1, 91:1, 93:1, 95:1, 97:1 or 99: 1.

Preferably, the polyol comprises any one of glycerol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-propanediol, or polyethylene glycol, or a combination of at least two thereof.

The polyhydric alcohol provided by the invention interacts with water to provide a large amount of hydrogen bonds; on one hand, the spin-coated protective film has the function of moisturizing and prevents the drying of the film layer; on the other hand, a large number of hydrogen bonding groups can absorb a large amount of heat, so that excessive carbonization of the film layer is prevented. In addition, the solvent of the water-soluble resin can be kept nonvolatile, which is beneficial to cleaning;

preferably, the polyethylene glycol has a weight average molecular weight of less than 700g/mol, such as 600g/mol, 500g/mol, 400g/mol, 300g/mol, 200g/mol, 100g/mol or 50g/mol, and the like.

Preferably, the mass percentage of the water-soluble ultraviolet absorber in the laser cutting protection solution is 0.1-1%, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%.

Preferably, the water-soluble ultraviolet absorber includes any one of 4, 4' -2 carboxybenzophenone, benzophenone-4-carboxylic acid, 2-carboxyanthraquinone, 1, 2-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, sodium salt, potassium salt, ammonium salt, 2, 6-anthraquinone disulfonic acid sodium salt or 2, 7-anthraquinone disulfonic acid sodium salt, or a combination of at least two thereof.

The water-soluble ultraviolet absorbent in the laser cutting protection liquid is mainly used for UV laser absorption, so that the wavelength of laser is in the maximum absorption wavelength range of the water-soluble ultraviolet absorbent, and the high-efficiency UV absorption rate of the water-soluble ultraviolet absorbent is ensured; the mass percentage of the water-soluble ultraviolet absorbent in the laser cutting protection liquid is 0.1-1%; on the one hand, if the absorbent is selected to absorb in an inappropriate wavelength range or in an insufficient amount so that the absorption capacity is insufficient, the thermal decomposition of the protective film layer is significantly lower than that of the substrate to be cut, the substrate is preferentially thermally decomposed and gasified, and the pressure generated by gasification causes the protective film to fall off, resulting in the accumulation of chips on the outer peripheral portion of the cut; on the other hand, if the amount is too large to cause too strong ultraviolet absorption capability, the laser light reflected by the substrate also causes thermal decomposition of the protective film, which results in a significant widening of the laser processing width and failure to ensure a narrow and small cutting requirement.

Preferably, the content of the water-soluble antioxidant in the laser cutting protection liquid is 0.1-0.5%, such as 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%.

Preferably, the water-soluble antioxidant comprises any one or a combination of at least two of ascorbic acid, tannic acid, tea polyphenol, cysteine or sodium sulfite; the water-soluble antioxidant mainly improves the heat resistance of the resin and prevents oxidative decomposition of the water-soluble resin during storage.

Preferably, the pH adjuster comprises an organic acid or an organic base.

Preferably, the organic acid comprises any one of formic acid, acetic acid, lactic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, tartaric acid, benzoic acid, salicylic acid, maleic acid or glycolic acid, or a combination of at least two thereof.

Preferably, the organic base comprises any one of or a combination of at least two of monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methyldiethanolamine, monomethylethanolamine, diethyleneglycol amine, dimethylaminopropylamine, N-dimethylcyclohexylamine, ethylenediamine, diethylenetriamine, or triethylenetetramine.

Preferably, the mass percentage of the anticorrosive in the laser cutting protection solution is 0.1-1%, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%, and more preferably 0.1-0.2%.

Preferably, the corrosion inhibitor comprises a metal corrosion inhibitor.

The anticorrosive agent can prevent the electrolyte in the laser cutting film from corroding tin balls, copper surfaces and the like on devices.

Preferably, the metal corrosion inhibitor comprises a heterocyclic non-phosphoric acid metal corrosion inhibitor and/or an organic phosphoric acid metal corrosion inhibitor.

Preferably, the heterocyclic non-phosphoric acid metal corrosion inhibitor comprises any one or a combination of at least two of triazole, benzotriazole, benzothiazole or mercaptobenzothiazole.

Preferably, the organic phosphoric acid metal corrosion inhibitor comprises any one of amino trimethylene phosphonic acid, hydroxy ethylidene diphosphonic acid, ethylene diamine tetra methylene phosphonic acid, 2-phosphoric acid-1, 2, 4-tricarboxylic acid butane or diethylene triamine pentamethylene phosphonic acid or a combination of at least two of the amino trimethylene phosphonic acid, the hydroxy ethylidene diphosphonic acid, the ethylene diamine tetra methylene phosphonic acid, the 2-phosphoric acid-1, 2, 4-tricarboxylic acid butane or the diethylene triamine pentamethylene phosphonic acid.

In a second aspect, the present invention provides a method for preparing the laser cutting protection solution according to the first aspect, wherein the method comprises mixing water-soluble resin, azeotropic solvent and polyol, adding water-soluble antioxidant, water-soluble ultraviolet absorbent and anticorrosive agent, adding pH regulator after dissolving, and filtering to obtain the laser cutting protection solution.

Preferably, the pH value of the system after adding the pH regulator is 2 to 6, such as 2.5, 3, 3.5, 4, 4.5, 5 or 5.5.

The pH value is selected within the range, because the components in the system can more easily form a large amount of hydrogen bond networks under the condition that the pH value is 2-6, and the heat absorption capacity of a film layer after the film is formed can be further improved.

Preferably, the filtering is a filter element with the wavelength of 20-100 nm (such as 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 90 nm).

In a third aspect, the invention provides an application of the laser cutting protection solution in the first aspect in ultraviolet laser cutting, green laser cutting or infrared laser cutting.

Compared with the prior art, the invention has the following beneficial effects:

(1) the laser cutting protection solution provided by the invention is formed by blending a high-boiling-point solvent with a boiling point of over 145 ℃ and water, and the mass ratio of the high-boiling-point solvent to the water is further limited to (3-11): 1, so that the obtained laser cutting protection solution can ensure that the surface of a substrate material has low carbonization residue after being used.

(2) After the chip adopting the laser cutting protection solution provided by the invention is cut, the protection film layer formed by the laser cutting protection solution can be completely removed by using pure water, and the photoelectric property of the chip is not influenced.

(3) The laser cutting protection solution provided by the invention is also added with a water-soluble antioxidant, so that the laser cutting protection solution can be prevented from yellowing in the processes of transportation, storage and use, and the quality guarantee period of the laser cutting protection solution is prolonged.

Drawings

FIG. 1 is a picture of the laser cutting protective solution obtained in example 1 after UV cutting and cleaning;

FIG. 2 is a picture of the laser cutting protection solution obtained in example 2 after UV cutting and cleaning;

FIG. 3 is a picture of the laser cutting protective solution obtained in comparative example 5 after UV cutting and cleaning;

FIG. 4 is a picture of the laser cutting protection solution obtained in comparative example 6 after UV cutting and cleaning;

fig. 5 is a picture after UV cutting cleaning using the laser cutting protection solution obtained in comparative example 7.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Preparation example 1

An azeotropic solvent having an azeotropic point of 97.2 ℃ and comprising water and propylene glycol methyl ether in a mass ratio of 80.5: 19.5.

Preparation example 2

An azeotropic solvent having an azeotropic point of 98.8 ℃ and comprising water and diacetone alcohol in a mass ratio of 87.3: 12.7.

Preparation example 3

An azeotropic solvent having an azeotropic point of 98.7 ℃ and comprising water and n-heptanol in a mass ratio of 83: 17.

Preparation example 4

An azeotropic solvent having an azeotropic point of 99.7 ℃ and comprising water and resorcinol diethyl ether in a mass ratio of 91: 9.

Preparation example 5

An azeotropic solvent having an azeotropic point of 98.9 ℃ and comprising water and resorcinol diethyl ether in a mass ratio of 75.1: 24.9.

Comparative preparation example 1

An azeotropic solvent comprises water and propylene glycol methyl ether in a mass ratio of 60: 40.

Comparative preparation example 2

An azeotropic solvent comprises water and propylene glycol methyl ether in a mass ratio of 95: 5.

Example 1

The laser cutting protection solution comprises the following components in percentage by weight: 8% of water-soluble resin (polyvinylpyrrolidone, number average molecular weight of 1500000g/mol), 88% of azeotropic solvent (preparation example 1), 1% of propylene glycol, 0.5% of water-soluble ultraviolet absorbent (benzophenone-4-carboxylic acid), 0.25% of water-soluble antioxidant (tannic acid), 0.5% of pH regulator (ethanolamine) and 1% of anticorrosive agent (benzotriazole);

the preparation method of the laser cutting protection solution provided by the embodiment comprises the following steps: mixing water-soluble resin, an azeotropic solvent and propylene glycol, adding a water-soluble antioxidant, a water-soluble ultraviolet absorbent and an anticorrosive agent, dissolving, adding a pH regulator to enable the pH value of a system to be 3.5, and filtering by adopting an 80nm filter element to obtain the laser cutting protection solution.

Example 2

The laser cutting protection solution comprises the following components in percentage by weight: 5% of water-soluble resin (polyvinylpyrrolidone, number average molecular weight of 1500000g/mol), 91% of azeotropic solvent (preparation example 2), 0.5% of triethylene glycol, 1% of water-soluble ultraviolet absorber (4, 4' -2 carboxybenzophenone), 0.5% of water-soluble antioxidant (sodium sulfite), 1% of pH regulator (acetic acid) and 0.5% of anticorrosive agent (mercaptobenzothiazole);

the preparation method of the laser cutting protection solution provided by the embodiment comprises the following steps: mixing water-soluble resin, an azeotropic solvent and propylene glycol, adding a water-soluble antioxidant, a water-soluble ultraviolet absorbent and an anticorrosive agent, dissolving, adding a pH regulator to enable the pH value of a system to be 3.5, and filtering by adopting a 20nm filter element to obtain the laser cutting protection solution.

Example 3

The laser cutting protection solution comprises the following components in percentage by weight: 2% of water-soluble resin (polyvinylpyrrolidone, number average molecular weight of 1500000g/mol), 96% of azeotropic solvent (preparation example 3), 0.5% of triethylene glycol, 0.1% of water-soluble ultraviolet absorber (4, 4' -2 carboxybenzophenone), 0.1% of water-soluble antioxidant (sodium sulfite), 1% of pH regulator (acetic acid) and 0.1% of anticorrosive agent (mercaptobenzothiazole);

Example 4

A laser cutting protection solution which is different from example 1 only in that the azeotropic solvent obtained in preparation example 1 is replaced with the azeotropic solvent obtained in preparation example 4, and the other components, the amounts and the preparation method are the same as those of example 1.

Example 5

A laser cutting protection solution which is different from example 1 only in that the azeotropic solvent obtained in preparation example 5 is used instead of the azeotropic solvent obtained in preparation example 1, and the other components, the amounts and the preparation method are the same as those of example 1.

Comparative example 1

A laser cutting protective solution which differs from example 1 only in that the azeotropic solvent obtained in comparative preparation example 1 is used instead of the azeotropic solvent obtained in preparation example 1, and the other components, amounts and preparation methods are the same as those of example 1.

Comparative example 2

A laser cutting protective solution which differs from example 1 only in that the azeotropic solvent obtained in comparative preparation example 2 is used instead of the azeotropic solvent obtained in preparation example 1, and the other components, amounts and preparation methods are the same as those of example 1.

Comparative example 3

A low-carbonization-residue laser cutting protection solution is different from example 1 only in that water is used for replacing an azeotropic solvent in example 1, and other components, the using amount and the preparation method are the same as those in example 1.

Comparative example 4

A low-carbonization-residue laser cutting protection solution is different from the protection solution in the embodiment 1 only in that propylene glycol methyl ether is used for replacing the azeotropic solvent in the embodiment 1, and other components, the using amount and the preparation method are the same as those in the embodiment 1.

Comparative example 5

A low-carbonization-residue laser cutting protection solution is different from that in example 1 in that a water-soluble ultraviolet absorbent is not added, and other components are distributed by 0.5 percent according to the specific proportion in example 1, and the preparation method is the same as that in example 1.

Comparative example 6

The laser cutting protection solution with low carbonization residue is different from the laser cutting protection solution in example 1 in that propylene glycol is not added, 1% of the propylene glycol is distributed according to the specific proportion in example 1, and the preparation method is the same as that of example 1.

Comparative example 7

A low-carbonization-residue laser cutting protection solution is different from that in example 1 in that a water-soluble antioxidant is not added, and other components are distributed by 0.25 percent according to the specific proportion in example 1, and the preparation method is the same as that in example 1.

And (3) performance testing:

coating the laser protection solution on a wafer to be cut or an LED to form a film in a spin coating mode, wherein the spin coating parameters are as follows: 1500-2000 rpm, 30sec, acceleration ACC: 1000, parts by weight; after spin coating, laser cutting is carried out within 3h at room temperature, otherwise, the cleaning is not clean due to excessive volatilization of a protective film solvent; and subsequently, cutting by adopting UV laser. And cleaning with two fluids after cutting for 2-5 min, wherein the condition that no protective film is left is taken as the standard. The ultraviolet laser cutting parameters are that 355nm ultraviolet light is used for cutting, the number of knives is 2, the scribing speed is 400nm/s, and the power is 3.5W and 8W.

The test results obtained by testing the laser cutting protection solutions provided in the embodiments 1 to 2 and the comparative examples 5 to 7 according to the test method are shown in fig. 1 to 5; wherein, fig. 1 is a picture obtained by using the laser cutting protection solution obtained in example 1 and subjected to UV cutting cleaning; FIG. 2 is a picture of the laser cutting protection solution obtained in example 2 after UV cutting and cleaning; FIG. 3 is a picture of the laser cutting protective solution obtained in comparative example 5 after UV cutting and cleaning; FIG. 4 is a picture of the laser cutting protection solution obtained in comparative example 6 after UV cutting and cleaning; FIG. 5 is a picture of the laser cutting protective solution obtained in comparative example 7 after UV cutting and cleaning; as can be seen by comparing FIGS. 1-2 and FIGS. 3-5, the cutting edges in FIGS. 3-5 have obvious black edges caused by carbide accumulation, which proves that the addition of the water-soluble ultraviolet absorber, the polyol and the water-soluble antioxidant in combination with the azeotropic solvent is helpful for reducing the carbonization residue after the chip is cut.

The laser cutting protection solutions provided in examples 1 to 5 and comparative examples 1 to 7 were tested according to the above test method, and the test results are summarized in table 1:

TABLE 1

As can be seen from the data in table 1: the laser cutting protection solution obtained in the embodiments 1 to 5 is qualified after being cut under the power of 3.5W and 8W; and the laser cutting protection solution provided by the comparative examples 1 to 7 can generate serious black edges on the surface of the substrate after cutting under the power of 3.5W and 8W, which proves that more carbide residues exist.

The applicant states that the present invention is described by the above embodiments, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims

1. The laser cutting protection solution is characterized by comprising a combination of water-soluble resin, an azeotropic solvent, polyol, a water-soluble ultraviolet absorbent, a water-soluble antioxidant, a pH regulator and an anticorrosive agent;

the azeotropic solvent consists of water and a high-boiling-point solvent with the boiling point higher than 145 ℃, and the mass ratio of the water to the high-boiling-point solvent is (3-11): 1.

2. The laser cutting protection solution according to claim 1, wherein the mass percentage of the water-soluble resin in the laser cutting protection solution is 1-20%, preferably 2-8%;

preferably, the water-soluble resin comprises any one of or a combination of at least two of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone-acetic acid homopolymer, polyethylene oxide, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, or a block copolymer of polyvinyl alcohol-polyacrylic acid;

preferably, the molecular weight of the water-soluble resin is 150000-1500000 g/mol.

3. The laser cutting protection solution according to claim 1 or 2, wherein the mass percentage of the high-boiling-point solvent in the laser cutting protection solution is 5-30%;

preferably, the high boiling point solvent comprises any one of diacetone alcohol, n-heptanol, resorcinol diethyl ether, phenyl acetate, ethylene glycol monophenyl ether, diacetone alcohol, ethylene glycol butyl ether, ethylene glycol t-butyl ether, diethylene glycol ethyl ether or diethylene glycol butyl ether, or a combination of at least two thereof.

4. The laser cutting protection solution according to any one of claims 1 to 3, wherein the mass percentage of the polyhydric alcohol in the laser cutting protection solution is 0.5 to 5%, preferably 0.5 to 2%;

preferably, the mass ratio of the azeotropic solvent to the polyhydric alcohol is (85-100): 1;

preferably, the polyol comprises any one of glycerol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-propanediol, or polyethylene glycol, or a combination of at least two thereof;

preferably, the polyethylene glycol has a weight average molecular weight of less than 700 g/mol.

5. The laser cutting protection solution according to any one of claims 1 to 4, wherein the mass percentage content of the water-soluble ultraviolet absorber in the laser cutting protection solution is 0.1 to 1%;

6. The laser cutting protection solution according to any one of claims 1 to 5, wherein the mass percentage content of the water-soluble antioxidant in the laser cutting protection solution is 0.1 to 0.5%;

preferably, the water-soluble antioxidant comprises any one of ascorbic acid, tannic acid, tea polyphenol, cysteine or sodium sulfite or a combination of at least two of them.

7. The laser cutting protection solution of any one of claims 1 to 6, wherein the pH regulator comprises an organic acid or an organic base;

preferably, the organic acid comprises any one of formic acid, acetic acid, lactic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, tartaric acid, benzoic acid, salicylic acid, maleic acid or glycolic acid or a combination of at least two thereof;

preferably, the organic base comprises any one or a combination of at least two of monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methyldiethanolamine, monomethylethanolamine, diethyleneglycol amine, dimethylaminopropylamine, N-dimethylcyclohexylamine, ethylenediamine, diethylenetriamine, or triethylenetetramine;

preferably, the mass percentage of the anticorrosive agent in the laser cutting protection liquid is 0.1-1%, and further preferably 0.1-0.2%;

preferably, the corrosion inhibitor comprises a metal corrosion inhibitor;

preferably, the metal corrosion inhibitor comprises a heterocyclic non-phosphoric acid metal corrosion inhibitor and/or an organic phosphoric acid metal corrosion inhibitor;

preferably, the heterocyclic non-phosphoric acid metal corrosion inhibitor comprises any one or a combination of at least two of triazole, benzotriazole, benzothiazole or mercaptobenzothiazole;

8. A preparation method of the laser cutting protection solution as claimed in any one of claims 1 to 7, wherein the preparation method comprises the steps of mixing water-soluble resin, azeotropic solvent and polyol, adding water-soluble antioxidant, water-soluble ultraviolet absorbent and anticorrosive agent, adding pH regulator after dissolving, and filtering to obtain the laser cutting protection solution.

9. The preparation method according to claim 8, wherein the pH value of the system after the pH regulator is added is 2-6, preferably 4-6;

preferably, the filtering adopts a filter element with the diameter of 20-100 nm.

10. The application of the laser cutting protection solution as claimed in any one of claims 1 to 7 in ultraviolet laser cutting, green laser cutting or infrared laser cutting.