Acid-corrosion-resistant protective glue and preparation method thereof

Abstract

The invention belongs to the field of protective glue, and particularly relates to acid-corrosion-resistant protective glue and a preparation method thereof. The acid-corrosion-resistant protective glue is prepared from the following raw materials by mass: 1 to 2 g of acrylic monomer, 90 to 100 g of acrylate monomer, 100 to 200 g of diluent, 0.1 to 0.3 g of initiator, 0.1 to 0.3 g of catalyst, 10 to 50 g of solvent, 0.1 to 0.5 g of polymerization inhibitor and 10 to 30 g of functional raw material with carboxyl. Wherein the functional raw material with carboxyl is prepared from the following raw materials: an acrylic monomer, tackifying resin, a solvent and an initiator. The acid-corrosion-resistant protective glue prepared by the invention has excellent adhesive property and acid corrosion resistance, does not have residual glue after being used, and is particularly suitable for chip etching processing.

Description

Technical Field

[0001] The present invention belongs to the field of protective adhesives, and particularly relates to an acid-resistant corrosion protective adhesive and a preparation method thereof. Background Art

[0002] Acid-resistant etching protective adhesives have extensive application value in the high-end manufacturing field, including precision machining, optical manufacturing, and semiconductor manufacturing fields. In these fields, the protective adhesive plays a crucial role. It can effectively prevent the etching solution from causing chemical corrosion damage to the surface of the workpiece, thereby ensuring the stability of the processing quality and precision. The reasonable use of the protective adhesive greatly improves the quality and reliability of the product.

[0003] In practical applications, the use steps of acid-resistant etching protective adhesives need to strictly follow a certain order. Before the etching operation, the protective adhesive must be evenly coated on the surface of the workpiece to ensure that it can firmly adhere to the workpiece. After the coating is completed, the protective adhesive can play an isolation and protection role during the etching process, preventing the etching solution from directly contacting the surface of the workpiece, thereby avoiding any damage to the workpiece.

[0004] The protective adhesive is mainly coated on the release film, and then through film transfer, the adhesive film is transferred to a specific film. During the chip etching process, the protective adhesive film will be attached to the wafer to be protected, and then the acid etching operation is carried out. The whole process usually only takes a few minutes to complete. The etching solution for acid etching usually consists of strong acids such as concentrated sulfuric acid, nitric acid, hydrofluoric acid, and hydrochloric acid. Therefore, there are extremely high requirements for the acid-resistant corrosion performance of the protective adhesive. During the etching process, it is required that there is a high peel strength between the adhesive film and the wafer, and the joint must be tight and leak-free to prevent the acidic etching solution from penetrating in, thereby ensuring that the protected part is not etched by strong acids. At present, the relevant high-performance raw materials in this field are mainly provided by Japanese companies. For example, the patent CN103842461A applied by Nippon Electric Glass Co., Ltd. discloses a protective sheet for glass etching, and there are relatively few relevant reports on acid-resistant corrosion protective adhesives in China. Summary of the Invention

[0005] To solve the above technical problems, in the first aspect of the present invention, an acid-resistant corrosion protective adhesive is provided, and its preparation raw materials include: 1-2 g of acrylic monomer, 90-100 g of acrylate monomer, 100-200 g of diluent, 0.1-0.3 g of initiator, 0.1-0.3 g of catalyst, 10-50 g of solvent, 0.1-0.5 g of inhibitor, and 10-30 g of functional raw material with carboxyl group.

[0006] As an implementable case, the preparation raw materials of the functional raw material with carboxyl group include, by mass: 20-40 parts of acrylic monomer, 5-20 parts of tackifying resin, 50-80 parts of solvent, and 0.1-0.5 parts of initiator.

[0007] As an implementable case, the acrylic monomer includes acrylic acid and / or methacrylic acid.

[0008] Furthermore, the acrylic monomer includes acrylic acid and methacrylic acid.

[0009] Furthermore, the mass ratio of the acrylic acid to the methacrylic acid is (1 - 2):1.

[0010] As an implementable case, the acrylate monomer includes one or more of butyl acrylate, isooctyl acrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, 2-hydroxypropyl acrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

[0011] Furthermore, the acrylate monomer is butyl acrylate, isooctyl acrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate.

[0012] Furthermore, the mass ratio of the butyl acrylate, isooctyl acrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate is (10 - 25):(60 - 75):(3 - 10):(0.5 - 2):(0.5 - 2):(1 - 10).

[0013] In the present invention, the mass ratio of the acrylic monomer to the acrylate monomer is defined as (1 - 2):(90 - 100), which can ensure that the protective adhesive has excellent bonding performance while further reducing the residual adhesive situation after the use of the protective adhesive. The inventors speculate that: a small amount of acrylic monomer can significantly improve the bonding strength of the protective adhesive through polar groups, but excessive use will lead to over-crosslinking, resulting in a hardening of the colloid, a decrease in flexibility, an excessive interfacial bonding strength, and an easy residue of the adhesive layer on the substrate surface during peeling. A high proportion of acrylate monomer ensures that the colloid has sufficient flexibility and a low glass transition temperature (Tg), so that during peeling, the colloid breaks mainly by itself rather than the colloid detaching from the substrate, thereby reducing the residual adhesive. When the mass ratio of the acrylic monomer to the acrylate monomer is (1 - 2):(90 - 100), through the synergistic effect of polar groups and flexible chain segments, the best balance between bonding performance and residual adhesive rate is achieved. This ratio can not only meet the high adhesion requirements of the protective adhesive but also reduce the occurrence of residual adhesive through the cohesive fracture mechanism of flexible chain segments.

[0014] As an implementable case, the solvent includes one or more of dichloromethane, ethyl acetate, chloroform, and toluene.

[0015] Further, the solvent is toluene.

[0016] As an implementable case, the diluent includes one or more of: dichloromethane, ethyl acetate, chloroform, toluene.

[0017] Further, the diluent is toluene.

[0018] As an implementable case, the initiator includes one or more of: ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide (BPO), lauroyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, tert-butyl peroxybenzoate, cumene hydroperoxide, tert-butyl hydroperoxide.

[0019] Further, the initiator is BPO.

[0020] As an implementable case, the catalyst includes one or more of: triethylamine, N,N-dimethylbenzylamine, 2-methylpyridine, tetramethylammonium chloride.

[0021] Further, the catalyst is tetramethylammonium chloride.

[0022] As an implementable case, the inhibitor includes one of: hydroquinone, p-benzoquinone, monomethyl ether of hydroquinone.

[0023] Further, the inhibitor is hydroquinone.

[0024] Further, the tackifying resin includes one of: petroleum resin, phenolic resin, rosin resin, polyurethane resin.

[0025] Further, the tackifying resin is petroleum resin.

[0026] Further, the petroleum resin is C5 petroleum resin.

[0027] Further, the preparation method of the functional raw material with carboxyl group includes: adding acrylic monomer, tackifying resin, initiator, and solvent into a reaction kettle, heating to 75 - 90 °C, reacting for 6 - 10 h, then cooling to 20 - 30 °C, filtering and discharging to obtain.

[0028] Acrylic acid and methacrylic acid can undergo chemical cross-linking polymerization through an initiator to form a spatial macromolecule. The combined action of the cross-linking network and the hydrophobic C5 petroleum resin prevents the acidic etching solution from penetrating into the material interior. Through the chemical stability of the carboxyl monomer, the structural compactness of the cross-linking network, as well as the hydrophobicity and toughening effect of the C5 petroleum resin, the protective glue is endowed with excellent acid corrosion resistance.

[0029] The second aspect of the present invention provides a method for preparing an acid corrosion-resistant protective glue, which includes: mixing acrylic monomers, acrylate monomers, diluents, initiators, catalysts, solvents, inhibitors, and functional raw materials with carboxyl groups to obtain the product.

[0030] Further, the method for preparing the acid corrosion-resistant protective glue includes: adding butyl acrylate, isooctyl acrylate, butyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate into a reaction kettle, adding ethyl acetate, heating up to 60 - 75 °C, adding 50 - 70% of the total amount of BPO, continuing to heat up to 80 - 85 °C, reacting for 3 - 5 h, adding the remaining BPO, heating up to 90 - 95 °C, and reacting for 2 - 3 h; then adding tetramethylammonium chloride, toluene, hydroquinone, and functional raw materials with carboxyl groups, continuing to react for 8 - 10 h, cooling down to 20 - 30 °C, filtering and discharging, and packaging.

[0031] Beneficial effects

[0032] (1) Through specific formulation design, the acid corrosion-resistant protective glue prepared by the present invention has excellent bonding performance, can firmly adhere to the surfaces of various workpieces, and ensures that it will not fall off or fail during the etching process.

[0033] (2) Although general high-adhesion resin glues have a linear structure and a relatively small molecular weight, their acid corrosion resistance is generally average. To improve the acid corrosion resistance, it is necessary to properly match the molecular weight distribution and reaction raw material monomers, so as to achieve a balance among adhesion, residual glue performance, and acid corrosion resistance. In the present invention, the mass ratio of acrylic monomers to acrylate monomers is defined as (1 - 2) : (90 - 100), and further, the acrylate monomers are a compound of butyl acrylate, isooctyl acrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate, which can achieve the optimal dynamic balance among high bonding performance, no residual glue performance, and acid corrosion resistance.

[0034] (3) When the protective glue colloid prepared by the present invention is peeled off, it mainly breaks by itself rather than falling off from the substrate surface, so the appearance of residual glue is reduced; a low residual glue rate helps to keep the surface of the workpiece clean and intact, and reduces the difficulty of subsequent processing work.

[0035] (4) Due to the addition of specific functional raw materials with carboxyl groups, the protective glue provided by the present invention has excellent acid corrosion resistance, can remain stable in a strong acid environment for a long time, effectively prevents the penetration of acidic etching solution into the material interior, and thus protects the workpiece from being damaged by the acidic etching solution.

[0036] (5) All the raw materials used in the present invention are relatively conventional, with low costs, and the preparation method is relatively simple, without the need for complex and expensive instruments and equipment. Therefore, the protective glue product can be mass-produced to replace imported products of the same type. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a schematic diagram of the appearance of the acid-resistant protective glue film obtained in Example 1 after the residual glue test.

[0038] Figure 2 It is a schematic diagram of the appearance after the acid resistance test of Example 1.

[0039] Figure 3 It is a schematic diagram of the appearance of the protective glue film obtained in Comparative Example 1 after the residual glue test. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0040] Example 1

[0041] In the first aspect of this example, an acid-resistant protective glue is provided. The raw materials for its preparation are as follows by mass: 24 g of butyl acrylate, 60 g of isooctyl acrylate, 6 g of butyl methacrylate, 0.5 g of methacrylic acid, 0.5 g of acrylic acid, 1.5 g of 2-hydroxyethyl methacrylate, 1.5 g of 2-hydroxyethyl acrylate, 8 g of glycidyl acrylate, 100 g of ethyl acetate, 0.3 g of BPO, 0.1 g of tetramethylammonium chloride, 20 g of toluene, 0.3 g of hydroquinone, and 20 g of a functional raw material with a carboxyl group.

[0042] The raw materials for the preparation of the functional raw material with a carboxyl group are specifically: acrylic acid, methacrylic acid, C5 petroleum resin, toluene, BPO; the mass ratio of acrylic acid, methacrylic acid, C5 petroleum resin, toluene, BPO is 20:10:10:50:0.4.

[0043] The C5 petroleum resin is purchased from Puyang Ruisen Petroleum Resin Co., Ltd.

[0044] The preparation method of the functional raw material with a carboxyl group includes: adding acrylic monomers, tackifying resins, initiators, and solvents to a reaction kettle, heating to 80°C, reacting for 8 h, then cooling to 25°C, filtering and discharging to obtain the product.

[0045] In the second aspect of this example, a preparation method of an acid-resistant protective glue is provided, specifically:

[0046] Add butyl acrylate, isooctyl acrylate, butyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate into a reaction kettle, add ethyl acetate, heat up to 60°C, add 0.2 g of BPO, continue to heat up to 80°C, react for 4 h, add the remaining BPO, heat up to 90°C, and react for 2 h; then add tetramethylammonium chloride, toluene, and hydroquinone, and the functional raw material with a carboxyl group, continue to react for 8 h, cool down to 25°C, filter and discharge the material, and package.

[0047] Example 2

[0048] The specific implementation method of this example is the same as that of Example 1. The difference is that the raw materials for preparing the protective colloid are as follows by mass: 25 g of butyl acrylate, 65 g of isooctyl acrylate, 7 g of butyl methacrylate, 0.6 g of methacrylic acid, 0.6 g of acrylic acid, 2 g of 2-hydroxyethyl methacrylate, 2 g of 2-hydroxyethyl acrylate, 6 g of glycidyl acrylate, 100 g of ethyl acetate, 0.3 g of BPO, 0.1 g of tetramethylammonium chloride, 20 g of toluene, 0.3 g of hydroquinone, and 20 g of the functional raw material with a carboxyl group.

[0049] Comparative Example 1

[0050] In the first aspect of this example, a protective colloid is provided. The raw materials for its preparation are as follows by mass: 14 g of butyl acrylate, 73 g of isooctyl acrylate, 3 g of butyl methacrylate, 1.5 g of methacrylic acid, 1.5 g of acrylic acid, 0.5 g of 2-hydroxyethyl methacrylate, 0.5 g of 2-hydroxyethyl acrylate, 4 g of glycidyl acrylate, 120 g of ethyl acetate, 0.3 g of BPO, 0.1 g of tetramethylammonium chloride, 20 g of toluene, 0.3 g of hydroquinone, and 20 g of the functional raw material with a carboxyl group.

[0051] The raw materials for the functional raw material with a carboxyl group are specifically: acrylic acid, C5 petroleum resin, toluene, BPO; the mass ratio of acrylic acid, C5 petroleum resin, toluene, BPO is 30:10:60:0.4.

[0052] The C5 petroleum resin is purchased from Puyang Ruisen Petroleum Resin Co., Ltd.

[0053] The preparation method of the functional raw material with a carboxyl group includes: adding acrylic acid monomer, tackifying resin, initiator, and solvent into a reaction kettle, heating up to 80°C, reacting for 8 h, then cooling down to 25°C, filtering and discharging the material to obtain it.

[0054] In the second aspect of this example, a method for preparing a protective colloid is provided, specifically:

[0055] Add butyl acrylate, isooctyl acrylate, butyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and glycidyl acrylate into a reaction kettle, add ethyl acetate, heat up to 60 °C, add 0.2 g of BPO, continue to heat up to 80 °C, react for 4 h, add the remaining BPO, heat up to 90 °C, and react for 2 h; then add tetramethylammonium chloride, toluene, and hydroquinone, and the functional raw material with a carboxyl group, and continue to react for 8 h. Cool down to 25 °C, filter and discharge, and package.

[0056] Performance Test

[0057] 1. Bonding Performance Test

[0058] Test Object: Acid-resistant Corrosion Protection Adhesives Prepared in Examples 1-2 and Comparative Example 1.

[0059] Test Method: After applying the acid-resistant corrosion protection adhesive to the coating film, stick it on a stainless steel plate. After 20 min, test the 180° peel strength. The test results are shown in Table 1; where the 180° peel strength not less than 1 N / 2.5 cm is qualified.

[0060] 2. Residual Adhesive Test

[0061] Test Object: Acid-resistant Corrosion Protection Adhesives Prepared in Examples 1-2 and Comparative Example 1.

[0062] Test Method: After applying the acid-resistant corrosion protection adhesive to the coating film, stick it on a stainless steel plate. After 24 h, peel it off and observe whether there is residual adhesive on the surface. The test results are shown in Table 1. The schematic diagram of the appearance after tearing the adhesive film of the acid-resistant corrosion protection adhesive prepared in Example 1 is as Figure 1 shown; the schematic diagram of the appearance after tearing the adhesive film of the protection adhesive prepared in Comparative Example 1 is as Figure 3 shown.

[0063] 3. Acid-resistant Corrosion Performance Test

[0064] Test Object: Protection Adhesives Prepared in Examples 1-2 and Comparative Example 1.

[0065] Test Method: Apply the acid-resistant corrosion protection adhesive to the chip to be etched, and then use an acidic etching solution for etching. Observe whether the chip components are corroded. The test results are shown in Table 1. The schematic diagram of the appearance after the acid-resistant corrosion performance test of Example 1 is as Figure 2 shown.

[0066] Table 1

[0067]

[0068]

[0069] As can be seen from the experimental results in Table 1, the acid-resistant corrosion protection glue prepared by the present invention has excellent bonding performance, acid-resistant corrosion performance, and no residual glue after use. The product is particularly suitable for chip etching processing.

Claims

1. An acid corrosion resistant protective adhesive, characterized in that: The raw materials for preparation include, by weight, 1-2 g of acrylic acid monomer, 90-100 g of acrylate monomer, 100-200 g of diluent, 0.1-0.3 g of initiator, 0.1-0.3 g of catalyst, 10-50 g of solvent, 0.1-0.5 g of inhibitor, and 10-30 g of functional raw materials with carboxyl groups.

2. The acid corrosion resistant protective glue according to claim 1, characterized in that: The acrylic acid monomer includes acrylic acid and / or methacrylic acid.

3. The acid corrosion resistant protective glue according to claim 2, characterized in that: The acrylic acid monomers include acrylic acid and methacrylic acid, and the mass ratio of acrylic acid to methacrylic acid is (1-2):

1.

4. The acid corrosion resistant protective glue according to claim 1, characterized in that: The acrylic acid ester monomers include one or more of butyl acrylate, isooctyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, glycidyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, hydroxypropyl acrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

5. The acid corrosion resistant protective glue according to claim 4, characterized in that: The acrylic acid ester monomers are butyl acrylate, isooctyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and glycidyl acrylate; the mass ratio of butyl acrylate, isooctyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and glycidyl acrylate is (10-25): (60-75): (3-10): (0.5-2): (0.5-2): (1-10).

6. The acid corrosion resistant protective glue according to claim 1, characterized in that: The catalyst comprises one or more of triethylamine, N,N-dimethylbenzylamine, 2-methylpyridine and tetramethylammonium chloride.

7. The acid corrosion resistant protective adhesive according to any one of claims 1 to 6, characterized in that: The raw materials for preparing the functional raw material with carboxyl group include 20-40 parts of acrylic acid monomer, 5-20 parts of tackifying resin, 50-80 parts of solvent and 0.1-0.5 parts of initiator according to the weight percentage.

8. The acid corrosion resistant protective adhesive according to claim 7, characterized in that: The tackifying resin includes one of petroleum resin, phenolic resin, rosin resin and polyurethane resin.

9. The acid corrosion resistant protective adhesive according to claim 7, characterized in that: The preparation method of the functional raw material with carboxyl group comprises: Add acrylic acid monomer, tackifying resin, initiator and solvent into a reaction kettle, heat to 75-90°C, react for 6-10h, then cool to 20-30°C, filter out the material and obtain the product.

10. A method for preparing the acid corrosion resistant protective glue according to any one of claims 1 to 9, characterized in that: include: The preparation method is obtained by mixing acrylic acid monomer, acrylic ester monomer, diluent, initiator, catalyst, solvent, inhibitor and functional raw material with carboxyl group.

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