Debonding adhesive as well as preparation method and application thereof

Abstract

The invention provides a debonding adhesive as well as a preparation method and application thereof, and the debonding adhesive is prepared from the following raw materials in parts by mass: 15-40 parts of acrylate resin, 12-35 parts of epoxy acrylate dual-curing resin, 10-20 parts of epoxy resin, 5-25 parts of acrylate monomer, 5-15 parts of epoxy diluent, 2-8 parts of photoinitiator and 2-8 parts of assistant. The photoinitiator comprises a free radical photoinitiator and a cationic initiator. According to the invention, the ethylene-epoxy double-group curing component is composed of the components according to the dosage, and the waveband-divided initiator is used for curing, so that the product can be controlled by light sources with different wavebands to be cured step by step, and the initial adhesion and stripping force of the adhesive film are moderate; and the debonding energy is low and no adhesive residue exists.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of adhesives, and particularly relates to a debonding adhesive as well as a preparation method and application thereof. BACKGROUND

[0002] UV debonding adhesive is an adhesive with strong adhesion under normal conditions, and the adhesion can be rapidly reduced after UV irradiation. It has a wide application in the electronic industry, such as surface treatment of computer screens, mobile phones, and cutting of silicon wafers in the chip manufacturing process.

[0003] In the prior art, acrylic pressure-sensitive adhesive is used together with UV curing resin or monomer to achieve initial adhesion, and UV curing reduces adhesion to achieve UV debonding effect. However, the molecular weight of the acrylic pressure-sensitive adhesive is low, and the adhesion has poor high-temperature resistance and solvent resistance before UV curing, and it is difficult to repair and has a risk of residue. SUMMARY

[0004] Therefore, the present application aims to provide a debonding adhesive as well as a preparation method and application thereof. The debonding adhesive contains ethylene-epoxy double groups, and has moderate initial adhesion and peeling force, and debonding energy is 1500 mJ / cm 2 and no residue, and exhibits excellent workability, rapid debonding, no residue, and temporary bonding strength.

[0005] The present application provides a debonding adhesive, which contains the following raw materials in mass fraction:

[0006] 15-40 parts of an acrylic ester resin, 12-35 parts of an epoxy acrylate double-curing resin, 10-20 parts of an epoxy resin, 5-25 parts of an acrylic ester monomer, 5-15 parts of an epoxy diluent, 2-8 parts of a photoinitiator, and 2-8 parts of an additive;

[0007] The photoinitiator includes a free radical photoinitiator and a cationic initiator.

[0008] Preferably, the acrylic resin is selected from one or more of an epoxy-modified acrylic ester resin, a polyurethane acrylic ester resin, and a polyester acrylic ester resin;

[0009] The acrylic ester monomer is selected from one or more of butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, acryloyl morpholine, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0010] Preferably, the epoxy acrylate dual-curing resin is selected from one or more of an epoxy vinyl resin, an epoxy polyurethane acrylate resin, and an epoxy polyester acrylate resin.

[0011] The epoxy resin is selected from one or more of a bisphenol A epoxy resin, a bisphenol F epoxy resin, an aliphatic epoxy resin, and a cycloaliphatic epoxy resin.

[0012] Preferably, the epoxy diluent is selected from one or more of butyl glycidyl ether, glycidyl acrylate, and epoxy polyethylene glycol acrylate.

[0013] The free radical photoinitiator is selected from a long-wave 365 nm~405 nm photoinitiator; and the cationic initiator is selected from a short-wave 340 nm photoinitiator.

[0014] Preferably, the auxiliary agent is selected from one or more of a tackifier, a plasticizer, a toughener, a leveling agent, a defoamer, a polymerization inhibitor, and a stabilizer.

[0015] The present application provides a preparation method of the debonding adhesive described in the above technical solution, comprising the following steps:

[0016] The acrylate resin, the epoxy acrylate dual-curing resin, the epoxy resin, the acrylate monomer, the epoxy diluent, the photoinitiator, and the auxiliary agent are mixed and stirred to obtain the debonding adhesive.

[0017] The present application provides a debonding adhesive film prepared by the following method:

[0018] The debonding adhesive described in the above technical solution is coated on a PET heavy release film to a thickness of 95~105 μm, a PET light release film is attached, and light curing is performed under 395 nm, and aging is performed to obtain the debonding adhesive film.

[0019] Preferably, the energy of the light curing is 1580~1620 J / cm 2 .

[0020] Preferably, the temperature of the aging is 35~45℃, and the time of the aging is 2.5~3 days.

[0021] The present application provides a peeling method of the debonding adhesive film described in the above technical solution, comprising the following steps:

[0022] The debonding adhesive film prepared by the above technical solution is attached to a substrate and pressed, and curing is performed using an electrodeless mercury lamp, with a curing energy of 1950~2050 mJ / cm 2 , and peeling.

[0023] The application provides a debonding adhesive, which comprises the following raw materials in mass parts: 15-40 parts of an acrylate resin, 12-35 parts of an epoxy-based acrylate dual-curing resin, 10-20 parts of an epoxy resin, 5-25 parts of an acrylate monomer, 5-15 parts of an epoxy diluent, 2-8 parts of a photoinitiator and 2-8 parts of an auxiliary agent; the photoinitiator comprises a free radical photoinitiator and a cationic initiator. The product can be controlled to be cured in stages by different waveband light sources, the initial adhesive force and the peeling force of the adhesive film are moderate, and the debonding energy is low and there is no residual adhesive. DETAILED DESCRIPTION

[0024] The application provides a debonding adhesive, which comprises the following raw materials in mass parts:

[0025] 15-40 parts of an acrylate resin, 12-35 parts of an epoxy-based acrylate dual-curing resin, 10-20 parts of an epoxy resin, 5-25 parts of an acrylate monomer, 5-15 parts of an epoxy diluent, 2-8 parts of a photoinitiator and 2-8 parts of an auxiliary agent;

[0026] The photoinitiator comprises a free radical photoinitiator and a cationic initiator.

[0027] The preparation raw materials of the debonding adhesive provided by the application comprise 15-40 parts of an acrylate resin, and the amount can be specifically 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts or 40 parts. The acrylate resin in the application is selected from one or more of an epoxy-modified acrylate resin, a polyurethane acrylate resin and a polyester acrylate resin; preferably, the polyurethane acrylate resin has high flexibility and a TG lower than -20 DEG C. In specific embodiments, the acrylate resin is polyurethane acrylate resin CR93600.

[0028] The preparation raw materials of the debonding adhesive provided by the application comprise 12-35 parts of an epoxy-based acrylate dual-curing resin, and the amount can be specifically 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts. The epoxy-based acrylate dual-curing resin is selected from one or more of an epoxy vinyl resin, an epoxy-based polyurethane acrylate resin and an epoxy-based polyester acrylate resin; preferably, the epoxy-based polyurethane acrylate resin has high flexibility. In specific embodiments, the epoxy-based acrylate dual-curing resin is CR92261.

[0029] The preparation raw material of the debonding adhesive provided by the present application comprises 10-20 parts of epoxy resin, and the specific amount can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts. The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, aliphatic epoxy resin and alicyclic epoxy resin, preferably selected from alicyclic epoxy resin. In a specific embodiment, the epoxy resin is selected from Hexion CYRACURE® UVR-6110 vinyl cyclohexene dioxide.

[0030] The preparation raw material of the debonding adhesive provided by the present application comprises 5-25 parts of acrylic ester monomer, and the specific amount can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts. The acrylic ester monomer is selected from one or more of butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, acryloyl morpholine, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl acrylate, hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

[0031] The preparation raw material of the debonding adhesive provided by the present application comprises 5-15 parts of epoxy diluent, and the specific amount is 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts. The epoxy diluent is preferably selected from one or more of butyl glycidyl ether, glycidyl acrylate, epoxy polyethylene glycol acrylate; more preferably selected from epoxy diluents containing both epoxy and vinyl structures, such as glycidyl acrylate, epoxy polyethylene glycol acrylate.

[0032] The preparation raw material of the debonding adhesive provided by the present application comprises 2-8 parts of a photoinitiator, and the amount can be specifically 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts. The photoinitiator is selected from a free radical photoinitiator and a cationic initiator, and is more preferably selected from one or more of TPO, 819, 1173, 184, 261 and UVI-6976. In the present application, the free radical photoinitiator is preferably a long-wave photoinitiator under 365-405 nm, such as TPO and 819; and the cationic initiator is preferably a short-wave photoinitiator below 340 nm, and such a photoinitiator has substantially no reactivity above 365 nm, such as the UVI-6976 photoinitiator. The combination of the above photoinitiators can achieve the following effects: after UV irradiation of a specific wavelength light source (365-405 nm), such as a 395 nm LED lamp, only the free radical component is activated to achieve a solidification state I (a low-hardness semi-solidification state), and after subsequent UV irradiation of the solidification state I, a 340 nm or lower wavelength UV irradiation light source, such as a mercury lamp, is selected to activate the cationic component to achieve a solidification state II.

[0033] The preparation raw material of the debonding adhesive provided by the present application comprises 2-8 parts of an additive, and the amount can be specifically 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts. The additive is selected from one or more of a tackifier, a plasticizer, a toughener, a leveling agent, a defoaming agent and a stabilizer. The tackifier can improve the adhesion after each solidification. The tackifier is selected from one or more of a terpene resin, a rosin resin, a C9 resin and a phenolic resin; the plasticizer is selected from one or more of naphthenic oil, terephthalate plastic (such as DOTP), epoxy soybean oil and polyolefin oligomer (such as PIB); the toughener is selected from one or more of SBS (styrene-isoprene-styrene block copolymer), polyester elastomer, polyolefin elastomer and SIS (styrene-butadiene-styrene block copolymer); the leveling agent is selected from one or more of BYK333, BYK355, BYK354 and Glide420; the defoaming agent is selected from one or more of BYK055, BYK077 and TEGO Antifoam 920; and the stabilizer is selected from one or more of an antioxidant (such as hindered phenol 1010), a polymerization inhibitor (such as MEHQ) and a phosphite (such as 168).

[0034] In the present application, the epoxy resin and the epoxy diluent are cationic curing components, which can improve the hardness of the adhesive film after solidification and increase the shrinkage stress to achieve the effect of reducing adhesion. The epoxy acrylate dual-curing resin and the epoxy diluent participate in the reaction of free radical curing and cationic curing, which can promote the formation of a three-dimensional network structure of the final cured product to improve the molecular weight and strength of the adhesive film, so as to improve the solvent resistance, increase the strength and improve the mold release property, and reduce the risk of residual glue.

[0035] In a specific embodiment, the raw materials of the debonding adhesive include 30 parts of polyurethane acrylic resin CR93600, 24 parts of polyurethane acrylic resin CR93600, 15 parts of CYRACURE® UVR-6110 epoxy resin, 13 parts of isooctyl acrylate, 10 parts of glycidyl acrylate, 4 parts of a mixture of TPO, 184 and UVI-6976 at a mass ratio of 4:1:2, and 5 parts of rosin resin;

[0036] or the raw materials of the debonding adhesive include 40 parts of polyurethane acrylic resin CR93600, 14 parts of polyurethane acrylic resin CR93600, 20 parts of CYRACURE® UVR-6110 epoxy resin, 20 parts of isooctyl acrylate, 5 parts of glycidyl acrylate, 2 parts of a mixture of TPO, 184 and UVI-6976 at a mass ratio of 4:1:2, and 2 parts of rosin resin;

[0037] or the raw materials of the debonding adhesive include 15 parts of polyurethane acrylic resin CR93600, 29 parts of polyurethane acrylic resin CR93600, 20 parts of CYRACURE® UVR-6110 epoxy resin, 16 parts of isooctyl acrylate, 12 parts of glycidyl acrylate, 8 parts of a mixture of TPO, 184 and UVI-6976 at a mass ratio of 4:1:2, and 5 parts of rosin resin;

[0038] or the raw materials of the debonding adhesive include 25 parts of polyurethane acrylic resin CR93600, 35 parts of polyurethane acrylic resin CR93600, 15 parts of CYRACURE® UVR-6110 epoxy resin, 10 parts of isooctyl acrylate, 8 parts of glycidyl acrylate, 3 parts of a mixture of TPO, 184 and UVI-6976 at a mass ratio of 4:1:2, and 8 parts of rosin resin;

[0039] or the raw materials of the debonding adhesive include 35 parts of polyurethane acrylic resin CR93600, 19 parts of polyurethane acrylic resin CR93600, 10 parts of CYRACURE® UVR-6110 epoxy resin, 25 parts of isooctyl acrylate, 15 parts of glycidyl acrylate, 6 parts of a mixture of TPO, 184 and UVI-6976 at a mass ratio of 4:1:2, and 4 parts of rosin resin.

[0040] The present application provides a preparation method of the debonding adhesive described in the above technical solution, comprising the following steps:

[0041] The acrylate resin, the epoxy acrylate dual-curing resin, the epoxy resin, the acrylate monomer, the epoxy diluent, the photoinitiator and the auxiliary agent are mixed and stirred to obtain the debonding adhesive.

[0042] The present application preferably mixes the acrylate resin, epoxy acrylate dual-curing resin, epoxy resin, acrylate monomer, epoxy diluent, photoinitiator and auxiliary agent at 40-50 DEG C; stirs at 1000-1500 rpm for 30-90 min until the photoinitiator is completely dissolved and the raw materials are uniformly mixed.

[0043] The present application provides a debonding adhesive film prepared by the following method:

[0044] The debonding adhesive film prepared by the above technical solution is coated on a PET heavy release film with a coating thickness of 95-105 mu m, a PET light release film is attached, and light curing is performed under 395 nm, and aging is performed to obtain the debonding adhesive film.

[0045] The present application preferably performs light curing under a 395 nm LED lamp; the energy of the light curing is 1580-1620 J / cm 2 , preferably 1590-1610 J / cm 2 . The present application preferably ages at 40 DEG C for 2.5-3 days, more preferably 3 days.

[0046] The present application performs first light curing when preparing the debonding adhesive film, and the product after the first light curing is in a low-hardness semi-cured state, so that the adhesive film has pressure-sensitive properties and meets the actual production process requirements of customers; meanwhile, the semi-cured state has further reaction components, which can participate in the reaction in the second irradiation curing to form a larger molecular weight product and a more dense network cross-linking structure, thereby avoiding the problems of mutual independence of secondary curing, debonding and film strength or initial adhesion in the prior art.

[0047] The present application prepares the debonding adhesive film by UV curing, and the debonding process of the end customer is also UV curing, which has no solvent and no baking or curing stage at room temperature, thereby greatly improving the production efficiency and energy saving and environmental protection.

[0048] The present application provides a peeling method of the debonding adhesive film prepared by the above technical solution, which comprises the following steps:

[0049] The debonding adhesive film prepared by the above technical solution is attached to a substrate and pressed, and cured by irradiation of a non-polar mercury lamp, and the curing energy is 1950-2050 mJ / cm 2 , and then peeled.

[0050] The present application adopts non-polar mercury lamp irradiation in the debonding process of the customer end to perform second curing, so that a larger molecular weight product and a more dense network cross-linking structure are formed.

[0051] In order to further illustrate the present application, the debonding adhesive, the preparation method and the application thereof provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the present application.

[0052] Examples 1-5 and Comparative Examples 1-2

[0053] According to the dosage in Table 1, acrylate resin (polyurethane acrylate resin CR93600), epoxy acrylate dual-curing resin CR92261, epoxy resin (CYRACURE® UVR-6110), epoxy diluent (glycidyl acrylate), acrylate monomer (isooctyl acrylate), photoinitiator (TPO, 184, and UVI-6976 in a mass ratio of 4:1:2) and additives (rosin resin) are placed in an environment of 40~50℃ and stirred at a speed of 1000~1500 rpm for 30~90 minutes until the photoinitiator is completely dissolved and the raw materials are evenly mixed to obtain the adhesive release agent.

[0054] Table 1

[0055]

[0056] Product testing:

[0057] 1. Preparation of adhesive tape:

[0058] The release adhesives prepared in the examples and comparative examples were coated onto a PET heavy release film with a coating thickness of 100 μm. A PET light release film was then attached to the adhesive, and the mixture was cured using a 395 nm LED light source at a curing energy controlled at 1600 mJ / cm². 2 The adhesive film was obtained by aging at 40℃ for 3 days.

[0059] 2. Performance Testing:

[0060] i. Initial tack: Test the initial tack according to GBT4852-2002.

[0061] ii. 180° peel force: Refer to GB / T 2792-2014 to test the 180° peel force.

[0062] iii. 180° peel strength after unbonding: After pressing the unbonding tape onto the substrate, cure it by irradiation with an electrodeless mercury lamp at a curing energy of 2000 mJ / cm². 2 Then test the 180° peel force.

[0063] iv. Residual Rate: Referring to GB / T 2792-2014, after testing the 180° peel force after unbonding, visually inspect the peeled panel surface under a standard light source (such as D65 standard light source) and evaluate the grade:

[0064] Grade 0: The surface is completely clean, with no visible residue or oil residue.

[0065] Grade 1: The surface has a slight oily sheen or a very small amount of dot-like residue, but it is not sticky to the touch.

[0066] Level 2: The surface has visible, discontinuous residue.

[0067] Level 3: The surface has a large amount of continuous residue.

[0068] The test results of the above examples and comparative examples are shown in Table 2:

[0069] Table 2

[0070]

[0071] As can be seen from Table 2, the initial adhesion and peeling force of the debonding adhesive film prepared by the debonding adhesive prepared in Examples 1-5 are moderate, the debonding energy is less than 1500 mJ / cm 2 and no residue, showing excellent workability, rapid debonding, no residue and temporary bonding strength. Compared with the examples, the initial adhesion and peeling force of Comparative Example 1 are low, the debonding effect of Comparative Example 2 is poor, the residue rate is high, and it is difficult to meet the actual process requirements.

[0072] As can be seen from the above examples, the present application provides a debonding adhesive, which comprises the following raw materials in mass fraction: 15-40 parts of acrylate resin, 12-35 parts of epoxy acrylate dual-curing resin, 10-20 parts of epoxy resin, 5-25 parts of acrylate monomer, 5-15 parts of epoxy diluent, 2-8 parts of photoinitiator and 2-8 parts of auxiliary agent; the photoinitiator comprises a free radical photoinitiator and a cationic initiator. The present application uses the above amount of components to form an ethylene-epoxy dual-base curing component and a waveband initiator curing, so that the product can be controlled by different waveband light sources to realize step-by-step curing, realize moderate initial adhesion and peeling force of the adhesive film, and low debonding energy and no residue. Experimental results show that the initial adhesion of the debonding adhesive film is 10-13; the 180° peeling force is 8-12.5 N / 25 mm; the 180° peeling force after debonding is 0.15-0.34 N / 25 mm; the debonding energy is less than 1500 mJ / cm 2 , and the residue rate is 0.

[0073] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A debonding adhesive, characterized by, by mass, comprising the following raw materials: acrylate resin 15~40 parts, epoxy-based acrylate dual-curing resin 12~35 parts, epoxy resin 10~20 parts, acrylate monomer 5~25 parts, epoxy diluent 5~15 parts, photoinitiator 2~8 parts and auxiliary agent 2~8 parts; The photoinitiator comprises a free radical photoinitiator and a cationic initiator.

2. The debonding adhesive according to claim 1, wherein The acrylate resin is selected from one or more of an epoxy-modified acrylate resin, a polyurethane acrylate resin and a polyester acrylate resin; The acrylate monomer is selected from one or more of butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, acryloyl morpholine, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl acrylate, hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

3. The debonding adhesive of claim 1, wherein, The epoxy-based acrylate dual-curing resin is selected from one or more of an epoxy vinyl resin, an epoxy-based polyurethane acrylate resin and an epoxy-based polyester acrylate resin; The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, aliphatic epoxy resin and alicyclic epoxy resin.

4. The debonding adhesive of claim 1, wherein The epoxy diluent is selected from one or more of butyl glycidyl ether, glycidyl acrylate, epoxy-based polyethylene glycol acrylate; The free radical photoinitiator is selected from a long-wave 365nm~405nm photoinitiator; the cationic initiator is selected from a short-wave 340nm or below photoinitiator.

5. The debonding adhesive of claim 1, wherein The auxiliary agent is selected from one or more of tackifier, plasticizer, toughener, leveling agent, defoamer, polymerization inhibitor and stabilizer.

6. A preparation method of the debonding adhesive according to any one of claims 1~5, comprising the following steps: mixing, stirring the acrylate resin, epoxy-based acrylate dual-curing resin, epoxy resin, acrylate monomer, epoxy diluent, photoinitiator and auxiliary agent to obtain the debonding adhesive.

7. A debonding adhesive film prepared by the following method: coating the debonding adhesive according to any one of claims 1~5 on a PET heavy release film, coating thickness 95~105μm, attaching a PET light release film, 395nm light curing, aging to obtain the debonding adhesive film.

8. The adhesive film according to claim 7, wherein The energy for photocuring is 1580-1620 J / cm 2 .

9. The adhesive film of claim 7, wherein the adhesive film is a double-sided adhesive film. The aging temperature is 35~45℃, and the aging time is 2.5~3 days.

10. A peeling method of the debonding adhesive film according to claim 7, comprising the following steps: The debonding adhesive film prepared in claim 7 is attached to a substrate and pressed, and cured by irradiation with a non-polar mercury lamp, and the curing energy is 1950-2050 mJ / cm 2 , and peeled.

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