CN112724888B

CN112724888B - Adhesive, wafer cutting protective film, and preparation method and application thereof

Info

Publication number: CN112724888B
Application number: CN202011599690.9A
Authority: CN
Inventors: 鄢家博; 吴喜来; 芋野昌三; 陈洪野; 吴小平
Original assignee: Cybrid Technologies Inc
Current assignee: Cybrid Technologies Inc
Priority date: 2020-12-29
Filing date: 2020-12-29
Publication date: 2022-05-31
Anticipated expiration: 2040-12-29
Also published as: CN112724888A

Abstract

The invention provides an adhesive, a wafer cutting protective film, and a preparation method and application thereof. The adhesive comprises the following raw material components in parts by weight: 20-40 parts of soft monomer, 1-10 parts of hard monomer, 5-20 parts of functional monomer, 0.1-5 parts of fluorine-containing monomer, 0.1-0.6 part of initiator and 0.1-2 parts of cross-linking agent. The adhesive is prepared by mixing a soft monomer, a hard monomer, a functional monomer, a solvent and an initiator, and then adding a fluorine-containing monomer for reaction to obtain a prepolymer; then mixing the prepolymer and the cross-linking agent. The wafer cutting protective film comprises a soft base material layer, an adhesive layer and a release film layer which are sequentially arranged; the adhesive layer is prepared from the adhesive. The wafer cutting protective film provided by the invention has better initial adhesion, stripping force, high temperature resistance and water resistance, no residual glue is left when the wafer is stripped, and the use requirement is met.

Description

Adhesive, wafer cutting protective film, and preparation method and application thereof

Technical Field

The invention belongs to the field of semiconductor manufacturing, and particularly relates to an adhesive, a wafer cutting protective film, and preparation methods and applications thereof.

Background

The wafer is a silicon wafer used for manufacturing a silicon semiconductor integrated circuit, and is called a wafer because the shape of the wafer is circular, and the silicon wafer can be processed into various circuit element structures to become an integrated circuit product with specific electrical functions. In the semiconductor manufacturing process, a semiconductor wafer is fixed on a wafer cutting protective film, the wafer is subjected to design processing, then segmentation and thinning processing are carried out, then the wafer is divided into smaller chips through cutting, and the chips are adhered to a supporting element through bonding, so that the required chips can be manufactured.

The cutting process is an essential process in the semiconductor chip manufacturing process flow and belongs to the subsequent process in wafer manufacturing. The existing cutting procedure is that a blade cuts off a wafer or a laser cuts off the wafer, but the width of a cutting channel of the wafer is narrowed, the cutting channel is easy to crack and break, so that the fraction defective of a chip is improved, a high-precision semiconductor cutting device can generate a heat effect when in use, for example, when laser irradiates and cuts along the cutting channel of the wafer, the generated heat energy is easy to be absorbed by the wafer, so that the heat energy is accumulated on the wafer, the wafer is easy to crack in the laser processing process, the generated heat energy is easy to cause silicon melting or thermal decomposition, silicon vapor generated by silicon dissolution or thermal decomposition is condensed and deposited on the wafer, scraps are generated at the peripheral edge of the wafer, the reliability of a product is influenced, and the wafer is usually required to be cleaned before the wafer is cut, so the wafer cutting protective film has higher initial adhesion and stripping force, it is also desirable to have better high temperature and water resistance.

Currently, the dicing protective film generally includes a thermal de-bonding protective film and a UV de-bonding protective film. For example, CN109161367A discloses a UV photosensitive adhesive, a UV protective film for a wafer using the same, and a preparation method thereof. The UV photosensitive adhesive comprises the following components in percentage by mass: the anti-aging coating comprises, by weight, 10-15% of star-shaped SIS, 10-15% of polymerized terpene A, 1-5% of polymerized terpene B, 0.5-0.8% of a light stabilizer, 1-4% of an aging agent, 3-20% of hollow microspheres and 60-75% of a solvent. The UV protective film prepared from the UV photosensitive adhesive provided by the technical scheme has good initial adhesion, but has poor high temperature resistance and can only resist the high temperature of 100 ℃ in a short time.

CN110396332A discloses a protective film solution for laser cutting of wafers and a method for processing wafers. The protective film solution comprises water-soluble resin containing polyvinyl alcohol, a water-soluble ultraviolet absorbent and a solvent; the addition amount of the water-soluble ultraviolet absorbent is more than 10 parts by weight based on 100 parts by weight of the polyvinyl alcohol, and the solvent is 60-92 parts by weight. The wafer processing method comprises the following steps: s1: providing a substrate, wherein a wafer is placed on the substrate; s2: forming a protective film on the wafer, wherein the protective film is formed by coating the protective film solution and then drying; s3: performing a pre-cutting manufacturing process by using an energy beam to form at least 2 grooves in the protective film and the material layer; s4: and removing the protective film by using pure water or deionized water, and performing a cutting manufacturing process to cut the substrate from the groove to form at least 2 chips. Although the technical scheme can effectively avoid silicon vapor generated by silicon dissolution or thermal decomposition from condensing and depositing on the wafer, the protective film prepared on the wafer by the protective film solution has poor water resistance, and the processing process of the wafer is complex.

CN210743920U discloses an anti-sticking protective film for dicing semiconductor wafer package. The packaging and cutting protective film is of a multilayer structure and sequentially comprises a release layer, a packaging adhesive layer, an anti-static bonding adhesive layer, a cutting adhesive layer and a PET (polyethylene terephthalate) film layer, wherein the packaging adhesive layer is formed on a peelable surface of the release layer. Although the packaging and cutting protective film provided by the technical scheme has better initial adhesion and can reduce the probability of the problems of wafer corner breakage, wafer flying and the like in the wafer cutting process, the packaging and cutting protective film has a more complex structure.

Therefore, it is a technical problem to be solved to provide a dicing protective film having high initial adhesion and peeling strength, high temperature resistance and water resistance, and a simple structure.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an adhesive, a wafer cutting protective film, and a preparation method and application thereof. The adhesive prepared from the fluorine-containing monomer has good water resistance and ductility, and further has good initial adhesion and stripping force and good high-temperature resistance through the matched use of the functional monomer and the crosslinking agent and the matched use of the soft monomer and the hard monomer, and meanwhile, no residual adhesive is left when the wafer is stripped, so that the use requirement is met.

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

in a first aspect, the invention provides an adhesive, which comprises the following raw material components in parts by weight: 20-40 parts of soft monomer, 1-10 parts of hard monomer, 5-20 parts of functional monomer, 0.1-5 parts of fluorine-containing monomer, 0.1-0.6 part of initiator and 0.1-2 parts of cross-linking agent.

According to the invention, the adhesive is prepared by adopting the fluorine-containing monomer, and the proportion range of the fluorine-containing monomer in the adhesive is further controlled, so that the fluorine-containing monomer and other components of the adhesive have good compatibility, and the wafer cutting protective film with good water resistance can be prepared. If the weight part of the fluorine-containing monomer is less, the water resistance of the prepared wafer cutting protective film is poor; if the weight part of the fluorine-containing monomer is more, the fluorine-containing monomer has poor compatibility with other components of the adhesive, and the fluorine-containing monomer can migrate in the preparation process of the adhesive, so that the water resistance of the wafer cutting protective film is poor.

According to the invention, through the matching use of the soft monomer and the hard monomer, the prepared wafer cutting protective film has high initial adhesion, good flexibility and good high temperature resistance, and no adhesive residue is left in the wafer stripping process. And through the matching use of the functional monomer and the cross-linking agent, the prepared wafer cutting protective film has good initial adhesion and good stripping force, and meets the use requirements.

In the present invention, the weight parts of the soft monomer may be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, or the like.

The hard monomer may be present in an amount of 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or the like.

The functional monomer may 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, or the like, by weight.

The weight portion of the fluorine-containing monomer may be 0.1 part, 0.2 part, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or the like.

The initiator may be present in an amount of 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, or the like, by weight.

The crosslinking agent may be present in an amount of 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, or the like.

The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.

In a preferred embodiment of the present invention, the soft monomer is selected from any one of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, lauryl acrylate, and n-propyl acrylate, or a combination of at least two thereof.

Preferably, the hard monomer is selected from any one of acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate or methyl methacrylate or a combination of at least two thereof.

Preferably, the mass ratio of the soft monomer to the hard monomer is (4-20: 1), and may be, for example, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, or 20: 1.

According to the invention, the use of the soft monomer can enable the wafer cutting protective film to have higher initial adhesion and better flexibility, the use of the hard monomer can enable the wafer cutting protective film to have better high temperature resistance, and the wafer cutting protective film can not have residual glue in the wafer peeling process. According to the invention, the soft monomer and the hard monomer are used in a matched manner, and the mass ratio of the soft monomer to the hard monomer is further controlled within a specific range of (4-20): 1, so that the prepared wafer cutting protective film has high initial adhesion, good flexibility and good high temperature resistance, and no adhesive residue is left in the wafer peeling process. If the content of the soft monomer is high, the prepared wafer cutting protective film has residual glue left in the wafer stripping process, the use requirement is not met, and the high temperature resistance of the prepared wafer cutting protective film is poor; if the content of the soft monomer is less, the initial adhesion of the prepared wafer cutting protective film is lower, and in the wafer cutting process, the wafer can move, so that the reject ratio of the chip is improved, and the use requirement is not met.

Preferably, the functional monomer is selected from any one of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-methylolacrylamide, glycidyl methacrylate or acrylonitrile or a combination of at least two of the above.

Preferably, the fluorine-containing monomer is selected from any one of allyl trifluoroacetate, trifluoromethyl methacrylate, trifluoroethyl methacrylate or trifluoroethyl acrylate or a combination of at least two of them.

Preferably, the initiator is selected from any one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, benzoyl peroxide or tert-butyl hexahydro peroxyterephthalate or a combination of at least two of the above.

Preferably, the crosslinking agent is selected from any one of pentaerythritol glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycerol glycidyl ether, glycerol glycidyl ether, and the like, or a combination of at least two thereof.

Preferably, the mass ratio of the functional monomer to the crosslinking agent is (6-20): 1, and may be, for example, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, or 20: 1.

In the invention, in the process of preparing the adhesive, the functional monomer can perform a crosslinking reaction with the crosslinking agent, so that the wafer cutting protective film has high initial adhesion and high elongation at break, and no residual adhesive is left in the process of peeling the wafer. If the content of the functional monomer is high, the prepared wafer cutting protective film has high initial adhesion, but residual glue is left in the wafer peeling process and does not meet the use requirement; if the content of the functional monomer is less, the initial adhesion of the prepared wafer cutting protective film is lower, and in the wafer cutting process, the wafer can generate corner breakage, flying and the like, so that the use requirement is not met.

Preferably, the adhesive further comprises a solvent.

Preferably, the solvent is selected from any one of dimethyl carbonate, ethyl acetate, toluene, isopropanol or methyl acetate or a combination of at least two thereof.

Preferably, the weight part of the solvent in the adhesive is 40 to 70 parts, such as 40 parts, 42 parts, 46 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 63 parts, 66 parts, 68 parts or 70 parts.

In a second aspect, the present invention provides a method for preparing the adhesive according to the first aspect, including the following steps:

(1) mixing a soft monomer, a hard monomer, a functional monomer, a solvent and an initiator, and adding a fluorine-containing monomer for reaction to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with a crosslinking agent to obtain the adhesive.

As a preferred embodiment of the present invention, the temperature of the mixing in the step (1) is 65 to 80 ℃ and may be, for example, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, or 80 ℃.

Preferably, the mixing time in step (1) is 30-60 min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60 min.

Preferably, the mixing of step (1) is carried out in the presence of an inert gas.

Preferably, the inert gas is selected from nitrogen and/or argon.

Preferably, the reaction temperature in step (1) is 65-80 ℃, for example, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 80 ℃.

Preferably, the reaction time in step (1) is 6-8 h, for example, 6h, 6.2h, 6.4h, 6.6h, 6.8h, 7h, 7.2h, 7.4h, 7.6h, 7.8h, or 8 h.

Preferably, the reaction of step (1) is carried out in the presence of an inert gas.

Preferably, the inert gas is selected from nitrogen and/or argon.

Preferably, the step (1) further comprises a pretreatment step before the mixing.

Preferably, the pretreatment method comprises the following steps: mixing the soft monomer, the hard monomer, the functional monomer and the solvent.

Preferably, the temperature of mixing in the pretreatment is 50 to 60 ℃, and may be, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ or 60 ℃.

Preferably, the mixing time in the pretreatment is 50-70 min, for example, 50min, 52min, 54min, 56min, 58min, 60min, 62min, 64min, 66min, 68min or 70 min.

Preferably, the pretreatment is carried out in the presence of an inert gas.

Preferably, the inert gas is selected from nitrogen and/or argon.

Preferably, the mixing temperature in step (2) is 20-50 deg.C, such as 20 deg.C, 24 deg.C, 26 deg.C, 30 deg.C, 33 deg.C, 36 deg.C, 39 deg.C, 42 deg.C, 46 deg.C or 50 deg.C.

Preferably, the mixing time in step (2) is 20-50 min, such as 20min, 22min, 25min, 28min, 30min, 33min, 36min, 38min, 40min, 42min, 46min or 50 min.

As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:

(1) in the presence of inert gas, mixing a soft monomer, a hard monomer, a functional monomer and a solvent at 50-60 ℃ for 50-70 min, heating to 65-80 ℃, adding an initiator, mixing for 30-60 min, adding a fluorine-containing monomer, and reacting for 6-8 h to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with a cross-linking agent at the temperature of 20-50 ℃ for 20-50 min to obtain the adhesive.

In a third aspect, the invention provides a wafer cutting protective film, which comprises a soft substrate layer, an adhesive layer and a release film layer, which are sequentially arranged;

the adhesive layer is prepared from the adhesive according to the first aspect.

In a preferred embodiment of the present invention, the material of the soft substrate layer is selected from a PO film, a PVC film or a PE film which is subjected to corona treatment.

Preferably, the thickness of the adhesive layer is 9 to 11 μm, and may be, for example, 9 μm, 9.3 μm, 9.6 μm, 9.8 μm, 10 μm, 10.2 μm, 10.5 μm, 10.8 μm, or 11 μm.

Preferably, the release film layer is made of a PET release film.

In a fourth aspect, the present invention provides a method for preparing a wafer dicing protective film according to the third aspect, including the following steps:

(A) coating an adhesive on one corona-treated side of the soft base material layer to obtain an adhesive layer;

(B) and (C) compounding a release film on the adhesive layer obtained in the step (A) to obtain the wafer cutting protective film.

As a preferred embodiment of the present invention, the step (a) further comprises a post-treatment step after the step of applying the adhesive.

Preferably, the method of post-treatment comprises drying.

Preferably, the drying temperature is 90-110 ℃, for example, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃ or 110 ℃.

Preferably, the drying time is 2-5 min, for example, 2min, 2.2min, 2.5min, 2.8min, 3min, 3.3min, 3.6min, 3.8min, 4min, 4.2min, 4.6min or 5 min.

In a fifth aspect, the invention provides a use of the dicing protective film according to the third aspect in semiconductor manufacturing.

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

(1) according to the invention, through the use of the fluorine-containing monomer, the weight part of the fluorine-containing monomer in the adhesive is further controlled, so that the fluorine-containing monomer and other raw material components of the adhesive have better compatibility, and meanwhile, the wafer cutting protective film has excellent water resistance, and the wafer cutting protective film has no obvious change after being soaked in water at 25 ℃ for 6 hours;

(2) according to the invention, through the matching use of the components, the mass ratio of the soft monomer to the hard monomer is further controlled within a specific range of (4-20): 1 and the mass ratio of the functional monomer to the cross-linking agent is controlled within a specific range of (6-20): 1, the solid content of the prepared adhesive is 44.9-46.2%, and the viscosity is 724-896 cps; the thickness of the wafer cutting protective film obtained by further preparation is 9-11 mu m, the wafer cutting protective film has high initial adhesion, 180-degree peeling force and elongation at break, the initial adhesion is 10-13 #, the 180-degree peeling force is 522-864 g/25mm, the elongation at break is 126.7-192.9%, the wafer cutting protective film also has good high temperature resistance and water resistance, the wafer is adhered to the wafer cutting protective film and placed in a 100 ℃ oven for 6 hours, no residual glue is left on the surface of the wafer after the wafer is peeled, and after the wafer is placed in 25 ℃ water for soaking for 6 hours, the wafer cutting protective film has no obvious whitening phenomenon and meets the use requirements.

Drawings

Fig. 1 is a schematic structural diagram of a wafer dicing protective film according to the present invention;

the adhesive comprises a base material layer, a soft base material layer, a 2-adhesive layer and a 3-release film layer, wherein the base material layer comprises 1-soft base material layers, 2-adhesive layers and 3-release film layers.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples. 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.

Example 1

The embodiment provides an adhesive, a wafer cutting protective film and a preparation method thereof, wherein the adhesive comprises the following raw material components in parts by weight:

the preparation method of the adhesive comprises the following steps:

(1) in the presence of nitrogen, mixing n-butyl acrylate, acrylic acid, acrylonitrile and ethyl acetate at 55 ℃ for 60min, heating to 70 ℃, adding azobisisobutyronitrile, mixing for 40min, adding trifluoroethyl acrylate, and reacting for 7h to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with pentaerythritol glycidyl ether at 40 ℃ for 30min to obtain the adhesive.

The structural schematic diagram of the wafer cutting protective film is shown in fig. 1, and the wafer cutting protective film comprises a soft base material layer 1, an adhesive layer 2 and a release film layer 3 which are sequentially arranged; the material of soft substrate layer 1 is the PO membrane through corona treatment, gluing agent layer 2 is obtained by the preparation of above-mentioned gluing agent, the material of leaving type rete 3 is PET release film.

The preparation method of the wafer cutting protective film comprises the following steps:

(A) coating an adhesive on one side of the PO membrane subjected to corona treatment, and drying at 105 ℃ for 3min to obtain an adhesive layer 2;

(B) and (C) compounding a PET release film on the adhesive layer 2 obtained in the step (A) to obtain the wafer cutting protective film.

Example 2

the preparation method of the adhesive comprises the following steps:

(1) in the presence of nitrogen, mixing ethyl acrylate, methacrylic acid, hydroxyethyl acrylate and dimethyl carbonate at 52 ℃ for 50min, heating to 65 ℃, adding azodiisoheptanonitrile, mixing for 30min, adding allyl trifluoroacetate, and reacting for 8h to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with diglycerol glycidyl ether at 20 ℃ for 50min to obtain the adhesive.

The structure schematic diagram of the wafer cutting protective film is shown in fig. 1, and the wafer cutting protective film comprises a soft base material layer 1, an adhesive layer 2 and a release film layer 3 which are sequentially arranged; the material of soft substrate layer 1 is the PVC membrane through corona treatment, gluing agent layer 2 is obtained by above-mentioned gluing agent preparation, the material of leaving type rete 3 is PET release film.

(A) coating an adhesive on one side of the PO membrane subjected to corona treatment, and drying at 90 ℃ for 5min to obtain an adhesive layer 2;

Example 3

the preparation method of the adhesive comprises the following steps:

(1) in the presence of argon, mixing isobutyl acrylate, methyl acrylate, 2-hydroxypropyl acrylate and toluene at 55 ℃ for 60min, heating to 80 ℃, adding azodiisovaleronitrile, mixing for 35min, adding trifluoromethyl methacrylate, and reacting for 6h to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with resorcinol diglycidyl ether at the temperature of 30 ℃ for 40min to obtain the adhesive.

The structure schematic diagram of the wafer cutting protective film is shown in fig. 1, and the wafer cutting protective film comprises a soft base material layer 1, an adhesive layer 2 and a release film layer 3 which are sequentially arranged; the material of soft substrate layer 1 is the PE membrane through corona treatment, gluing agent layer 2 is obtained by above-mentioned gluing agent preparation, the material of leaving type rete 3 is PET release film.

(A) coating an adhesive on one side of the PO membrane subjected to corona treatment, and drying at 100 ℃ for 4min to obtain an adhesive layer 2;

(B) and (B) compounding a PET release film on the adhesive layer 2 obtained in the step (A) to obtain the wafer cutting protective film.

Example 4

the preparation method of the adhesive comprises the following steps:

(1) in the presence of nitrogen, lauryl acrylate, ethyl methacrylate, N-hydroxymethyl acrylamide and isopropanol are mixed for 55min at 58 ℃, heated to 75 ℃, added with benzoyl peroxide, mixed for 45min, added with trifluoroethyl methacrylate, and reacted for 6.5h to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with neopentyl glycol diglycidyl ether at 25 ℃ for 35min to obtain the adhesive.

The structure schematic diagram of the wafer cutting protective film is shown in fig. 1, and the wafer cutting protective film comprises a soft base material layer 1, an adhesive layer 2 and a release film layer 3 which are sequentially arranged; the material of soft substrate layer 1 is the PO membrane through corona treatment, gluing agent layer 2 is obtained by the preparation of above-mentioned gluing agent, the material of leaving type rete 3 is PET release film.

(A) coating an adhesive on one side of the PO film subjected to corona treatment, and drying at 110 ℃ for 2min to obtain an adhesive layer 2;

Example 5

the solvent consists of ethyl acetate and methyl acetate according to the mass ratio of 3: 1.

The preparation method of the adhesive comprises the following steps:

(1) in the presence of argon, mixing n-propyl acrylate, methyl methacrylate, glycidyl methacrylate and a solvent at 60 ℃ for 50min, heating to 65 ℃, adding tert-butyl peroxyhexahydro terephthalate, mixing for 50min, adding trifluoroethyl acrylate, and reacting for 7h to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with glycerol glycidyl ether at 40 ℃ for 25min to obtain the adhesive.

Example 6

the preparation method of the adhesive comprises the following steps:

(1) in the presence of nitrogen, lauryl acrylate, ethyl methacrylate, 2-hydroxypropyl acrylate and ethyl acetate are mixed at 55 ℃ for 70min, then the temperature is raised to 68 ℃, azobisisobutyronitrile is added into the mixture, after the mixture is mixed for 55min, trifluoroethyl acrylate is added, and the reaction is carried out for 7.5h, so as to obtain a prepolymer;

(2) and (2) mixing the prepolymer obtained in the step (1) with pentaerythritol glycidyl ether at 35 ℃ for 40min to obtain the adhesive.

Example 7

the preparation method of the adhesive comprises the following steps:

(1) in the presence of nitrogen, mixing n-butyl acrylate, acrylic acid, acrylonitrile and ethyl acetate at 55 ℃ for 60min, heating to 70 ℃, adding azobisisobutyronitrile, mixing for 60min, adding trifluoroethyl acrylate, and reacting for 7h to obtain a prepolymer;

Example 8

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from example 1 only in that 27.2 parts by weight of n-butyl acrylate and 6.8 parts by weight of acrylic acid are used, and the other conditions are the same as example 1.

Example 9

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 only in that the weight parts of n-butyl acrylate is 32.4 parts, the weight parts of acrylic acid is 1.6 parts, and other conditions are the same as those of example 1.

Example 10

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 only in that 25.5 parts by weight of n-butyl acrylate and 8.5 parts by weight of acrylic acid are used, and the other conditions are the same as those of example 1.

Example 11

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 only in that the weight parts of n-butyl acrylate is 32.7 parts, the weight parts of acrylic acid is 1.3 parts, and other conditions are the same as those of example 1.

Example 12

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from example 1 only in that 12 parts by weight of acrylonitrile and 2 parts by weight of pentaerythritol glycidyl ether are used, and the other conditions are the same as example 1.

Example 13

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from example 1 only in that 13.3 parts by weight of acrylonitrile and 0.7 part by weight of pentaerythritol glycidyl ether are used, and the other conditions are the same as example 1.

Example 14

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from example 1 only in that 10 parts by weight of acrylonitrile and 2 parts by weight of pentaerythritol glycidyl ether are used, and the other conditions are the same as example 1.

Example 15

This example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from example 1 only in that 13.5 parts by weight of acrylonitrile and 0.5 part by weight of pentaerythritol glycidyl ether are used, and the other conditions are the same as example 1.

Comparative example 1

This comparative example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 in that trifluoroethyl acrylate is 0.05 parts by weight, and the other conditions are the same as those of example 1.

Comparative example 2

This comparative example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 in that trifluoroethyl acrylate is present in 6 parts by weight, and the other conditions are the same as those of example 1.

Comparative example 3

The present comparative example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 in that the adhesive does not contain acrylic acid, the weight part of n-butyl acrylate is 34 parts, and other conditions are the same as those of example 1.

Comparative example 4

The present comparative example provides an adhesive, a dicing protective film and a method for manufacturing the same, which are different from those of example 1 in that the adhesive does not contain n-butyl acrylate, acrylic acid is 34 parts by weight, and other conditions are the same as those of example 1.

Comparative example 5

The present comparative example provides an adhesive, a dicing protective film, and a method for manufacturing the same, which are different from those of example 1 in that the adhesive does not contain acrylonitrile, and that the weight part of pentaerythritol glycidyl ether is 12 parts, and the other conditions are the same as those of example 1.

Comparative example 6

The comparative example provides an adhesive, a wafer dicing protective film and a preparation method thereof, and is different from the adhesive in example 1 in that the adhesive does not contain pentaerythritol glycidyl ether, acrylonitrile is 12 parts by weight, and other conditions are the same as those in example 1.

Comparative example 7

The present comparative example provides an adhesive, a wafer dicing protective film, and a method for preparing the same, which are different from those in example 1 only in that the adhesive comprises the following raw material components in parts by weight:

other conditions were the same as in example 1.

Comparative example 8

other conditions were the same as in example 1.

The adhesive and the dicing protective film provided by the above examples and comparative examples were tested for their performance, with the following test criteria:

solid content: GB/T2793-1995;

viscosity: GB/T21059-2007;

thickness of the adhesive layer: GB/T7125-1999;

initial adhesion: GB/T4852-2002;

180 ° peel force: GB/T2792-;

elongation at break: ASTM-D-882;

high temperature resistance: after wafers are adhered to the wafer cutting protective films provided in the above embodiments and comparative examples and placed in an oven (model: DHG-9146A) at 100 ℃ for 6 hours, the wafers are peeled off, and whether residual glue is left on the surfaces of the wafers is observed;

water resistance: soaking the wafer cutting protective glue provided by the embodiment and the comparative example in water at 25 ℃ for 6h at 25 ℃, and observing the change of the wafer cutting protective film; if the surface of the dicing protective film is not significantly whitened, the water resistance is good, if the surface of the dicing protective film is whitened, the water resistance is good, and if the surface of the dicing protective film is widely whitened, the water resistance is poor.

The performances of the adhesive and the dicing protective film provided by the above examples and comparative examples are shown in the following table 1 after testing:

TABLE 1

The results in Table 1 show that the adhesive prepared by using the components in a matched manner and further controlling the mass ratio of the soft monomer to the hard monomer within the specific ratio range of (4-20): 1 and the mass ratio of the functional monomer to the crosslinking agent within the specific ratio range of (6-20): 1 has the solid content of 44.9-46.2% and the viscosity of 724-896 cps; the thickness of the prepared wafer cutting protective film is 9-11 mu m, the wafer cutting protective film has high initial adhesion, 180-degree peeling force and elongation at break, the initial adhesion is 10-13 #, the 180-degree peeling force is 522-864 g/25mm, the elongation at break is 126.7-192.9%, the wafer cutting protective film also has good high temperature resistance and water resistance, the wafer is adhered to the wafer cutting protective film and placed in an oven at 100 ℃ for 6 hours, no residual glue is left on the surface of the wafer after the wafer is peeled, and the wafer cutting protective film meets the use requirements.

Compared with example 1, if the mass of the soft monomer and the hard monomer in the adhesive is relatively small (example 10), the initial adhesion of the prepared wafer cutting protective film is lower by 8#, and the elongation at break of the prepared wafer cutting protective film is lower by 106.7%; if the mass ratio of the soft monomer to the hard monomer in the adhesive is large (example 11), the initial adhesion of the prepared wafer cutting protective film is large # 15, the adhesion to the wafer is large, and the wafer peeling process is difficult. Therefore, when the mass ratio of the soft monomer to the hard monomer in the adhesive is not in a specific range, the initial adhesion of the prepared wafer cutting protective film is too large or too small, and the use requirement is not met.

Compared with example 1, if the ratio of the functional monomer to the crosslinking agent in the adhesive is small (example 14), the initial adhesion of the prepared dicing protective film is low # 7, corner breakage, piece flying and the like occur in the dicing process of the wafer, the use requirement is not met, and the breaking elongation of the wafer is low 116.8%; if the ratio of the functional monomer to the cross-linking agent in the adhesive is large (example 15), the prepared dicing protective film has a high initial adhesion of 15#, and has a large adhesion to a wafer, so that the wafer peeling process is difficult, and the water resistance is poor. Therefore, when the mass ratio of the functional monomer to the cross-linking agent in the adhesive is not in a specific range, the initial adhesion of the prepared wafer cutting protective film does not meet the use requirement.

Compared with the example 1, if the weight part of the fluorine-containing monomer in the adhesive is less (comparative example 1), the prepared wafer cutting protective film has poor water resistance, and after the wafer cutting protective film is soaked in water at 25 ℃ for 6 hours, a large-area whitening phenomenon occurs; if the weight part of the fluorine-containing monomer in the adhesive is large (comparative example 2), the fluorine-containing monomer is poor in compatibility with other components of the adhesive, and the fluorine-containing monomer is easy to migrate and separate out in the process of preparing the adhesive, so that the prepared wafer cutting protective film is poor in water resistance, low in initial adhesion which is No. 4, and in the process of wafer cutting, the wafer can be subjected to corner breakage, piece flying and the like, so that the use requirement is not met, and the breaking elongation of the wafer is low and is 103.3%. Therefore, if the weight part of the fluorine-containing monomer in the adhesive is less or more, the prepared wafer cutting protective film cannot have good water resistance, high initial adhesion and high elongation at break at the same time.

Compared with example 1, if the adhesive does not contain a hard monomer (comparative example 3), the prepared wafer cutting protective film has poor high temperature resistance and water resistance, and adhesive residues are left when the wafer is peeled; if the adhesive does not contain the soft monomer (comparative example 4), the initial adhesion of the prepared wafer protective film is lower than 7#, and in the wafer cutting process, the wafer can move, so that the reject ratio of the chip is improved, the use requirement is not met, and the elongation at break is lower than 101.9%.

Compared with the example 1, if the adhesive does not contain a functional monomer (comparative example 5), the initial adhesion of the prepared wafer cutting protective film is lower than 5#, and the use requirement is not met; if the adhesive does not contain a cross-linking agent (comparative example 6), the prepared wafer cutting protective film has a high initial adhesion of No. 15, the initial adhesion is too high, the wafer is difficult to peel, the high temperature resistance is poor, and residual adhesive is left in the wafer peeling process and does not meet the use requirement.

Compared with the example 1, if the adhesive does not contain the fluorine-containing monomer (comparative example 7 and comparative example 8), the prepared wafer cutting protective film has lower initial adhesion, and the water resistance and the high temperature resistance are poor, so that the use requirement is not met.

In conclusion, the wafer cutting protective film prepared by using the components in a matched manner and further controlling the mass ratio of the soft monomer to the hard monomer and the mass ratio of the functional monomer to the cross-linking agent to be within a specific ratio range has high initial adhesion, 180-degree peeling force and elongation at break, and also has good high-temperature resistance and water resistance, and no residual glue is left when a wafer is peeled.

The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications, equivalent substitutions of selected elements of the present invention, additions of auxiliary elements, selection of specific forms, etc., are intended to fall within the scope and disclosure of the present invention.

Claims

1. The adhesive is characterized by comprising the following raw material components in parts by weight: 20-40 parts of soft monomer, 1-10 parts of hard monomer, 5-20 parts of functional monomer, 0.1-5 parts of fluorine-containing monomer, 0.1-0.6 part of initiator and 0.1-2 parts of cross-linking agent;

the mass ratio of the soft monomer to the hard monomer is (10-20): 1;

the mass ratio of the functional monomer to the cross-linking agent is (11-20): 1.

2. The adhesive of claim 1 wherein the soft monomer is selected from any one of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, lauryl acrylate or n-propyl acrylate or a combination of at least two thereof.

3. The adhesive of claim 1, wherein the hard monomer is selected from any one of acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate or methyl methacrylate or a combination of at least two of the foregoing.

4. The adhesive of claim 1, wherein the functional monomer is selected from the group consisting of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and mixtures thereof,N-any one or a combination of at least two of methylolacrylamide, glycidyl methacrylate or acrylonitrile.

5. The adhesive of claim 1 wherein the fluorine-containing monomer is selected from any one of allyl trifluoroacetate, trifluoromethyl methacrylate, trifluoroethyl methacrylate or trifluoroethyl acrylate or a combination of at least two of them.

6. The adhesive of claim 1 wherein the initiator is selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butyl hexahydro peroxyterephthalate, or a combination of at least two thereof.

7. The adhesive of claim 1, wherein the cross-linking agent is selected from any one of pentaerythritol glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycerin glycidyl ether, and glycerol glycidyl ether, or a combination of at least two thereof.

8. The adhesive of claim 1, further comprising a solvent.

9. The adhesive of claim 8, wherein the solvent is selected from any one of dimethyl carbonate, ethyl acetate, toluene, isopropanol or methyl acetate or a combination of at least two of the above.

10. The adhesive according to claim 8, wherein the solvent is 40-70 parts by weight of the adhesive.

11. A process for the preparation of the adhesive according to any one of claims 1 to 10, comprising the steps of:

12. The method according to claim 11, wherein the mixing temperature in step (1) is 65 to 80 ℃.

13. The method according to claim 11, wherein the mixing time in step (1) is 30 to 60 min.

14. The method according to claim 11, wherein the mixing in step (1) is carried out in the presence of an inert gas.

15. The method according to claim 14, wherein the inert gas is selected from nitrogen and/or argon.

16. The method according to claim 11, wherein the temperature of the reaction in the step (1) is 65 to 80 ℃.

17. The preparation method according to claim 11, wherein the reaction time in the step (1) is 6-8 h.

18. The method according to claim 11, wherein the reaction in step (1) is carried out in the presence of an inert gas.

19. The method of claim 18, wherein the inert gas is selected from nitrogen and/or argon.

20. The method of claim 11, wherein the step of mixing in step (1) further comprises a step of pre-treatment.

21. The method of claim 20, wherein the pre-treating is performed by: mixing the soft monomer, the hard monomer, the functional monomer and the solvent.

22. The method according to claim 21, wherein the temperature of mixing in the pretreatment is 50 to 60 ℃.

23. The method according to claim 21, wherein the mixing time in the pretreatment is 50 to 70 min.

24. The method of claim 20, wherein the pre-treatment is performed in the presence of an inert gas.

25. The method of claim 24, wherein the inert gas is selected from nitrogen and/or argon.

26. The method according to claim 11, wherein the mixing temperature in the step (2) is 20 to 50 ℃.

27. The method according to claim 11, wherein the mixing in step (2) is carried out for 20-50 min.

28. The method according to claim 11, wherein the method comprises the steps of:

29. A wafer cutting protective film is characterized by comprising a soft base material layer, an adhesive layer and a release film layer which are sequentially arranged;

the adhesive layer is prepared from the adhesive as described in any one of claims 1-10.

30. The dicing protective film according to claim 29, wherein the material of the soft base layer is selected from a PO film, a PVC film, or a PE film subjected to corona treatment.

31. The dicing protective film according to claim 29, wherein the adhesive layer has a thickness of 9 to 11 μm.

32. The wafer dicing protective film according to claim 29, wherein the material of the release film layer is a PET release film.

33. A method for preparing a wafer dicing protective film according to any one of claims 29 to 32, comprising the steps of:

34. The method according to claim 33, wherein the step (A) further comprises a post-treatment step after the step of applying the adhesive.

35. The method of claim 34, wherein the post-treating comprises drying.

36. The method according to claim 35, wherein the drying temperature is 90 to 110 ℃.

37. The method according to claim 35, wherein the drying time is 2 to 5 min.

38. Use of a dicing protective film according to any one of claims 29 to 32 in semiconductor manufacturing.