TW201813817A - Sheet for forming protective film in cutting substrate, method for preparing the same, circuit board including the same, and preparation method thereof capable of effectively forming a protective film on any surface of a cut semiconductor substrate, thereby promoting production efficiency - Google Patents

Abstract

The present invention relates to a sheet for forming a protective film in cutting a substrate, comprising a first release sheet and a protective film forming layer formed on the peelable surface of the first release sheet, wherein the protection film forming layer includes silicon dioxide and epoxy resin modified with an amine-based silane coupling agent or an epoxy-oxonane coupling agent; and a method for preparing the same; and a circuit cutting substrate having the abovementioned protection film on any sides thereof. The silane coupling agent has the following structure: Si(R1)n(R2)4-n, in which R1 represents a cationic polymerizable functional group linked to a deuterium atom, for example, a functional group of cyclic ether group or vinyloxy group, R2 represents hydrogen attached to a silicon atom, a hydrocarbyl, an alkyl, or an alkoxy, and n is an integer from 1 to 4.

Description

   Sheet for forming cutting substrate protective film and preparation method thereof, circuit substrate containing same and preparation method   

The present invention relates to a sheet for forming a protective film for a dicing substrate, which can effectively form a protective film on any side of a circuit dicing substrate for a semiconductor, thereby promoting the production efficiency of the dicing substrate.

Integrated circuits have been widely used in semiconductor technology; integrated circuit wafers, such as semiconductor wafers formed in the preparation of circuit substrates, are separated by tabular dividing lines (so-called streets). The semiconductor wafers are defined by regions separated by boundary roads. That is, the wafer is cut along the boundary to obtain a plurality of semiconductor wafers.

The cutting of the circuit cutting substrate along the boundary is usually performed by a cutting device (so-called cutter). The cutting device includes a chuck table for fixing a circuit substrate (which is a work object), a cutting member for cutting a circuit cutting substrate clamped on the chuck table, and a chuck table and a cutting member for moving the chuck table. Relative position of the moving member. The cutting member includes a rotating shaft to be rotated at a high speed, and a cutting blade provided on the shaft. This cutting blade includes a disc-shaped bottom and an annular cutting edge provided on a peripheral portion of a side surface of the bottom. This cutting edge, for example, contains diamond abrasive grains, the grain size of which is about 3 micrometers, and is fixed to the peripheral portion of the bottom side surface by electroforming to form a thickness of about 20 micrometers.

The aforementioned circuit cutting substrate is usually a material with high brittleness, and it is easy to cause micro scratches on the back surface due to mechanical grinding. Therefore, when a circuit cutting substrate (such as a semiconductor wafer) is cut into a circuit substrate (such as a semiconductor wafer) with a dicing blade (cutting edge), a resin is often used to seal the cutting substrate (such as a wafer) to the resin in accordance with protection requirements. Alternatively, the back surface of the dicing substrate is coated with a resin to obtain a semiconductor element. The disadvantage of the resin sealing method is that it is difficult to drip an appropriate amount of resin, resulting in too much resin. Therefore, there is currently a sheet of protective film for protecting a circuit cutting substrate, such as Taiwan Invention Patent Publication No. 533532, which is convenient for forming a highly uniform protective film on a circuit cutting substrate. On the backside, it avoids the bad effects caused by scratching.

However, the present inventor has discovered that the wafer protective film sheet disclosed in Shangkai Taiwan Invention Patent Publication No. 533532 includes a release sheet and a protective film forming layer formed on the release surface of the release sheet, wherein The protective film forming layer includes a thermosetting or energy ray hardenable component and a binder polymer component. However, since the protective film-forming layer must be added with a binder polymer and hardened by thermosetting or energy rays, when it is attached to the back of the wafer, it needs to be heated at high temperature (such as 160 ° C) or energy rays (such as ultraviolet light). ) Irradiation to form a protective film, so it is not convenient to use.

Therefore, the inventors have surprisingly found that after using various tests, if the silicon dioxide and epoxy resin modified by the amine-based siloxane coupling agent or epoxy siloxane coupling agent are used to form the protective film, the above-mentioned protection can be avoided. The patented protective film forming layer requires high temperature heating (such as 160 ° C) or irradiation with energy rays (such as ultraviolet light) to form the inconvenience of the protective film, and only needs to be baked to form a protective film without adding an adhesive. Can be adhered to the back of the cutting substrate.

Therefore, an aspect of the present invention is to provide a sheet for forming a cutting substrate protective film, including a first release sheet and a protective film layer, the protective film layer being formed on a peelable surface of the first release sheet, wherein The protective film layer includes silicon dioxide and epoxy resin modified by an amine-based siloxane coupling agent or an epoxy siloxane coupling agent.

Another aspect of the present invention is to provide a method for preparing a sheet for forming a dicing substrate protective film according to the present invention, which comprises the following steps: (a) providing a first release sheet; (b) mixing and coupling via an aminosiloxane Agent or epoxy siloxane coupling agent modified silicon dioxide and epoxy resin to obtain an epoxy resin / silica dioxide slurry; (c) coating the epoxy resin / silica dioxide slurry on the first A wet film is formed on the peelable surface of the release sheet and dried to form a protective film layer.

Another aspect of the present invention is to provide a method for producing a circuit-cut substrate. The circuit-cut substrate has a protective film on a back surface. The method includes adhering a protective film layer of the sheet forming the protective film of the dicing substrate of the present invention to a surface having a circuit. The circuit cuts the substrate on any side, peels off the first release sheet, and cuts the circuit cut substrate for each circuit together with the protective film layer.

Another aspect of the present invention is to provide a circuit-cut substrate with a protective film on the back surface, which is prepared by the method described above, wherein the protective film is coupled by an amine-based siloxane coupling agent or epoxy siloxane. It is composed of protective film layer of modified silica and epoxy resin.

10a, 10b ‧‧‧ forming a sheet for cutting substrate protection film

1a, 1b ‧‧‧ the first release film

2a, 2b‧‧‧protective film layer

3b‧‧‧Second Release Film

4a, 4b‧‧‧‧Circuit cutting substrate

FIG. 1 (a) is a schematic view of a first embodiment of a sheet for forming a dicing substrate protective film of the present invention; FIG. 1 (b) is a schematic view of a second embodiment of a sheet for forming a dicing substrate protective film of the present invention.

Fig. 2 (a) is a flow chart for preparing the first embodiment of the sheet for forming a dicing substrate protective film of the present invention; Fig. 2 (b) is a second embodiment of the sheet for forming the dicing substrate protective film of the present invention; Preparation flow chart.

FIG. 3 (a) is a schematic diagram of a third embodiment of a sheet for forming a dicing substrate protective film of the present invention; FIG. 1 (b) is a schematic diagram of a fourth embodiment of a sheet for forming a dicing substrate protective film of the present invention.

The details of the present invention are described below with reference to the drawings.

FIG. 1 (a) is a first embodiment of a sheet 10a for forming a dicing substrate protective film according to the present invention. The sheet 10a for forming a cutting substrate protective film includes a first release sheet 1a and a protective film layer 2a. The protective film layer 2a is formed on a peelable surface of the first release sheet 1a, wherein the protective film layer 2a includes silicon dioxide and epoxy resin modified by amine-based siloxane coupling agent or epoxy siloxane coupling agent.

FIG. 1 (b) is a second embodiment of the sheet 10b for forming a cutting substrate protective film according to the present invention. The sheet 10b for forming a cutting substrate protective film includes a first release sheet 1b and a protective film layer 2a. The protective film layer 2a is formed on a peelable surface of the first release sheet 1b, wherein the protective film layer 2a includes silicon dioxide and epoxy resin modified by an amine-based siloxane coupling agent or an epoxy siloxane coupling agent; and the protective film layer further includes a second release sheet 3b.

The first release sheet 1a, 1b and the second release sheet 3b may be composed of a film made of the following materials, such as polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride , Vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polysuccinate, polyurethane, ethylene-vinyl acetate, ion Crosslinked polymer resin, ethylene / (methene) acrylic copolymer, ethylene / (methene) acrylate copolymer, polystyrene, polycarbonate, cellulose acetate, cellulose triacetate, polyimide and containing Fluororesin. A crosslinked product film of the polymer or a laminated film of the film can also be used. When the protective film-forming layer is cured and released from the release sheet, polymethylpentene, polyethylene naphthalate, cellulose triacetate, and polyimide film are particularly preferable because of its excellent heat resistance Sex.

The first release sheets 1a, 1b and the second release sheet 3b have a surface tension of 40 mN / m or less, preferably 37 mN / m or less, and more preferably 35 mN / m or less. The low surface tension of the release sheet 1 can be achieved by appropriately selecting a sheet material or by performing a release treatment on the surface of the sheet 1 by applying a silicone resin. The thickness of the release sheet 1 is usually 5 to 300 microns, preferably 10 to 200 microns, and more preferably 20 to 150 microns.

The protective film layers 2a, 2b formed on the peelable surface of the first release sheet 1a, 1b include silicon dioxide and epoxy resin modified by an amine-based siloxane coupling agent or an epoxy siloxane coupling agent. . The modified silicon dioxide referred to in this article refers to the Si-OH chemical group on the surface of silicon dioxide and functional groups on the coupling agent that have compatibility and chemical properties with Si-O to form the surface of silicon dioxide. The chemical bonding is formed by the graft reaction of the -OH group on the surface of the silicon dioxide with the functional group of the coupling agent.

The epoxy siloxane coupling agent used in the present invention has a structure of the following formula: Si (R ₁ ) _n (R ₂ ) _4-n , where R ₁ represents a cationic polymerizable functional group connected to a silicon atom For example, a functional group containing a cyclic ether group or a vinyloxy group, and R ₂ represents hydrogen, a hydroxyl group, an alkyl group, or an alkoxy group attached to a silicon atom, Is an integer from 1 to 4; examples but not limited to the following siloxane coupling agents such as: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane), 3-glycidoxypropyl trimethoxy silane, glycidoxypropyl methyldiethoxy silane, epoxypropyl Glycidoxypropyl triethoxy silane, vinyltrimethoxy silane or vinyltriethoxy silane.

Examples of the aminosilane coupling agent used in the present invention include: N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3 -Aminopropyltrimethoxysilane, N-2 (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Ethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzene (Methyl) -2-aminoethyl-3-aminopropyltrimethoxysilamidine, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropane Methylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, imidazolesilane, and the like.

These amine-based siloxane coupling agents or epoxy siloxane coupling agents may be used alone or in combination of two or more.

The epoxy resin in the present invention is not particularly limited, and can be used for encapsulation, such as bisphenol A epoxy resin, brominated epoxy resin, novolac epoxy resin, and bisphenol F-ring. Oxygen resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bis-di Cresol-type or bisphenol-type epoxy resin or a mixture thereof, bisphenol S-type epoxy resin, bisphenol A novolac-type epoxy resin, tetraphenylphenol ethane-type epoxy resin, miscellaneous Cyclic epoxy resin, diglycidyl benzoate resin, tetraglycidyl xylenol ethane resin, naphthyl-containing epoxy resin, nitrogen-containing epoxy resin, dicyclopentadiene skeleton Epoxy resin, glycidyl methacrylate copolymer epoxy resin, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin; CTBN modified epoxy resin, etc. It is not limited to these contents. These epoxy resins can be used individually or in combination of 2 or more types.

The epoxy resin is preferably used together with a hardener during use. Examples of usable hardeners include amine-based hardeners, guanamine-based hardeners, imidazole-based hardeners, phenol-based hardeners, and naphthol. Type hardener, acid anhydride type hardener, or epoxy adduct thereof, etc. In the present invention, one kind of hardener may be used or two or more kinds may be used in combination; the blending ratio of resin and hardener may be based on the resin and hardener The type and the like are appropriately selected, for example, the mixing ratio of the epoxy resin and the hardener is the case of a phenol-based hardener or a naphthol-based hardener. The phenolic hydroxyl equivalent of these hardeners is 1 epoxy equivalent of the epoxy resin. A range ratio of 0.4 to 2.0 is preferable, and a range ratio of 0.5 to 1.0 is more preferable.

The above-mentioned amine-based siloxane coupling agent or epoxy siloxane coupling agent modified silicon dioxide and epoxy resin are both 10:90 to 90:10 parts by weight, preferably 45:55 to 75: 25 parts by weight.

Hereinafter, referring to FIG. 2, a method for preparing the dicing substrate protective film-forming sheets 10 a and 10 b of the present invention and the method for producing a circuit dicing substrate from the dicing substrate protective film-forming sheets 10 a and 10 b will be described.

FIG. 2 (a) is a preparation flow chart of the first embodiment of the sheet 10a for forming a cutting substrate protective film according to the present invention, which first provides a first release sheet 1a; the mixture is coupled via an amine siloxane Agent or epoxy siloxane coupling agent modified silicon dioxide and epoxy resin to obtain an epoxy resin / silica dioxide slurry; coating the epoxy resin / silica dioxide slurry on the first release sheet A wet film is formed on the peelable surface of 1a, and a protective film layer 2a is formed by drying.

The above steps of applying the epoxy resin / silica dioxide slurry to the peelable surface of the first release sheet 1a can be performed using a conventional coating machine such as a roll knife coating machine, a gravure coating machine, or a stamper. The coating machine and the reverse coating machine are directly coated on the detachable surface of the first release sheet 1a, and then the protective film layer 2a is formed by baking, and the sheet 10a for forming the protective film for the cutting substrate can be completed. The baking conditions are 70 ~ 120 ° C, 5 ~ 12 minutes, such as 70, 75, 80, 85, 90, 95, 100, 110, 120 ° C, 5, 6, 7, 8, 9, 10, 11 or 12 minutes; preferably 90 ° C for 10 minutes. Below this temperature and time, the protective film may not be dried into a dry film, and above this temperature and time may cause the protective film to form a dry film, and overheating may cause the dry film to curl or crack.

When the sheet 10a for forming the cutting substrate protective film is obtained, it can be further used for laminating on any side of the circuit cutting substrate 4a. The step includes adhering the protective film layer 2a of the sheet 10a for forming the cutting substrate protective film to the surface having the circuit. The circuit-cutting substrate 4a has a back surface, and the first release sheet 1a is peeled off to obtain a circuit-cutting substrate 4a with a protective film layer 2a. Then, the circuit-cutting substrate 4a (not shown) can be cut for each circuit together with the protective film layer.

FIG. 2 (b) is a preparation flow chart of the second embodiment of the sheet 10b for forming a cutting substrate protective film according to the present invention, which first provides a first release sheet 1b; the mixture is coupled via an amine siloxane Agent or epoxy siloxane coupling agent modified silicon dioxide and epoxy resin to obtain an epoxy resin / silica dioxide slurry; coating the epoxy resin / silica dioxide slurry on the first release sheet A wet film is formed on the peelable surface of 1b, and a protective film layer 2b is formed by drying, and a second release sheet 3b is further pasted on the protective film layer 2b, and the second release sheet 3b is the same The peelable surface is pasted on the protective film layer 2b to obtain the second embodiment of the sheet 10b for forming a dicing substrate protective film of the present invention.

In this second embodiment, the sheet 10b for forming a cutting substrate protective film can be further used to be attached to any side of the circuit cutting substrate 4b. The step includes forming a second release sheet 3b of the sheet 10b for forming a cutting substrate protective film. After peeling, the protective film layer 2b is adhered to any surface of the circuit-cutting substrate 4b having a circuit on the surface, and the first release sheet 1b is peeled off to obtain the circuit-cutting substrate 4b with the protective film layer 2b. Then, each circuit can be protected with The film cuts the circuit cutting substrate 4b (not shown).

Fig. 3 (a) A third embodiment of the present invention is different from the first embodiment only in that the protective film layer 2a is not entirely coated on the first release sheet 1a, but has a space, that is, It can be in a pre-cut state; Fig. 3 (b) shows a fourth embodiment of the present invention, which differs from the second embodiment only in that the protective film layer 2b is not entirely applied to the first The release sheet 1b has a space to form a pre-cut state. Therefore, in use, when the protective film layers 2a and 2b are attached to the circuit cutting substrate, the corresponding size can be obtained. No further cutting is required.

[Example]

10 g of silicon dioxide was mixed with 0.3 g of 3-glycidoxypropyltrimethoxysilane in tetrahydrofluoran at 60 ° C, and the reaction was performed for 4 hours to obtain 3-glycidyloxy Silyl dioxide modified by propyltrimethoxysilane.

5g of 3-glycidoxypropyltrimethoxysilane modified silica was mixed with 45g of CTBN modified epoxy resin and 45g of phenolic hardener to form a slurry, which was coated on polyterephthalic acid On the first release sheet of the glycol ester, the protective film layer is formed by baking in a continuous oven at 90 ° C. for 10 minutes to obtain a sheet for forming a cutting substrate protective film according to the present invention.

[Test example]

The sheet forming the protective film for the cutting substrate of the above embodiment is affixed to any surface of the circuit cutting substrate having a circuit on the surface, and the first release sheet is torn off; the circuit cutting substrate with the protective film is cut into shape using a cutting device To obtain the target cutting substrate (10 mm x 10 mm).

Claims (11)

    A sheet for forming a protective film for a cutting substrate includes a first release sheet and a protective film layer, the protective film layer is formed on a peelable surface of the first release sheet, wherein the protective film layer includes an amino group Silica coupling agent or epoxy silica coupling agent modified silicon dioxide and epoxy resin.     For example, the sheet for forming a cutting substrate protective film as claimed in claim 1, wherein the siloxane coupling agent has a structure of the following formula: Si (R ₁ ) _n (R ₂ ) _4-n , where R ₁ represents a silicon atom A cationic polymerizable functional group, such as a functional group containing a cyclic ether group or a vinyloxy group, and R ₂ represents hydrogen, a hydroxyl group, and an alkyl group attached to a silicon atom , Or an alkoxy group, is an integer from 1 to 4.     The sheet forming a protective film for a cutting substrate as claimed in claim 2, wherein the siloxane coupling agent is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane), 3-glycidoxypropyl trimethoxy silane, glycidoxypropyl methyldiethoxy silane, propylene oxide Glycidoxypropyl triethoxy silane, vinyltrimethoxy silane or vinyltriethoxy silane.         A sheet for forming a cutting substrate protective film as in claim 1, wherein the amine-based silane coupling agent is N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (amino (Ethyl) -3-aminopropyltrimethoxysilane, N-2 (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilamidine, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane , 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatetriethoxysilane, Imidazole silane.         The sheet for forming a protective film for a cutting substrate according to claim 1, wherein the protective film layer further includes a second release sheet.         A method for preparing a sheet for forming a cutting substrate protective film according to any one of claims 1 to 5, comprising the following steps: (a) providing a first release sheet; (b) mixing and coupling via an amine siloxane Agent or epoxy siloxane coupling agent modified silicon dioxide and epoxy resin to obtain an epoxy resin / silica dioxide slurry; (c) coating the epoxy resin / silica dioxide slurry on the first A wet film is formed on the peelable surface of the release sheet, and a protective film layer is formed by baking.         The method of claim 6, wherein the baking conditions are 70 to 120 ° C for 5 to 12 minutes.         The method of claim 7, further comprising attaching a peelable surface of a second release sheet to the protective film layer.         A method for producing a circuit-cut substrate, the circuit-cut substrate has a protective film on an arbitrary surface, and the method includes adhering a protective film layer of a sheet forming a protective film for a cutting substrate according to any one of claims 1 to 4 to a circuit having a circuit on a surface Cut any surface of the substrate, peel off the first release sheet, and cut the circuit cutting substrate for each circuit together with the protective film layer.         A method for producing a circuit-cut substrate, the circuit-cut substrate has a protective film on an arbitrary surface, and the method includes removing the second protective film layer of the sheet forming the protective film for the cutting substrate of claim 5 and adhering the surface with The circuit of the circuit cuts the back of the substrate, peels off the first release sheet, and cuts the circuit cut substrate for each circuit together with the protective film layer.         A circuit-cut substrate with a protective film on any side, which is prepared by the method of claim 9 or 10, wherein the protective film is modified by an amine-based siloxane coupling agent or an epoxy-based siloxane coupling agent. It is composed of a protective film layer of silicon dioxide and epoxy resin.