Composition for wafer protective film and wafer protective film

Abstract

A composition for a wafer protection film comprises an epoxy resin component, a polymer component, a thermal curing agent, a curing accelerator, a cross-linking agent component, an inorganic filler, a dispersant, a silicon-containing additive and a colorant, and the viscosity of the composition for the wafer protection film measured by a rheometer at 70 DEG C ranges from 1 * 10 < 6 > P to 2 * 10 < 6 > P. The invention also provides a wafer protection film which is formed by a colloidal solution containing the composition for the wafer protection film and a solvent. Through mutual matching of the components in the composition for the wafer protection film, particularly, the composition for the wafer protection film has the viscosity of 1 * 10 < 6 > P to 2 * 10 < 6 > P at 70 DEG C, so that the wafer protection film prepared from the composition for the wafer protection film has moderate hardness, and an excellent fitting effect between the wafer protection film and a wafer is achieved.

Description

Technical Field

[0001] The present invention relates to a protective film composition and the protective film, in particular to a wafer protective film composition and the wafer protective film. Background Art

[0002] Currently, most wafer protection films used in the industry are applied by automated film attaching machines, so that the wafer protection films are attached to the surface of the wafer. However, after the existing wafer protection films are attached to the surface of the wafer, there are often defects such as machine table pressure marks, bubbles, wrinkles and peeling on the surface of the wafer protection films, which results in poor yield of subsequent processes. In response to this, the industry has tried to adjust the operating parameters of the automated film attaching machines to solve the problem of defects in the wafer protection films, but adjusting the operating parameters of the automated die attaching machines has led to poor operation of the automated film attaching machines.

[0003] Based on the above, how to prevent defects such as machine platform pressure marks, bubbles, wrinkles and peeling from occurring after the wafer protection film is attached to the surface of the wafer is a problem that needs to be overcome at present. Summary of the invention

[0004] An object of the present invention is to provide a composition for a wafer protection film that can prevent defects from occurring during lamination of the wafer protection film.

[0005] The composition for wafer protection film of the present invention comprises epoxy resin component, polymer component, thermal curing agent, curing accelerator, crosslinking agent component, inorganic filler, dispersant, silicon-containing additive and colorant.

[0006] The epoxy resin component includes liquid epoxy resin and solid epoxy resin. The polymer component is selected from at least one of acrylate pressure-sensitive adhesive, polyurethane, polyester, rubber polymer and phenoxy resin. The thermosetting agent is used to perform a curing reaction with the epoxy resin component. The curing accelerator is used to perform a curing reaction with the epoxy resin component. The crosslinking agent component is used to perform a crosslinking reaction with the polymer component and includes a metal chelate and a polyisocyanate. The dispersant is used to disperse the inorganic filler.

[0007] The viscosity of the wafer protection film composition measured by a rheometer at 70°C is in the range of 1×10 6 P to 2×10 6 P.

[0008] In the wafer protection film composition of the present invention, the liquid epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, phenyl novolac epoxy resin and cresol novolac epoxy resin.

[0009] In the wafer protection film composition of the present invention, the solid epoxy resin is at least one selected from naphthalene epoxy resin, dicyclopentadiene epoxy resin and bisphenol A epoxy resin.

[0010] In the wafer protection film composition of the present invention, the acrylate pressure-sensitive adhesive is formed by polymerization of components including n-butyl acrylate, methyl acrylate, glycidyl methacrylate and hydroxyethyl acrylate.

[0011] In the wafer protection film composition of the present invention, the thermal curing agent is at least one selected from dicyandiamide, dibasic acid dihydrazide compounds, amine adducts and imidazole compounds.

[0012] In the wafer protection film composition of the present invention, the curing accelerator is at least one selected from 2-phenyl-4,5-dihydroxymethylimidazole, triethylenediamine, dimethylaminoethanol, triethanolamine, 2-methylimidazole, 2-phenylimidazole, tributylphosphine and triphenylphosphine.

[0013] In the wafer protection film composition of the present invention, the inorganic filler is selected from at least one of silicon dioxide, aluminum oxide, titanium oxide, iron oxide, calcium carbonate, boron nitride and silicon carbide.

[0014] In the wafer protection film composition of the present invention, the silicon-containing additive is selected from (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, At least one of 1,1-propylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane and a siloxane oligomer having an epoxy group.

[0015] In the wafer protection film composition described in the present invention, the colorant is selected from carbon black, cobalt pigments, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, indium tin oxide dyes, and antimony tin oxide dyes.

[0016] Another object of the present invention is to provide a wafer protection film that will not produce defects during bonding.

[0017] The wafer protection film of the present invention is formed by a colloidal solution containing the wafer protection film composition and a solvent.

[0018] The beneficial effects of the present invention are as follows: by matching the epoxy resin component, the polymer component, the thermal curing agent, the curing accelerator, the crosslinking agent component, the inorganic filler, the dispersant, the silicon-containing additive and the colorant, the wafer protection film composition has a rheometer measurement of 1×10 6 P to 2×10 6 P has a viscosity range of 1:1, so the wafer protection film prepared by the wafer protection film composition not only has moderate hardness, but also has an excellent bonding effect between the wafer protection film and the wafer. DETAILED DESCRIPTION

[0019] The wafer protection film composition of the present invention is a raw material for preparing a wafer protection film. The wafer protection film composition comprises an epoxy resin component, a polymer component, a thermal curing agent, a curing accelerator, a crosslinking agent component, an inorganic filler, a dispersant, a silicon-containing additive and a colorant. The viscosity of the wafer protection film composition measured by a rheometer at 70°C is in the range of 1×10 6 P to 2×10 6 P.

[0020] The epoxy resin component includes liquid epoxy resin and solid epoxy resin.

[0021] The liquid epoxy resin is mainly used to adjust the stress and strain properties of the wafer protection film, so as to give the wafer protection film appropriate hardness and softness. The liquid epoxy resin is, for example, but not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, phenyl novolac epoxy resin or cresol novolac epoxy resin. In some embodiments of the present invention, the liquid epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, phenyl novolac epoxy resin and cresol novolac epoxy resin. In some embodiments of the present invention, the liquid epoxy resin is at least one of bisphenol A epoxy resin and bisphenol F epoxy resin. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the liquid epoxy resin is in the range of 5wt% to 25wt% based on the total amount of the composition for the wafer protection film as 100wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the liquid epoxy resin is in the range of 5wt% to 15wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the liquid epoxy resin is in the range of 6wt% to 12wt%. The higher the amount of the liquid epoxy resin, the softer the wafer protection film; the lower the amount of the liquid epoxy resin, the harder the wafer protection film.

[0022] The solid epoxy resin is mainly used to prevent the surface of the wafer protection film from forming pressure marks caused by the automatic film mounting machine. The solid epoxy resin is, for example, but not limited to, naphthalene epoxy resin, dicyclopentadiene epoxy resin or bisphenol A epoxy resin. In some embodiments of the present invention, the solid epoxy resin is selected from at least one of naphthalene epoxy resin, dicyclopentadiene epoxy resin and bisphenol A epoxy resin. In some embodiments of the present invention, the solid epoxy resin is composed of naphthalene epoxy resin and dicyclopentadiene epoxy resin. In some embodiments of the present invention, the solid epoxy resin is composed of dicyclopentadiene epoxy resin and bisphenol A epoxy resin. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, based on the total amount of the wafer protection film composition as 100wt%, the amount of the naphthalene epoxy resin is in the range of 1wt% to 15wt%, the amount of the dicyclopentadiene epoxy resin is in the range of 1wt% to 15wt%, and the amount of the bisphenol A epoxy resin is in the range of 1wt% to 15wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the naphthalene epoxy resin is in the range of 2wt% to 10wt%, the amount of the dicyclopentadiene epoxy resin is in the range of 2wt% to 10wt%, and the amount of the bisphenol A epoxy resin is in the range of 1wt% to 8wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the naphthalene epoxy resin is in the range of 3wt% to 8wt%, the amount of the dicyclopentadiene epoxy resin is in the range of 3wt% to 8wt%, and the amount of the bisphenol A epoxy resin is in the range of 1wt% to 5wt%. The higher the amount of the naphthalene epoxy resin, the dicyclopentadiene epoxy resin and the bisphenol A epoxy resin, the harder the wafer protection film is; the lower the amount of the naphthalene epoxy resin, the dicyclopentadiene epoxy resin and the bisphenol A epoxy resin, the softer the wafer protection film is.

[0023] The polymer component is mainly used to match the epoxy resin component, so that the wafer protection film has appropriate film-forming properties and gives the wafer protection film appropriate hardness and softness. The polymer component is selected from at least one of acrylate pressure-sensitive adhesive, polyurethane, polyester, rubber polymer and phenoxy resin. In some embodiments of the present invention, the polymer component is an acrylate pressure-sensitive adhesive, and the acrylate pressure-sensitive adhesive is formed by polymerization reaction of components including n-butyl acrylate, methyl acrylate, glycidyl methacrylate and hydroxyethyl acrylate. The rubber polymer is, for example, but not limited to, styrene-butadiene rubber, nitrile rubber, butadiene rubber, etc., and the rubber polymer is not an acrylate rubber. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the weight average molecular weight of the polymer component ranges from 10,000 g / mol to 1.5 million g / mol. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the weight average molecular weight of the polymer component ranges from 100,000 g / mol to 1 million g / mol. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the weight average molecular weight of the polymer component ranges from 200,000 g / mol to 800,000 g / mol. The larger the weight average molecular weight of the polymer component, the harder the wafer protection film; the smaller the weight average molecular weight of the polymer component, the softer the wafer protection film. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the amount of the polymer component ranges from 15wt% to 40wt%, based on the total amount of the composition for the wafer protection film as 100wt%. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the amount of the polymer component ranges from 15wt% to 30wt%. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the amount of the polymer component ranges from 20wt% to 30wt%. The higher the amount of the polymer component, the softer the wafer protection film; the lower the amount of the polymer component, the harder the wafer protection film.

[0024] The thermal curing agent is used to perform a curing reaction with the epoxy resin component. The thermal curing agent is, for example, but not limited to, dicyandiamide, dibasic acid dihydrazide compounds, amine adducts or imidazole compounds. In some embodiments of the present invention, the thermal curing agent is selected from at least one of dicyandiamide, dibasic acid dihydrazide compounds, amine adducts and imidazole compounds. In some embodiments of the present invention, in order to further ensure the reactivity of the curing reaction and avoid the presence of unreacted thermal curing agent, so that the small molecules produced by the cleavage of the unreacted thermal curing agent escape from the wafer protection film, causing the surface of the wafer protection film to form a depression or contamination, the total amount of the composition for the wafer protection film is 100wt%, and the amount of the thermal curing agent is in the range of 0.05wt% to 8wt%. In some embodiments of the present invention, in order to further adjust the reactivity of the curing reaction, the amount of the thermal curing agent is in the range of 0.05wt% to 5wt%. In some embodiments of the present invention, in order to further adjust the reactivity of the curing reaction, the amount of the thermal curing agent is in the range of 0.1 wt % to 2 wt %.

[0025] The curing accelerator is used to carry out a curing reaction with the epoxy resin component and promote the curing reaction. The curing accelerator is, for example, but not limited to, 2-phenyl-4,5-dihydroxymethylimidazole, triethylenediamine, dimethylaminoethanol, triethanolamine, 2-methylimidazole, 2-phenylimidazole, tributylphosphine or triphenylphosphine. In some embodiments of the present invention, the curing accelerator is selected from at least one of 2-phenyl-4,5-dihydroxymethylimidazole, triethylenediamine, dimethylaminoethanol, triethanolamine, 2-methylimidazole, 2-phenylimidazole, tributylphosphine and triphenylphosphine. In some embodiments of the present invention, in order to further ensure the reactivity of the curing reaction and avoid the presence of unreacted curing accelerator, so that the small molecules generated by the cleavage of the unreacted curing accelerator escape from the wafer protection film, causing the surface of the wafer protection film to form depressions or contamination, and to prevent the wafer protection film from being too hard and brittle, the amount of the curing accelerator is in the range of 0.05wt% to 5wt% based on the total amount of the composition for the wafer protection film as 100wt%. In some embodiments of the present invention, in order to further adjust the reactivity of the curing reaction, the amount of the curing accelerator is in the range of 0.05wt% to 3wt%. In some embodiments of the present invention, in order to further adjust the reactivity of the curing reaction, the amount of the curing accelerator is in the range of 0.1wt% to 2wt%.

[0026] The crosslinking agent component is used to crosslink with the polymer component and give the wafer protection film good film-forming properties, and the crosslinking agent component can also adjust the stress and strain properties of the wafer protection film, thereby giving the wafer protection film appropriate hardness and softness. The crosslinking agent component includes a metal chelate and a polyisocyanate. In some embodiments of the present invention, the metal chelate is zinc acetylacetonate. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the total amount of the composition for the wafer protection film is 100wt%, and the amount of the metal chelate is in the range of 0.05wt% to 5wt%, and the amount of the polyisocyanate is in the range of 0.1wt% to 10wt%. In some embodiments of the present invention, in order to further adjust the hardness and softness of the wafer protection film, the amount of the metal chelate is in the range of 0.05wt% to 3wt%, and the amount of the polyisocyanate is in the range of 0.1wt% to 8wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the metal chelate is in the range of 0.1wt% to 2wt%, and the amount of the polyisocyanate is in the range of 0.1wt% to 3wt%. The higher the amount of the metal chelate and the polyisocyanate, the harder the wafer protection film; the lower the amount of the metal chelate and the polyisocyanate, the softer the wafer protection film.

[0027] The inorganic filler is used to give the wafer protection film good film-forming properties. The inorganic filler is, for example, but not limited to, silicon dioxide, aluminum oxide, titanium oxide, iron oxide, calcium carbonate, boron nitride or silicon carbide. In some embodiments of the present invention, the inorganic filler is selected from at least one of silicon dioxide, aluminum oxide, titanium oxide, iron oxide, calcium carbonate, boron nitride and silicon carbide. In some embodiments of the present invention, the silicon dioxide is, for example, hollow silicon dioxide. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the inorganic filler is in the range of 30wt% to 65wt% based on the total amount of the composition for the wafer protection film as 100wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the inorganic filler is in the range of 40wt% to 60wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film, the amount of the inorganic filler is in the range of 50wt% to 60wt%. The higher the amount of the inorganic filler used, the harder the wafer protection film is; the lower the amount of the inorganic filler used, the softer the wafer protection film is.

[0028] The dispersant is used to disperse the inorganic filler so that the inorganic filler can be evenly dispersed in the wafer protection film, thereby giving the wafer protection film a stable thermal expansion coefficient and a smooth surface, which is beneficial to the subsequent processing of the wafer protection film. In some embodiments of the present invention, in order to effectively disperse the inorganic filler evenly in the wafer protection film and avoid the presence of unreacted dispersant, so that the small molecules generated by the cracking of the unreacted dispersant escape from the wafer protection film, causing the surface of the wafer protection film to form a depression or contamination, the total amount of the composition for the wafer protection film is 100wt%, and the amount of the dispersant is in the range of 0.1wt% to 10wt%. In some embodiments of the present invention, in order to further adjust the dispersion degree of the inorganic filler in the wafer protection film, the amount of the dispersant is in the range of 0.5wt% to 5wt%. In some embodiments of the present invention, in order to further adjust the dispersion degree of the inorganic filler in the wafer protection film, the amount of the dispersant is in the range of 0.5wt% to 3wt%.

[0029] The silicon-containing additive is used to match with other components in the composition for the wafer protection film, so as to give the wafer protection film appropriate hardness and softness. At the same time, the silicon-containing additive can also make the wafer protection film have good weather resistance to water vapor, so that the wafer protection film can pass the PCT test and have a test grade of 5B. In some embodiments of the present invention, the silicon-containing additive is selected from (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyl At least one of methyl diethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, γ-ureidopropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl methyl dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, imidazole silane and siloxane oligomers having epoxy groups. In some embodiments of the present invention, the silicon-containing additive includes a silane compound having an epoxy group and a siloxane compound having an epoxy group, and the siloxane compound having an epoxy group can further give the wafer protection film good adhesion. In some embodiments of the present invention, the silicon-containing additive includes a trimethoxysilane compound having an epoxy group, a triethoxysilane compound having an epoxy group and a siloxane compound having an epoxy group. In some embodiments of the present invention, in order to give the wafer protection film good copper foil peeling strength and avoid the presence of unreacted silicon-containing additives, so that the small molecules generated by the cracking of the unreacted silicon-containing additives escape from the wafer protection film, causing depressions or contamination on the surface of the wafer protection film, based on the total amount of the composition for the wafer protection film as 100wt%, the amount of the trimethoxysilane compound with an epoxy group ranges from 0.1wt% to 10wt%, the amount of the triethoxysilane compound with an epoxy group ranges from 0.1wt% to 10wt%, and the amount of the siloxane compound with an epoxy group ranges from 0.1wt% to 10wt%. In some embodiments of the present invention, in order to more effectively avoid the presence of the unreacted silicon-containing additive, the amount of the trimethoxysilane compound having an epoxy group is in a range of 0.1 wt% to 5 wt%, the amount of the triethoxysilane compound having an epoxy group is in a range of 0.1 wt% to 5 wt%, and the amount of the siloxane compound having an epoxy group is in a range of 0.1 wt% to 5 wt%.In some embodiments of the present invention, in order to further avoid the presence of the unreacted silicon-containing additive and adjust the copper foil peel strength of the wafer protection film, the amount of the trimethoxysilane compound having an epoxy group is in a range of 0.2wt% to 3wt%, the amount of the triethoxysilane compound having an epoxy group is in a range of 0.2wt% to 3wt%, and the amount of the siloxane compound having an epoxy group is in a range of 0.2wt% to 3wt%.

[0030] The colorant is used to match with other components in the composition for the wafer protection film, so as to give the wafer protection film an appropriate hardness and softness. At the same time, the colorant also serves as a laser mark in the wafer protection film and is used for subsequent judgment of whether to use infrared light to check the cracking of the cutting edge of the wafer. In some embodiments of the present invention, the colorant is selected from carbon black, cobalt pigments, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, indium tin oxide dyes, and antimony tin oxide dyes. In some embodiments of the present invention, in order to make the wafer protection film have a good laser engraving effect and low production cost, the colorant is carbon black. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film and give the wafer protection film different infrared light penetration properties, the amount of the colorant is 0.1wt% to 30wt% based on the total amount of the composition for the wafer protection film as 100wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film and adjust the infrared light penetration properties of the wafer protection film, the amount of the colorant ranges from 0.1wt% to 20wt%. In some embodiments of the present invention, in order to further adjust the hardness of the wafer protection film and adjust the infrared light penetration properties of the wafer protection film, the amount of the colorant ranges from 0.2wt% to 5wt%. The lower the amount of the colorant, the softer the wafer protection film, and the higher the infrared light penetration of the wafer protection film; the higher the amount of the colorant, the harder the wafer protection film, and the lower the infrared light penetration of the wafer protection film.

[0031] In the present invention, the wafer protection film composition is made by combining the epoxy resin component, the polymer component, the thermal curing agent, the curing accelerator, the crosslinking agent component, the inorganic filler, the dispersant, the silicon-containing additive and the colorant, so that the wafer protection film has good film-forming properties and appropriate hardness. In addition, after measuring the wafer protection film composition with a rheometer at 70°C, the wafer protection film composition has a 1×10 6 P to 2×10 6 The viscosity range of P is such that after the wafer protection film made of the wafer protection film composition is bonded to the back side of a wafer, there will be no pressure marks, wrinkles, bubbles and peeling problems on the wafer protection film, thus having an excellent bonding effect.

[0032] The present invention also provides a wafer protection film, which is formed by a colloidal solution comprising a wafer protection film composition and a solvent as described above. The type of the solvent is not particularly limited, as long as it can dissolve the wafer protection film composition and uniformly mix the components in the wafer protection film composition. The reagent is suitable for the present invention. In some embodiments of the present invention, the solvent is composed of ethyl acetate and butanone. In some embodiments of the present invention, the solid content range of the colloidal solution is 30wt% to 40wt%, or, the solid content range of the colloidal solution is 35wt% to 40wt%. In some embodiments of the present invention, the viscosity range of the colloidal solution is 150cps to 600cps, or, the viscosity range of the colloidal solution is 150cps to 550cps, or, the viscosity range of the colloidal solution is 200cps to 600cps. In some embodiments of the present invention, the thickness of the wafer protection film ranges from 1 μm to 150 μm, or the thickness of the wafer protection film ranges from 10 μm to 100 μm, or the thickness of the wafer protection film ranges from 10 μm to 50 μm, or the thickness of the wafer protection film ranges from 25 μm to 40 μm. In detail, the wafer protection film is prepared by coating the colloidal solution on a substrate surface and baking. The substrate is, for example, but not limited to, a release film.

[0033] The present invention will be further described with reference to the following examples, but it should be understood that the examples are only used for illustration and should not be construed as limitations of the present invention.

[0034] [Example 1] Wafer protection film composition and wafer protection film

[0035] 7.85wt% of bisphenol A epoxy resin (as liquid epoxy resin, brand: Nan Ya Plastics Industry Co., Ltd., model: NPEL-128), 4.8wt% of dicyclopentadiene epoxy resin (as solid epoxy resin, brand: DIC Corporation, model: HP-7200HH), 1.8wt% of bisphenol A epoxy resin (as solid epoxy resin, brand: Nan Ya Plastics Industry Co., Ltd., model: NPES-904), 26wt% of acrylate pressure-sensitive adhesive (as polymer component, formed by polymerization reaction of 65wt% of n-butyl acrylate, 15wt% of methyl acrylate, 12wt% of glycidyl methacrylate and 8wt% of hydroxyethyl acrylate, with a glass transition temperature of -1°C and a weight average molecular weight of 740,000 g / mol), 0.5wt% of dicyandiamide (as thermal curing agent, brand: AlzChem, model: DYHRD 100S), 1wt% of 2-phenyl-4,5-dihydroxymethylimidazole (as a curing accelerator, brand: Shikoku Chemical Industry Co., Ltd., model: 2PHZ-PW), 0.3wt% of zinc acetylacetonate (as a metal chelate, brand: Huangyu Chemical Materials Co., Ltd.), 0.4wt% of polyisocyanate (brand: Risheng Chemical Co., Ltd., model: SC-7100NY), 55wt% of silica (as an inorganic filler, brand: Suzhou Jinyi New Materials, D50 particle size is 0.42μm), 1.2wt% of dispersant (brand: BASF, model: EFKAPX 4701), 0.3wt% of (3-glycidoxypropyl)triethoxysilane (as a silicon-containing additive, brand: Hengqiao Industrial Co., Ltd., model: CB-660E), 0.3wt% of (3-glycidoxypropyl)trimethoxysilane (as a silicon-containing additive, brand: Hengqiao Industrial Co., Ltd., model: CB-660M), 0.3wt% of a siloxane oligomer having an epoxy group (as a silicon-containing additive, brand: Shin-Etsu Chemical Co., Ltd., model: KR-516) and 0.25wt% of carbon black (as a colorant, brand: Micro Control Precision Co., Ltd., model: B533, particle size is 23nm) are mixed to obtain a composition for a wafer protective film.

[0036] The wafer protection film composition is mixed with a solvent consisting of ethyl acetate and butanone to obtain a colloidal solution. The volume ratio of the ethyl acetate to the butanone in the solvent is 8:2, the solid content of the colloidal solution is 35.5wt%, and the viscosity of the colloidal solution is 330cps.

[0037] The colloidal solution was coated on one surface of a first release film with a thickness of 50 μm using a slit coater (brand: Haijin Industrial Co., Ltd., coating width: 600 mm), and the first release film with the colloidal solution coated on the surface was placed in an oven for baking, so that the colloidal solution was transformed into a wafer protection film with a thickness of 25 μm. Afterwards, a second release film with a thickness of 38 μm was attached to the surface of the wafer protection film, so that the wafer protection film was sandwiched between the first release film and the second release film, and a composite film material was obtained.

[0038] [Examples 2 to 3] Wafer protection film composition and wafer protection film

[0039] Examples 2 to 3 are methods of obtaining a composition for a wafer protection film and a wafer protection film in a manner similar to Example 1, with the difference being that in Example 2, the amount of bisphenol A epoxy resin as a liquid epoxy resin is adjusted to 8.05 wt %, and the amount of polyisocyanate is adjusted to 0.2 wt %; and in Example 3, the weight average molecular weight of the acrylic pressure-sensitive adhesive as a polymer component is adjusted to 590,000 g / mol.

[0040] [Example 4] Wafer protection film composition and wafer protection film

[0041] Example 4 is a method similar to Example 1 to obtain a composition for a wafer protection film and a wafer protection film, except that: Example 4 is a method of preparing a composition for a wafer protection film and a wafer protection film by mixing 8.45 wt % of bisphenol A type epoxy resin (as a liquid epoxy resin, brand: Nan Ya Plastics Industry Co., Ltd., model: NPEL-128), 4 wt % of naphthalene type epoxy resin (as a solid epoxy resin, brand: DIC Corporation, model: HP-4710), and 5.5 wt % of dicyclopentadiene type epoxy resin (as a solid epoxy resin, brand: DIC Corporation, model: HP-4710). ion, model: HP-7200HH), 25wt% acrylate pressure-sensitive adhesive (as a polymer component, formed by polymerization of 65wt% n-butyl acrylate, 15wt% methyl acrylate, 12wt% glycidyl methacrylate and 8wt% hydroxyethyl acrylate, with a glass transition temperature of -1°C and a weight average molecular weight of 740,000 g / mol), 0.5wt% dicyandiamide (as a thermal curing agent, brand: AlzChem, model: DYHRD 100S), 1.2wt% of 2-phenyl-4,5-dihydroxymethylimidazole (as a curing accelerator, brand: Shikoku Chemical Industry Co., Ltd., model: 2PHZ-PW), 0.3wt% of zinc acetylacetonate (as a metal chelate, brand: Huangyu Chemical Materials Co., Ltd.), 0.8wt% of polyisocyanate (brand: Risheng Chemical Co., Ltd., model: SC-7100NY), 50wt% of silica (as an inorganic filler, brand: Suzhou Jinyi New Materials, D50 particle size is 0.42μm), 1.2wt% of dispersant (brand: BASF, model: EFKAPX 4701), 0.2wt% of (3-glycidoxypropyl)triethoxysilane (as a silicon-containing additive, brand: Hengqiao Industrial Co., Ltd., model: CB-660E), 0.3wt% of (3-glycidoxypropyl)trimethoxysilane (as a silicon-containing additive, brand: Hengqiao Industrial Co., Ltd., model: CB-660M), 0.3wt% of a siloxane oligomer with an epoxy group (as a silicon-containing additive, brand: Shin-Etsu Chemical Co., Ltd., model: KR-516) and 2.25wt% of carbon black (as a colorant, brand: Micro Control Precision Co., Ltd., model: B533, particle size is 23nm) are mixed to obtain a composition for a wafer protection film.

[0042] [Example 5] Wafer protection film composition and wafer protection film

[0043] Example 5 is a method of obtaining a composition for a wafer protection film and a wafer protection film in a manner similar to Example 4, with the difference that: in Example 5, the amount of bisphenol A epoxy resin as a liquid epoxy resin is adjusted to 8.65wt%, the amount of dicyclopentadiene epoxy resin as a solid epoxy resin is adjusted to 5wt%, the amount of polyisocyanate is adjusted to 0.6wt%, and the amount of inorganic filler is adjusted to 50.5wt%.

[0044] [Comparative Examples 1 to 3] Wafer Protection Film Composition and Wafer Protection Film

[0045] Comparative Examples 1 to 3 are similar to Example 1 in obtaining compositions for wafer protection films and wafer protection films, except that: in Comparative Example 1, the amount of dicyclopentadiene epoxy resin as a solid epoxy resin is adjusted to 5.2wt%, and no polyisocyanate is added; in Comparative Example 2, the amount of bisphenol A epoxy resin as a liquid epoxy resin is adjusted to 9.15wt%, the amount of dicyclopentadiene epoxy resin as a solid epoxy resin is adjusted to 5wt%, and the amount of bisphenol A epoxy resin as a liquid epoxy resin is adjusted to 1.5wt%. In comparative example 3, the amount of bisphenol A epoxy resin as a liquid epoxy resin is adjusted to 8.85wt%, the amount of dicyclopentadiene epoxy resin as a solid epoxy resin is adjusted to 5wt%, the amount of bisphenol A epoxy resin as a liquid epoxy resin is adjusted to 2wt%, the amount of polyisocyanate is adjusted to 1wt%, and the amount of inorganic filler is adjusted to 53wt%.

[0046] [Comparative Examples 4 to 5] Wafer Protection Film Composition and Wafer Protection Film

[0047] Comparative Examples 4 to 5 are compositions for wafer protection films and wafer protection films obtained in a manner similar to Example 4, with the following differences: In Comparative Example 4, the amount of bisphenol A type epoxy resin as a liquid epoxy resin is adjusted to 8.15wt%, the amount of naphthalene type epoxy resin as a solid epoxy resin is adjusted to 4.5wt%, the amount of dicyclopentadiene type epoxy resin as a solid epoxy resin is adjusted to 6.2wt%, the amount of acrylate type pressure-sensitive adhesive as a polymer component is adjusted to 23.5wt%, and the amount of polyisocyanate is adjusted to 1.4wt%; In Comparative Example 5, the amount of bisphenol A type epoxy resin as a liquid epoxy resin is adjusted to 8.75wt%, the amount of dicyclopentadiene type epoxy resin as a solid epoxy resin is adjusted to 6wt%, the amount of acrylate type pressure-sensitive adhesive as a polymer component is adjusted to 24wt%, and the amount of polyisocyanate is adjusted to 1wt%.

[0048] [Evaluation items]

[0049] The wafer protection film composition and the wafer protection film of Example 1 are used as an example for description below, and the wafer protection film compositions and the wafer protection films of the other Examples 2 to 5 and Comparative Examples 1 to 5 are prepared in the same manner.

[0050] Tensile test: The two ends of a wafer protection film of Example 1 (length 7cm, width 2cm) are respectively attached to two aluminum plates, and the aluminum plates are separated by 4cm of the wafer protection film of Example 1. Then, a universal tensile testing machine (brand: shimadzu, model: EZ-LX) is used to clamp the aluminum plates, and the aluminum plates are stretched in two opposite directions at a speed of 100mm / min to obtain the tensile stress, tensile strain rate and tensile fracture rate of the wafer protection film of Example 1. When the value of the tensile stress falls above 200gf / mm 2 And less than 400gf / mm 2 The value of the tensile strain rate falls within the range of greater than 0% and less than 500%, and the value of the tensile fracture rate falls within the range of greater than 0% and less than 600%, indicating that the wafer protection film has moderate hardness.

[0051] Copper foil peel strength test: A wafer protection film (length 10 cm, width 1 cm) of Example 1 is aligned with a piece of copper foil (length 15 cm, width 1 cm) and attached to one end of the copper foil to obtain a test sample. Next, the wafer protection film in the test sample is directed toward the grinding surface of a silicon wafer (diameter 200 mm, thickness 280 μm) ground by a No. 8000 grinding wheel, and the test sample is thermally attached to the grinding surface at 80°C. Then, the silicon wafer with the test sample attached is placed at 130°C for 2 hours of thermal curing treatment. After cooling, a universal tensile tester (brand: shimadzu, model: EZ-LX) is used to clamp the other end of the copper foil that is not attached to the wafer protection film, and a tensile test is performed at a speed of 100 mm / min at an angle of 180 degrees to obtain the copper foil peel strength of the wafer protection film of Example 1.

[0052] Shear strength test: A wafer protection film (length 1 cm, width 1 cm) of Example 1 was thermally attached at 80°C, so that the opposite sides of the wafer protection film of Example 1 were attached to two aluminum sheets with a width of 1 cm, and thermally cured at 130°C for 2 hours to obtain a test sample. After cooling, a universal tensile machine (brand: shimadzu, model: EZ-LX) was used to clamp the aluminum sheets of the test sample, and the aluminum sheets were pulled apart in two opposite directions at a speed of 100 mm / min, thereby obtaining the shear strength of the wafer protection film of Example 1.

[0053] Viscosity test: The wafer protection film composition of Example 1 was measured using a rheometer (brand: TA Instruments, model: HR20) to obtain the viscosity of the wafer protection film composition of Example 1 at 70° C. The test temperature range was 25° C. to 180° C., the heating rate was 10° C. / min, the axial force was 1 N, and the frequency was 1 Hz.

[0054] Grid test on wafer: The wafer protection film of Example 1 was measured using the Standard Test Methods for Rat ing Adhesion by Tape Test of ASTM D3359-2023. The wafer protection film of Example 1 was subjected to a thermal bonding treatment using a roller at 80°C, so that the wafer protection film of Example 1 was attached to the grinding surface of a silicon wafer (200 mm in diameter and 280 μm thick) ground by a No. 8000 grinding wheel, and a thermal curing treatment was performed at 130°C for 2 hours to obtain a test sample. After cooling, a cross scratch test was performed on the wafer protection film of Example 1 in the test sample using a grid knife, so as to evaluate the wafer grid test result of the wafer protection film of Example 1.

[0055] Grid test on wafer treated by pressure cooker: The wafer protection film of Example 1 was measured by Standard Test Methods for Rat ing Adhesion by Tape Test according to ASTM D3359-2023. The wafer protection film of Example 1 was subjected to thermal bonding treatment by a roller at 80°C so that the wafer protection film of Example 1 was attached to the grinding surface of a silicon wafer (200 mm in diameter and 280 μm in thickness) ground by a No. 8000 grinding wheel, and thermally cured at 130°C for 2 hours to obtain a sample to be treated. After cooling, the sample to be treated was placed in a pressure cooker and subjected to a Pressure Cooker Test (PCT) for 168 hours at 121°C and 100% humidity to obtain a test sample. Then, a cross scratch test is performed on the wafer protection film of Example 1 in the test sample using a cross scratch knife, so as to evaluate the PCT wafer cross scratch test result of the wafer protection film of Example 1.

[0056] The bonding condition of the wafer protection film: The wafer protection film of Example 1 was heated by a film bonding machine (brand: LINTEC Corporation, model: Advill RAD-3600F / 12), and the wafer protection film of Example 1 was bonded to the grinding surface of a silicon wafer (diameter 200 mm, thickness 280 μm) ground by a No. 8000 grinding wheel, and the bonding condition between the wafer protection film of Example 1 and the silicon wafer was observed during the process of the wafer protection film of Example 1 being bonded to the grinding surface. The temperature of the film bonding platform of the film bonding machine was set to 70°C, the temperature of the bonding roller was set to 60°C, and the bonding pressure was set to 0.26 mPa. The bonding condition between the wafer protection film and the silicon wafer will be represented by codes A to D, where A indicates that there are no pressure marks, no wrinkles, no bubbles, and no peeling in the wafer protection film; B indicates that there are no wrinkles, no bubbles, and no peeling in the wafer protection film, but there are pressure marks; C indicates that there are no pressure marks, no wrinkles, no peeling in the wafer protection film, but there are bubbles; D indicates that there are no pressure marks, no bubbles in the wafer protection film, but there are wrinkles and peeling.

[0057] Table 1

[0058]

[0059]

[0060] Table 2

[0061]

[0062]

[0063]

[0064] Referring to Table 1, the wafer protection films of Examples 1 to 5 have moderate hardness and softness by matching the liquid epoxy resin, the solid epoxy resin, the polymer component, the thermal curing agent, the curing accelerator, the metal chelate, the polyisocyanate, the inorganic filler, the dispersant, the silicon-containing additive and the colorant in types and amounts. Moreover, by matching the above components, the wafer protection film compositions of Examples 1 to 5 have 1×10 6 P to 2×10 6 The viscosity range of P is such that when the wafer protection films of Examples 1 to 5 are bonded to the surface of the wafer, the wafer protection films do not produce any pressure marks, wrinkles, bubbles or peeling. Therefore, the wafer protection films of Examples 1 to 5 have excellent bonding effects with the wafer.

[0065] Referring to Table 2, in contrast to Comparative Examples 1 to 5, although the wafer protection films of Comparative Examples 1 to 5 have moderate hardness, the viscosity of the wafer protection film composition of Comparative Examples 1 to 5 is less than 1×10 6 P, or greater than 2×10 6 P, so that when the wafer protection films of Comparative Examples 1 to 5 are bonded to the surface of the wafer, the wafer protection films have at least one of pressure marks, wrinkles, bubbles and peeling, so the bonding effect between the wafer protection films of Comparative Examples 1 to 5 and the wafer is not good.

[0066] In summary, the wafer protection film composition of the present invention is a combination of the epoxy resin component, the polymer component, the thermal curing agent, the curing accelerator, the crosslinking agent component, the inorganic filler, the dispersant, the silicon-containing additive and the colorant, especially the combination of the above components to make the wafer protection film composition have a rheometer measurement at 70°C of 1×10 6 P to 2×10 6 The viscosity range of P is, therefore, the wafer protection film prepared with the wafer protection film composition has moderate hardness and softness, and the wafer protection film has excellent bonding effect with the wafer, so the purpose of the present invention can be achieved.

[0067] However, the above is only an embodiment of the present invention and should not be used to limit the scope of the present invention. All simple equivalent changes and modifications made according to the claims and description of the present invention are still within the scope of the present invention.

Claims

1. A composition for a wafer protective film, characterized in that: The wafer protection film composition comprises: Epoxy resin components, including liquid epoxy resin and solid epoxy resin; The polymer component is selected from at least one of acrylic pressure-sensitive adhesive, polyurethane, polyester, rubber polymer and phenoxy resin; A thermal curing agent, used for performing a curing reaction with the epoxy resin component; A curing accelerator, used for carrying out a curing reaction with the epoxy resin component; A cross-linking agent component, used for cross-linking reaction with the polymer component, and comprising a metal chelate and a polyisocyanate; Inorganic fillers; A dispersant, used to disperse the inorganic filler; Silicon-containing additives; and Colorants; The viscosity of the wafer protection film composition measured by a rheometer at 70°C is in the range of 1×10 6 P to 2×10 6 P.

2. The wafer protection film composition according to claim 1, wherein: The liquid epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, phenyl novolac epoxy resin and cresol novolac epoxy resin.

3. The wafer protection film composition according to claim 1, wherein: The solid epoxy resin is selected from at least one of naphthalene epoxy resin, dicyclopentadiene epoxy resin and bisphenol A epoxy resin.

4. The wafer protection film composition according to claim 1, wherein: The acrylic ester pressure-sensitive adhesive is formed by polymerization of components including n-butyl acrylate, methyl acrylate, glycidyl methacrylate and hydroxyethyl acrylate.

5. The wafer protection film composition according to claim 1, wherein: The thermal curing agent is at least one selected from dicyandiamide, dibasic acid dihydrazide compounds, amine adducts and imidazole compounds.

6. The wafer protection film composition according to claim 1, wherein: The curing accelerator is at least one selected from 2-phenyl-4,5-dihydroxymethylimidazole, triethylenediamine, dimethylaminoethanol, triethanolamine, 2-methylimidazole, 2-phenylimidazole, tributylphosphine and triphenylphosphine.

7. The wafer protection film composition according to claim 1, wherein: The inorganic filler is at least one selected from silicon dioxide, aluminum oxide, titanium oxide, iron oxide, calcium carbonate, boron nitride and silicon carbide.

8. The wafer protection film composition according to claim 1, wherein: The silicon-containing additive is selected from at least one of (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane and siloxane oligomers having epoxy groups.

9. The wafer protection film composition according to claim 1, wherein: The colorant is selected from carbon black, cobalt pigments, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, indium tin oxide dyes, and antimony tin oxide dyes.

10. A wafer protection film; characterized in that: The wafer protection film is formed by a colloidal solution comprising the wafer protection film composition according to any one of claims 1 to 9 and a solvent.

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