CN110699000A

CN110699000A - Film material for grinding and packaging semiconductor

Info

Publication number: CN110699000A
Application number: CN201910963195.2A
Authority: CN
Inventors: 张程
Original assignee: Shanghai Solid Adhesive Tape Technology Co Ltd
Current assignee: Shanghai Solid Adhesive Tape Technology Co Ltd
Priority date: 2019-10-11
Filing date: 2019-10-11
Publication date: 2020-01-17

Abstract

The invention relates to the technical field of semiconductors, in particular to a film material for grinding and packaging semiconductors. The film material for grinding and packaging the semiconductor sequentially comprises a base material film and an adhesive layer from top to bottom; the base material membrane connects first corona layer, bright layer, antistatic layer, sandwich layer, antioxidation layer, matte layer, second corona layer crowded altogether including pasting in proper order. The film material has excellent heat resistance, aging resistance, antistatic property, expansibility, heat and humidity resistance stability and good heat dissipation capacity, and meanwhile, the film material is environment-friendly and safe in preparation raw materials and simple in preparation process, and can meet the requirements of semiconductor packaging process and semiconductor protection in transportation.

Description

Film material for grinding and packaging semiconductor

Technical Field

The invention belongs to the technical field of semiconductors, and particularly relates to a film material for grinding and packaging semiconductors.

Background

The semiconductor assembly technology is a process technology which utilizes a membrane technology and a micro-connection technology to connect a semiconductor chip with a conductor part in a frame or a substrate or a plastic sheet or a printed circuit board so as to lead out a wiring pin, and the semiconductor chip is encapsulated and fixed through a plastic insulating medium to form an integral three-dimensional structure.

With the development of semiconductor related technologies, on one hand, the chip has more and more powerful functions and more pins; on the other hand, in order to meet the requirement of miniaturization of devices such as mobile terminals, the size of the chip is smaller and smaller, so that the pin pitch of the chip is smaller and smaller, and the requirement on the required packaging film material is higher and higher. The existing packaging film has the problems of low thermal expansion coefficient, cracking of packaging materials caused by gasification and expansion of high-temperature, moisture and water molecules, poor quick-curing formability, poor heat dissipation capability and incapability of timely and effectively removing heat generated by circuits and chips, thereby reducing the yield of semiconductor chips. In addition, the films on the market have problems in safety and environmental protection, which affects the application of the films in the semiconductor packaging process.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a film material for grinding and packaging a semiconductor, which comprises a substrate film and a glue layer in sequence from top to bottom; the base material membrane connects first corona layer, bright layer, antistatic layer, sandwich layer, antioxidation layer, matte layer, second corona layer crowded altogether including pasting in proper order.

As a preferred technical solution, the film material for grinding and packaging semiconductors further comprises a silicon oil layer; the silicon oil layer is connected with the upper surface of the base material film.

As a preferred technical solution, the film material for semiconductor grinding and packaging further comprises a PET layer; the PET layer is connected with the lower surface of the adhesive layer.

As a preferable technical scheme, the raw materials for preparing the first corona layer and the second corona layer comprise polypropylene.

As a preferable technical scheme, the raw materials for preparing the bright layer and the matte layer comprise ethylene-ethyl acrylate copolymer.

As a preferred technical scheme, the preparation raw materials of the antistatic layer comprise: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 5-10 parts of antistatic agent and 2-6 parts of crosslinking agent.

As a preferred technical solution, the raw materials for preparing the anti-oxidation layer include: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 4-8 parts of antioxidant and 2-6 parts of crosslinking agent.

As a preferred technical scheme, the core layer preparation raw materials comprise: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 1-3 parts of color master batch and 2-4 parts of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.

As a most preferred technical scheme, the preparation raw materials of the modified polyethylene comprise: linear low-density polyethylene, silane coupling agent, phytic acid, magnesium oxide and wollastonite.

As a preferred embodiment, the elastomer is an ethylene-based elastomer and/or a propylene-based elastomer.

As a preferred technical scheme, the preparation raw materials of the antistatic agent comprise erucamide and polyoxyethylene-acrylic acid copolymer.

As a preferable technical scheme, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.

As a preferable technical scheme, the cross-linking agent is triethylene tetramine and/or methyl hydrogen-containing silicone oil.

The second aspect of the present invention provides a method for preparing a film material for semiconductor grinding and packaging as described above, which can be classified into a direct coating method and a spin coating method.

The third aspect of the invention provides the application of the film material for grinding and packaging semiconductors in semiconductor preparation process and transportation.

Has the advantages that: the invention provides a film material for grinding and packaging semiconductors. The preparation raw materials of the base material film are optimized and improved, so that the film material has excellent heat resistance, aging resistance, corrosion resistance, antistatic property, expansibility, moisture resistance and good heat dissipation capacity, and meanwhile, the preparation raw materials of the film material are environment-friendly and safe, simple in preparation process and convenient to use, the yield of semiconductor chips is improved, and the requirements of semiconductor packaging process and semiconductor protection in transportation can be met.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "including". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase will render the claim closed except for the materials described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein in the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received by modifying or otherwise modifying such quantity without substantially changing the basic function to which it is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In view of the above technical problems, a first aspect of the present invention provides a film material for semiconductor grinding and packaging, which comprises a substrate film and a glue layer in sequence from top to bottom; the base material membrane connects first corona layer, bright layer, antistatic layer, sandwich layer, antioxidation layer, matte layer, second corona layer crowded altogether including pasting in proper order.

[ substrate film ]

In one embodiment, the raw materials from which the first and second corona layers are made include polypropylene.

In one embodiment, the raw materials for preparing the clear layer and the matte layer include an ethylene-ethyl acrylate copolymer.

In one embodiment, the antistatic layer is prepared from the following raw materials: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 5-10 parts of antistatic agent and 2-6 parts of crosslinking agent.

In one embodiment, the raw material for preparing the anti-oxidation layer comprises: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 4-8 parts of antioxidant and 2-6 parts of crosslinking agent.

In one embodiment, the core layer preparation raw material comprises: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 1-3 parts of color master batch and 2-4 parts of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.

In a preferred embodiment, the polypropylene is a homopolypropylene.

In a preferred embodiment, the modified polyethylene is prepared from the following raw materials: linear low-density polyethylene, silane coupling agent, phytic acid, magnesium oxide and wollastonite.

In a most preferred embodiment, the silane coupling agent is N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane.

Homo-polypropylene

The homo-polypropylene of the present invention has very good flow properties over a wide range of flow rates and, therefore, has very good processability. It is also a very good moisture barrier.

In the examples, the homo-polypropylene was purchased from Guangdong petrochemical division of China oil and gas Co., Ltd under the designation T30S powder.

Ethylene-ethyl acrylate copolymer

The ethylene-ethyl acrylate copolymer disclosed by the invention has good flexibility, thermal stability and processability. The environmental stress cracking resistance, impact resistance, bending fatigue resistance and low temperature resistance are all superior to those of low density polyethylene, and the low density polyethylene has good compatibility with polyolefin and can be mixed with a large amount of filler without becoming brittle.

The ethylene-ethyl acrylate copolymer of the examples was purchased from Shanghai Yitong industries, Inc. under the designation 6200.

Linear low density polyethylene

The linear low-density polyethylene is non-toxic, tasteless and odorless milky white particles. The high-strength high-toughness high-strength high-toughness high-heat-resistance high-cold-resistance high-strength high-toughness high-strength high-toughness high-strength.

In the examples, the linear low density polyethylene was purchased from Guangdong petrochemical division of China oil and gas Co., Ltd under the designation 7042 powder.

Silane coupling agent

The molecular structural formula of the silane coupling agent is generally as follows: Y-R-Si (OR)₃(wherein Y-organic functional group, SiOR-siloxy). The siloxy group is reactive with inorganic species and the organofunctional group is reactive or compatible with organic species. Thus, when a silane coupling agent intervenes between the inorganic and organic interfaces, a bonding layer of organic matrix-silane coupling agent-inorganic matrix may be formed.

Examples N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (CAS: 3069-29-2) was purchased from Shanghai Pont chemical industries, Inc.

Phytic acid

The phytic acid is chemically named as phytic acid and is an organic phosphoric acid compound extracted from plant seeds.

Examples phytic acid (CAS: 83-86-3) was purchased from Guangzhou Chengyang Kongkushi Koncki Co.

Magnesium oxide

The magnesium oxide of the invention is an ionic compound. It is a white solid at normal temperature. Magnesium oxide exists in nature in the form of periclase, and is a raw material for smelting magnesium. Magnesium oxide has high refractory and insulating properties.

Examples magnesium oxide (CAS: 1309-48-4) was purchased from Guangzhou Chengyang Kongkushi Koncki Co.

Wollastonite

The wollastonite is a common calcium metasilicate mineral and belongs to a single-chain silicate mineral. The natural wollastonite usually has the glass luster to the pearl luster, and the color is from white to grey white, the density is high, and the hardness value is high. Compared with other inorganic fillers, the wollastonite powder not only plays a role in filling, but also can partially replace asbestos and glass fiber for reinforcing materials in the plastic industry. The composite material has excellent electrical insulating property, high thermal deformation temperature, low flammability, good permeability, acid and alkali corrosion resistance, and simultaneously has two-dimensional reinforcement, can enhance the modulus, rigidity, hardness, heat resistance and dimensional stability of a plastic matrix, and has particularly remarkable research and application values in the field of novel polymer composite materials.

Examples wollastonite was purchased from Clonoland wollastonite mining GmbH, Panshi, Jilin province, with an average particle size of 4.8. mu.m.

In one embodiment, the modified polyethylene is prepared by a process comprising:

(1) adding 6-8 parts of phytic acid, 3-6 parts of magnesium oxide and 1-3 parts of wollastonite into water, stirring and grinding until the average particle size is smaller than 1 mu m, adding 8-12 parts of silane coupling agent, continuously grinding for 13 h for surface treatment, filtering, washing with water until the pH value is 7, and drying to obtain the filler subjected to surface modification treatment.

Adding 40-60 parts of linear low-density polyethylene into an open mill, wherein the roll temperature is 140-180 ℃, adding a filler subjected to surface modification treatment after the linear low-density polyethylene is coated on a roll, discharging sheets after melt blending, and performing compression molding by a QLD-D type flat vulcanizing machine at the temperature of 150-240 ℃ to obtain the polyethylene.

The invention improves the heat resistance, moisture resistance and corrosion resistance of the material by blending the phytic acid, the magnesium oxide, the wollastonite and the low-density polyethylene. Probably, after the phytic acid is modified by a silane coupling agent, unreacted phosphorus and hydroxyl groups in the passivation process can be connected through hydrogen bonds or dehydration reaction to form a space network phytic acid (salt) passivation film with high crosslinking density on one hand, and can be reacted with-Si-OH-generated after silane hydrolysis to generate-P-O-Si-bond which can generate stable chelate with metal to form a colorless and transparent protective film with smooth surface, compact and uniform thickness and no microcrack on the metal surface to effectively prevent a corrosion medium from permeating into the metal surface, thereby slowing down the corrosion of the metal. Meanwhile, the compatibility of the phytic acid with other components is good, and the aging resistance and the heat resistance of the film can be further improved. The phytic acid treated by the silane coupling agent is also a coloring auxiliary agent, which is more beneficial to coloring the pigment and can improve the coloring uniformity. Magnesium oxide has high thermal conductivity and high heat dissipation capacity, but the stability of the composition is poor when the magnesium oxide is used alone, and wollastonite, which is a natural acicular structure inorganic substance, has excellent rigidity, toughness, filling property and thermal stability and can play a double-effect of toughening and strengthening materials. Therefore, the problem of the stability of the composite material can be solved with the addition of the wollastonite powder. In addition, the wollastonite powder carrying magnesium oxide has remarkable heat resistance and is an excellent heat-resistant agent. It also has better wet resistance properties, so that the modified polyolefin has better wet resistance.

Elastic body

The elastomer is a high polymer material which has obvious deformation under weak stress and can be quickly recovered to be close to the original state and size after the stress is relaxed.

In one embodiment, the elastomer is an ethylene-based elastomer and/or a propylene-based elastomer.

In a preferred embodiment, the elastomer is a propylene-based elastomer.

In the examples, the propylene-based elastomer was purchased from hong Koghai plastics, Inc. of Dongguan, under the designation 6202 FL.

Antistatic agent

The antistatic agent of the present invention is an additive which is added into plastics or coated on the surface of a molded article for the purpose of reducing static accumulation. Antistatic agents can be classified into two major types, internal type and external type, depending on the method of use, and the main type used for plastics is internal type antistatic agent. They can also be classified into two broad categories, temporary and permanent, according to the nature of the antistatic agent.

In one embodiment, the antistatic agent is prepared from raw materials including erucamide and a polyethylene oxide-acrylic acid copolymer.

In a preferred embodiment, the antistatic agent is prepared by a process comprising: mixing 12-24 parts of erucamide, 12-24 parts of polyoxyethylene-acrylic acid copolymer, 2-6 parts of copper sulfate, 8-10 parts of anhydrous potassium carbonate and

molecular sieves mixed in dimethyl sulfoxide, in N₂Under the protection, 110 ℃ and 130 ℃, and reacting for 22-26 h.

The invention adopts the combination of polyoxyethylene-acrylic acid copolymer and erucamide, thus achieving the technical effect of permanent antistatic. The possible reason is NH of carboxylic acid and amide group of the polyoxyethylene-acrylic acid copolymer₂The end bonds result in a permanent antistatic. The hydrophilic end of the antistatic agent is a polyethylene oxide end, the polyethylene oxide end is gathered on the surface of a base material and forms continuous lamellar distribution on the surface to form a discharge passage, so that the antistatic effect can be realized, and the hydrophobic end is a long chain end and has good compatibility with polyolefin materials, so that the antistatic additive maintains certain compatibility with the base material. Therefore, when the copolymer and the antistatic additive are cured together, the hydrophilic groups of the antistatic agent are arranged towards the air side, and the moisture in the air is adsorbed by the hydrophilic groups to form a monomolecular conductive layer, so that the antistatic effect is achieved. However, during processing, the antistatic performance is reduced due to the defect of the antistatic monolayer on the surface of the resin caused by stretching, rubbing, washing and the like, but after a while, due to the anti-oxidant molecules in the copolymerContinuously migrate to the surface, so that the monolayer with surface defects is replenished from the inside, and the permanent antistatic effect is achieved.

In addition, the inventor finds that the phytic acid can enable the antistatic effect of the antistatic agent to be optimal. The possible reason is that phosphate groups in the phytic acid are easily combined with the N end of the antistatic agent, after combination, when other phosphate groups in the phytic acid are complexed with metal, a layer of compact monomolecular protective film is formed on the surface, the processed metal surface is conducted with current by a monomolecular hole electron conducting layer and a passive metal film, so that the antistatic effect is achieved, and the phytic acid and the antistatic agent cooperate to perform double comprehensive antistatic protection.

Examples erucamide (CAS: 112-84-5), copper sulfate (CAS: 7758-99-8), anhydrous potassium carbonate (CAS: 584-08-7) and

molecular sieves (CAS: 63231-69-6) were purchased from Guangzhou honesty Change Industrial technology, Inc.

Antioxidant agent

The antioxidants of the present invention are chemical substances which, when present in the polymer system in only small amounts, retard or inhibit the progress of the oxidation process of the polymer, thereby preventing the aging of the polymer and extending its useful life, also known as "age resistors". Antioxidants help protect the above-mentioned polymers and the overall binder system from the effects of thermal and oxidative degradation that often occur during the manufacture and application of film compositions and in the ambient environment to which the final product is normally exposed, primarily as a result of deterioration in the appearance, physical properties, etc. of the composition.

In one embodiment, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

In the examples pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (CAS: 6683-19-8) was purchased from plastication technology Co., Ltd, Sheng, Dongguan.

Crosslinking agent

The cross-linking agent is an important component of the poly-hydrocarbon photoresist, the photochemical curing effect of the photoresist depends on the cross-linking agent with double photosensitive functional groups to participate in the reaction, the cross-linking agent generates double free radicals after exposure, and the double free radicals react with the poly-hydrocarbon resin to form bridge bonds between polymer molecular chains and become insoluble substances with three-dimensional structures.

In one embodiment, the cross-linking agent is triethylene tetramine and/or methyl hydrogen silicone oil.

In a preferred embodiment, the cross-linking agent is methyl hydrogen silicone oil.

In the examples, methyl hydrogen silicone oil (CAS: 63148-57-2) was purchased from Zhiyou Silicone materials, Inc., of Jiand.

Color masterbatch

The color master batch is called color master batch and also called color seed, is a special coloring agent for novel high polymer materials, and is also called a pigment preparation. Color concentrates are composed of three basic elements, a pigment or dye, a carrier and additives, and are aggregates prepared by uniformly supporting an excessive amount of pigment in a resin, and can be referred to as pigment concentrates, so that they have a higher tinctorial strength than the pigment itself. During processing, a small amount of color master batch is mixed with uncolored resin, and colored resin or products with designed pigment concentration can be obtained.

In one embodiment, the color concentrate is a PO color concentrate.

In the examples, the PO masterbatches were purchased from Astro, David, anti-static technology, Inc.

Octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl]Propionic acid ester

In one embodiment, the octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl]The preparation method of the propionate comprises the following steps: 0.1 part of A1 is weighed out₂O₃Putting the mixture into a high-pressure reaction kettle, adding 1 to 3 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate and 1.5 to 4.5 parts of propylene oxide, sealing the kettle, and introducing N₂Blowing to remove air in the kettle, opening condensed water, starting a mechanical stirrer to 500r.p.m., heating to 120 ℃ for catalytic reaction, and reactingAnd cooling after finishing.

The invention discovers that octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate has good solubility in alkane solvent, can effectively prevent thermal oxidation degradation of polymer materials in a long-term aging process, and can also improve the color change resistance of the polymer materials under high-temperature processing conditions. In addition, the heat resistance of the membrane material is enhanced by the propylene oxide chain introduced into the molecule.

In addition, the invention discovers that octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate can cooperate with tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to play a role in resisting oxidation, so that the membrane material has aging resistance and heat resistance. It is possible that pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate, in which active hydrogen atoms are present, which can be dissociated and combined with the macromolecular chain radical R.or ROO.to form hydrogen peroxide and a stable phenoxy radical. Protected by adjacent groups with larger volume, the phenoxy radical has high stability. In addition, the phenoxy radical and the benzene ring are in a large conjugated system, so that the chain reaction is stable, the activity is low, the chain reaction cannot be initiated, and only the phenoxy radical can be combined with another active free radical to stop one free radical again to generate a stable compound, thereby stopping the chain reaction. This stability of the phenoxy radical prevents the antioxidant from being consumed too quickly by direct oxidation and also reduces chain transfer reactions, thereby improving its antioxidant properties. Therefore, the antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester with high activity can effectively capture oxidation free radicals or peroxide free radicals, and the antioxidant octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate with low activity can supply hydrogen atoms, so that the antioxidant with high activity is regenerated, the antioxidant has long-term antioxidant effect, and the two antioxidants can generate synergistic effect after being compounded and used. When the ratio of the two is 2: 1, the performance of the membrane material is optimized, probably because if the amount of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate is excessive, the amount of highly active molecules in the molecule is small, the oxidation resistance is lowered, and if the amount is small, the durable oxidation resistance and the high temperature resistance cannot be exerted.

Examples n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS: 2082-79-3) was purchased from American plastication technology, Inc., Dongguan; propylene oxide (CAS: 75-56-9) was purchased from Guangzhou Chengyang Kongkushi Co.

In one embodiment, the substrate film is prepared by: and (2) conveying the first corona layer raw material, the bright layer raw material, the antistatic layer raw material, the core layer raw material, the antioxidation layer raw material, the matte layer raw material and the second corona layer raw material to a 7-layer co-extruder according to a formula, melting and extruding, casting onto a steel roller during melting, cooling and forming, flattening, and rolling to obtain the substrate film.

[ subbing layer ]

In one embodiment, the glue layer is obtained by drying raw materials used for the glue layer.

In one embodiment, the method for preparing the raw materials for the glue layer comprises the following steps: and (2) uniformly mixing 50-100 parts of acrylate resin, 60-80 parts of diluent, 0-10 parts of curing agent and 0-10 parts of stabilizer to obtain the acrylic resin.

In a preferred embodiment, the acrylate resin is an epoxy acrylate resin.

In a preferred embodiment, the diluent is ethyl acetate.

In a preferred embodiment, the curing agent is an n-butyl alcohol etherified melamine resin.

In a preferred embodiment, the stabilizer is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

The epoxy acrylate resins in the examples were purchased from Shanghai, Washington acrylic acid, Inc., under the designation S-812; the n-butyl alcohol etherified melamine formaldehyde resin is purchased from Shanghai Xinhua resin Co., Ltd; pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (CAS: 6683-19-8) was purchased from American plastication technology Co., Ltd, Dongguan.

[ Silicone oil layer ]

In one embodiment, the film material for semiconductor grinding and packaging further comprises a silicon oil layer.

In one embodiment, the silicone oil layer is attached to the upper surface of the substrate film.

In one embodiment, the silicon oil layer is obtained by drying raw materials used for the silicon oil layer.

In one embodiment, the preparation method of the raw materials for the silicon oil layer comprises the following steps: pouring 40-60 parts of simethicone into the diluent at a constant speed, stirring simultaneously, adding 3-5 parts of curing agent after stirring for 10-14min, stirring at a constant speed for 20-40min, adding 3-5 parts of stabilizer, and stirring at a constant speed for 20-30min to obtain the product.

In a preferred embodiment, the diluent is toluene.

Examples Dimethicone (CAS: 9006-65-9) was purchased from Guangzhou Weber chemical Co., Ltd.

[ PET layer ]

In one embodiment, the film material for semiconductor grinding and packaging further comprises a PET layer.

In one embodiment, the PET layer is attached to the lower surface of the adhesive layer.

In one embodiment, the PET layer is a PET film.

The PET film is a PET polyester film. Its advantages are high resistance to high temp, printing, easy machining and high voltage-insulating performance. The film is colorless, transparent and glossy, and has the advantages of excellent mechanical performance, high rigidity, hardness and toughness, puncture resistance, friction resistance, high temperature resistance, low temperature resistance, chemical resistance, oil resistance, air tightness and fragrance retention.

In the examples, the PET film was purchased from Shantou Runkang Plastic film Co., Ltd, and was designated PET-19.

In one embodiment, the direct coating method comprises the steps of:

s1: coating the raw material used for the silicon oil layer on the upper surface of the base material film after corona treatment, and placing the base material film in a drying oven for 1 to 2 days;

s2: coating the raw materials used for the adhesive layer on the lower surface of the base material film after corona treatment, and placing the base material film in an oven for 7 days for stabilization.

In one embodiment, the spin coating method comprises the steps of:

a: coating the raw material for the glue layer on the upper surface of the PET layer to obtain a transfer coating;

b: the corona and transfer coating on the lower surface of the substrate film is pressed and treated, and is stable after being placed for 15 days.

In one embodiment, the film material for semiconductor grinding and packaging has a thickness of 5-500 μm.

In a preferred embodiment, the thickness of the film material for semiconductor grinding and packaging is 50-200 μm.

Examples

In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.

Example 1

Embodiment 1 provides a film material for grinding and packaging a semiconductor, which comprises a substrate film and a glue layer from top to bottom in sequence; the base material membrane connects first corona layer, bright layer, antistatic layer, sandwich layer, antioxidation layer, matte layer, second corona layer crowded altogether including pasting in proper order.

The film material for grinding and packaging the semiconductor also comprises a silicon oil layer; the silicon oil layer is connected with the upper surface of the base material film.

The silicon oil layer is obtained by drying raw materials used by the silicon oil layer.

The preparation method of the raw materials used by the silicon oil layer comprises the following steps: and pouring 50 parts of simethicone into the toluene at a constant speed, stirring simultaneously, adding 4 parts of n-butyl alcohol etherified melamine resin after stirring for 12min, stirring at a constant speed for 30min, then adding 4 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and stirring at a constant speed for 25min to obtain the product.

The adhesive layer is obtained by drying raw materials used for the adhesive layer.

The preparation method of the raw materials used by the adhesive layer comprises the following steps: and uniformly mixing 75 parts of epoxy acrylate resin, 70 parts of ethyl acetate, 5 parts of n-butyl alcohol etherified melamine resin and 5 parts of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to obtain the epoxy acrylate resin.

The preparation raw materials of the first corona layer and the second corona layer comprise homopolymerized polypropylene.

The raw materials for preparing the bright layer and the matte layer comprise ethylene-ethyl acrylate copolymer.

The preparation raw materials of the antistatic layer comprise: 65 parts of modified polyethylene, 22 parts of elastomer, 7 parts of antistatic agent and 4 parts of crosslinking agent.

The preparation raw materials of the anti-oxidation layer comprise: 65 parts of modified polyethylene, 22 parts of elastomer, 6 parts of antioxidant and 4 parts of crosslinking agent.

The core layer preparation raw materials comprise: 65 parts of modified polyethylene, 22 parts of elastomer, 2 parts of color master batch and 3 parts of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.

The preparation method of the modified polyethylene comprises the following steps:

(1) adding 7 parts of phytic acid, 4.5 parts of magnesium oxide and 2 parts of wollastonite into water, stirring and grinding the mixture to enable the average particle size of the mixture to be less than 1 mu m, adding 10 parts of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, continuously grinding the mixture for 2h for surface treatment, then filtering the mixture, washing the mixture with water to enable the pH value to be 7, and drying the mixture to obtain the filler with the modified surface.

(2) Adding 50 parts of linear low-density polyethylene into an open mill, wherein the roll temperature is 160 ℃, adding a surface modified filler after the linear low-density polyethylene is coated on a roll, melting and blending, then discharging, and carrying out compression molding by a QLD-D type flat vulcanizing machine at the temperature of 195 ℃ to obtain the polyethylene.

The linear low density polyethylene is 7042 powder.

The ethylene-ethyl acrylate is 6200 powder.

The homo-polypropylene is powder T30S.

The elastomer is a propylene-based elastomer.

The propylene-based elastomer is under the designation 6202 FL.

The preparation method of the antistatic agent comprises the following steps: 18 parts of erucamide, 18 parts of polyoxyethylene-acrylic acid copolymer, 4 parts of copper sulfate, 9 parts of anhydrous potassium carbonate and

molecular sieves mixed in dimethyl sulfoxide, in N₂Reacting for 24 hours at 120 ℃ under protection to obtain the product.

The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.

The cross-linking agent is methyl hydrogen-containing silicone oil.

The color master batch is PO color master batch.

The octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl]The preparation method of the propionate comprises the following steps: 0.1 part of A1 is added into a reaction kettle₂O₃Then adding 2 parts of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate and 3 parts of propylene oxide, sealing the reaction kettle, and introducing N₂Blowing to remove air in the kettle, opening condensed water, starting a mechanical stirrer to 500r.p.m., heating to 120 ℃ for catalysisAnd (5) reacting, and cooling after the reaction is finished to obtain the product.

The preparation method of the substrate film comprises the following steps: and (2) conveying the first corona layer raw material, the bright layer raw material, the antistatic layer raw material, the core layer raw material, the antioxidation layer raw material, the matte layer raw material and the second corona layer raw material to a 7-layer co-extruder according to a formula, melting and extruding, casting onto a steel roller during melting, cooling and forming, flattening, and rolling to obtain the substrate film.

The preparation method of the film material for grinding and packaging the semiconductor comprises the following steps:

Example 2

Example 2 is essentially the same as example 1, except that:

the preparation raw materials of the antistatic layer comprise: 60 parts of modified polyethylene, 18 parts of elastomer, 5 parts of antistatic agent and 2 parts of crosslinking agent.

The preparation raw materials of the anti-oxidation layer comprise: 60 parts of modified polyethylene, 18 parts of elastomer, 3 parts of antioxidant and 2 parts of crosslinking agent.

The core layer preparation raw materials comprise: 60 parts of modified polyethylene, 18 parts of elastomer, 1 part of color master batch and 1.5 parts of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.

Example 3

Example 3 is essentially the same as example 1, except that:

the preparation raw materials of the antistatic layer comprise: 70 parts of modified polyethylene, 25 parts of elastomer, 10 parts of antistatic agent and 6 parts of crosslinking agent.

The preparation raw materials of the anti-oxidation layer comprise: 70 parts of modified polyethylene, 25 parts of elastomer, 8 parts of antioxidant and 6 parts of crosslinking agent.

The core layer preparation raw materials comprise: 70 parts of modified polyethylene, 25 parts of elastomer, 1 part of color master batch and 4 parts of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.

Example 4

Example 4 is essentially the same as example 1, except that:

the film material for semiconductor grinding and packaging also comprises a PET layer; the PET layer is connected with the lower surface of the adhesive layer.

The PET layer is a PET film.

a: the upper surface of the PET layer and the lower surface of the adhesive layer are compounded and then enter a drying oven to obtain a transfer coating;

Comparative example 1

Comparative example 1 is essentially the same as example 1 except that:

(1) adding 4.5 parts of magnesium oxide and 2 parts of wollastonite into water, stirring and grinding the mixture to ensure that the average particle size is less than 1 mu m, adding 10 parts of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, continuously grinding the mixture for 2 hours for surface treatment, filtering the mixture, washing the mixture with water to ensure that the pH value is 7, and drying the mixture to obtain the filler with the modified surface.

Comparative example 2

Comparative example 2 is essentially the same as example 1 except that:

(1) adding 7 parts of methacrylic acid-beta-hydroxyethyl ester, 4.5 parts of magnesium oxide and 2 parts of wollastonite into water, stirring and grinding the mixture to enable the average particle size of the mixture to be less than 1 mu m, adding 10 parts of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, continuously grinding the mixture for 2 hours for surface treatment, filtering the mixture, washing the mixture with water to enable the pH value to be 7, and drying the mixture to obtain the filler with the modified surface.

Comparative example 3

Comparative example 3 is essentially the same as example 1 except that:

(1) adding 7 parts of phytic acid and 4.5 parts of magnesium oxide into water, stirring and grinding to enable the average particle size of the phytic acid and the magnesium oxide to be less than 1 mu m, adding 10 parts of N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, continuously grinding for 2h for surface treatment, filtering, washing with water to enable the pH to be 7, and drying to obtain the filler with the modified surface.

Comparative example 4

Comparative example 4 is essentially the same as example 1 except that:

(1) adding 7 parts of phytic acid, 4.5 parts of magnesium oxide and 2 parts of wollastonite into water, stirring and grinding the mixture to enable the average particle size of the mixture to be less than 1 mu m, adding 10 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, continuously grinding the mixture for 2 hours for surface treatment, then filtering the mixture, washing the mixture with water to enable the pH value to be 7, and drying the mixture to obtain the filler with the modified surface.

Comparative example 5

Comparative example 5 is essentially the same as example 1, except that:

the antistatic agent is ethylene-sodium acrylate copolymer.

Comparative example 6

Comparative example 6 is essentially the same as example 1, except that:

the antistatic agent is erucamide.

Comparative example 7

Comparative example 7 is essentially the same as example 1 except that:

the core layer preparation raw materials comprise: 65 parts of modified polyethylene, 22 parts of elastomer and 2 parts of color master batch.

Comparative example 8

Comparative example 8 is essentially the same as example 1 except that: the antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.

The foregoing examples are merely illustrative and are provided to illustrate some of the features of the present disclosure. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. And that advances in science and technology will result in possible equivalents or sub-substitutes not currently contemplated for reasons of inaccuracy in language representation, and such changes should also be construed where possible to be covered by the appended claims.

Evaluation of Performance

(1) Heat resistance: and (3) pasting the film on a stainless steel plate with the surface roughness of 10, then placing the stainless steel plate in an oven with the temperature of 80 ℃ for aging for 12h, taking out the steel plate, naturally cooling to room temperature, and observing whether the residual glue or offset glue exists on the steel plate.

(2) Aging resistance:

a: polishing the surface of the copper rod smoothly and wiping the surface of the copper rod cleanly;

b: cutting the film into uniform strip samples, and winding the samples on a copper bar;

c: baking the copper bar wound with the sample at the constant temperature of 80-200 ℃, observing the surface condition of the film at intervals, recording the appearance condition of the film, and obtaining the aging resistant time of the film when the surface of the film is pulverized.

(3) Antistatic: the surface resistance of the membrane was measured with reference to the GB/T1410-78 standard.

(4) Deterioration of humid heat aged output power: the examples and comparative examples were fabricated with a Dow PO encapsulation adhesive film and tested according to GB/T18911-.

(5) Heat dissipation: the film thickness was 1mm and the thermal conductivity of the film was tested according to ASTM D5470.

The results of the experiment are shown in the following table:

table 1: performance test data of film materials obtained in examples and comparative examples

As can be seen from the table, the film material prepared by the invention has good heat resistance, high thermal conductivity, good heat dispersion, aging resistance, low surface resistance value, good antistatic property and low deterioration of damp-heat aging output power, and the film material is proved to have excellent damp-heat stability.

The film material prepared in the embodiment 1 has the thickness of 70 +/-3 mu m, the light transmittance is more than or equal to 75 percent, the tensile strength is more than or equal to 15MPa, the wetting tension is more than or equal to 36mN/m, and the breaking elongation is more than or equal to 500MD (%). In contrast, the performance data for the membrane materials made from the remaining examples were inferior to that of example 1.

Claims

1. The film material for grinding and packaging the semiconductor is characterized by comprising a base material film and a glue layer from top to bottom in sequence; the base material membrane connects first corona layer, bright layer, antistatic layer, sandwich layer, antioxidation layer, matte layer, second corona layer crowded altogether including pasting in proper order.

2. The film material for semiconductor grinding and packaging as claimed in claim 1, wherein the film material for semiconductor grinding and packaging further comprises a silicone oil layer; the silicon oil layer is connected with the upper surface of the base material film.

3. The film material for semiconductor grinding and packaging as claimed in claim 1, wherein the film material for semiconductor grinding and packaging further comprises a PET layer; the PET layer is connected with the lower surface of the adhesive layer.

4. The film material for semiconductor grinding and packaging as claimed in claim 1, wherein the raw material for preparing the first corona layer and the second corona layer comprises polypropylene.

5. The film material for grinding and packaging semiconductors as claimed in claim 1, wherein the raw material for preparing the bright layer and the matte layer comprises ethylene-ethyl acrylate copolymer.

6. The film material for grinding and packaging semiconductors as claimed in claim 1, wherein the antistatic layer is prepared from the following raw materials: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 5-10 parts of antistatic agent and 2-6 parts of crosslinking agent.

7. The film material for grinding and packaging semiconductors according to claim 1, wherein the raw material for preparing the antioxidation layer comprises: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 4-8 parts of antioxidant and 2-6 parts of crosslinking agent.

8. The film material for semiconductor grinding and packaging as claimed in claim 1, wherein the core layer preparation raw material comprises: 60-70 parts of modified polyethylene, 18-25 parts of elastomer, 1-3 parts of color master batch and 2-4 parts of octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.

9. A method for preparing a film material for grinding and packaging semiconductors according to any one of claims 1 to 8, wherein the method is classified into a direct coating method and a rotary coating method.

10. Use of a film material according to any one of claims 1-8 for semiconductor grinding and packaging in the preparation process and transportation of semiconductors.