TWI741886B - Heat-curing antistatic adhesive sheet - Google Patents

Abstract

The present invention is a thermosetting antistatic adhesive sheet with a surface resistivity equal to or less than 10 ¹¹ Ω, which is used in a high temperature sputtering process at 100 to 200°C, and includes: a polyimide film; And a thermosetting antistatic adhesive composition, which is adhered to the polyimide film, and includes a host polymer, a thermosetting group, a thermosetting agent, and a fluorine ionic liquid. The host polymerizes The saturated hydrocarbon C number of at least one monomer precursor of the substance is at least ≧4, the content of the thermal hardening group is between 0.5 and 8wt%, the decomposition temperature of the thermal hardening agent is lower than the temperature of the high-temperature sputtering process, The aliphatic long carbon chain C number of the fluorine ionic liquid is at least ≧3, and the S number contained in the unit structure of the fluorine ionic liquid is less than 2.

Description

Heat-curing antistatic adhesive sheet

The present invention is a heat-hardening antistatic adhesive sheet, and particularly refers to an adhesive sheet used to adhere electronic components, so that the electronic components undergo a high-temperature sputtering process to complete the electronic components after the EMI-resistant metal layer is plated. The components are removed from the adhesive sheet without residual glue, and the removal process does not damage the electronic components due to static electricity.

In the prior art, adhesive materials such as adhesive sheets have been widely used in the production process of various products (for example, semiconductor-related components). More specifically, it is generally applied to the adhesive sheet used in the high-temperature sputtering process. In order to prevent the sputtered metal from being plated on the electrode or pin of the electronic component during the process, the adhesion of the adhesive sheet must be sufficient The electronic components are fixed to each other without being separated from the electronic components during the sputtering process, that is, no peeling occurs. In addition, after the electronic component undergoes the sputtering process, in the pick-up step, it is necessary to separate the adhesive sheet from the electronic component. Therefore, for the high-temperature sputtering process of the EMI-resistant metal layer of electronic components, the required adhesive sheet needs to have both good adhesion and easy peeling characteristics after the sputtering treatment. And in response to more complex applications, such as the short-term fixation of electronic components with poor resistance to static electricity, such as electronic components for high-frequency Wi-Fi, it will be even more demanding that the components not only have the characteristics of being easy to remove after the process, but also the components When detaching from the adhesive sheet, it will not damage the electronic components and other elements due to static electricity.

In the existing adhesive sheet products used to adhere electronic components, the After that, the adhesive force between the adhesive sheet and the electronic component will increase, and therefore, the adhesive sheet and the electronic component are not easily peeled off, or the amount of peeling transfer pollution of the electronic component increases, which causes problems such as adhesive residue.

Therefore, in order to solve the above problems, the prior art document (TW106130993) has disclosed a thermosetting adhesive composition and an adhesive sheet, which can pass "the thermosetting adhesive composition meets the following equation: V=[(V0-V1) /V0]x100, where V is the rate of change of the adhesive force of the thermosetting adhesive composition and is between 80% and 98%, and V0 is the adhesive force of the thermosetting adhesive composition at room temperature , V1 is the technical solution that the hardened adhesive composition is heated to a predetermined temperature and then cooled to room temperature, so that the adhesive sheet can be adhered under the high-temperature heating step inherent in the semiconductor wafer production process The effect of force reduction, to achieve the effect of easy peeling. Moreover, the technical literature mentions that the base film on the composition adhesive sheet can achieve excellent antistatic properties through metal plating. However, in actual applications in some related processes for carrying or temporarily fixing electronic components, there will be problems with the use of opaque adhesives when the electronic components are fixed on the adhesive sheet due to the metal layer of the base film. .

As for the suppression of static electricity generated when electronic components are separated from the adhesive sheet, the conventional technology is to add conductive materials to the composition of the adhesive sheet to reduce the static electricity generated during the peeling process. There are many conductive materials known in the prior art, such as ionic liquids. , And the fluorine ionic liquid has the characteristics of high heat resistance, which can be used for the addition of the adhesive composition required by the general high-temperature process. The conductive network formed in the adhesive composition is not complete. Even if the amount of ionic liquid added is increased, the surface resistance cannot be reduced to a certain level, for example, it cannot be lower than 10 ¹¹ Ω. Therefore, in the prior art, there is still room for improvement in the adhesive sheet used to carry electronic components through the high-temperature metallization process.

The present invention provides a thermosetting antistatic adhesive sheet, the surface resistivity of which is equal to or less than 10 ¹¹ Ω, which is used in a high temperature sputtering process at 100 to 200°C, and includes: a polyimide film; And an adhesive composition, which is adhered to the polyimide film, and includes a host polymer, a thermosetting group, a thermosetting agent, and a fluorine ionic liquid, and at least one monomer of the host polymer The saturated hydrocarbon C number of the precursor is at least ≧4, the content of the thermal hardening group is between 0.5 to 8wt%, the decomposition temperature of the thermal hardening agent is lower than the temperature of the high-temperature sputtering process, the fluorine ionic liquid The C number of aliphatic long carbon chain is at least ≧3, and the number of S contained in the unit structure of the fluorine ionic liquid is less than 2.

Therefore, the adhesive sheet can be easily peeled off from the adhered electronic component at a selected temperature without generating static electricity to cause damage to the electronic component. Specifically, through the inherent heating step in the production process, the adhesive force of the thermosetting adhesive composition can be reduced, and the effect of easily peeling the thermosetting adhesive sheet can be achieved. At the same time, the amount of peeling transfer contamination on the adherend can be controlled to The minimum value, and then achieve the technical effect of not producing residual glue. In addition, the thermosetting adhesive composition contains a fluorine-based ionic liquid, which prevents the electronic components from being damaged by static electricity during the peeling process.

The benefit of the present invention is that the provided thermosetting antistatic adhesive sheet can produce the effect of reducing the adhesive force under the high-temperature heating step in the inherent high-temperature sputtering production process, achieve the effect of easy peeling, and find the thermosetting type The matching relationship between the adhesive composition and the fluorine ionic liquid effectively reduces the surface resistance of the adhesive sheet, thereby suppressing the generation of static electricity during the process of peeling the adhesive sheet from the electronic component.

In order to further understand the features and technical content of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description, and are not used to limit the present invention.

10: Polyimide film

12: Thermosetting antistatic adhesive composition

Figure 1 shows the first embodiment of the present invention.

Please refer to Figure 1. The thermosetting antistatic adhesive sheet of the present invention has a surface resistivity equal to or less than 10 ¹¹ Ω. It is used in a high-temperature sputtering process at 100~200°C. It includes: a polyamide The imine film 10; and the adhesive composition 12, which is adhered to the 10 polyimide film, which includes a host polymer, a thermosetting group, a thermosetting agent and a fluorine ionic liquid, the host polymer The saturated hydrocarbon C number of at least one monomer precursor is at least ≧4, the content of the thermal hardening group is between 0.5 and 8wt%, the decomposition temperature of the thermal hardening agent is lower than the temperature of the high-temperature sputtering process, the The aliphatic long carbon chain C number of the fluorine ionic liquid is at least ≧3, and the S number contained in the unit structure of the fluorine ionic liquid is less than 2.

The host polymer includes at least one structural unit derived from at least one monomer, and the above-mentioned monomer is an acrylic group containing a polymerizable carbon-carbon double bond or a methacrylic acid containing a polymerizable carbon-carbon double bond base. Hereinafter, an acrylic group containing a polymerizable carbon-carbon double bond or a methacrylic group containing a polymerizable carbon-carbon double bond will be referred to as a "monomer with a polymerizable carbon-carbon double bond group" ".

In addition, the monomer used to form at least one structural unit of the host polymer, for example, a methacrylic acid ester containing a polymerizable carbon-carbon double bond may be a (meth)acrylate of a saturated hydrocarbon. Saturated hydrocarbons may contain alkyl groups, cycloalkyl groups, or combinations thereof. For example, saturated hydrocarbon can be (formula Alkyl)acrylate or cycloalkyl(meth)acrylate. The alkyl group can be butyl, octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, or octadecyl, and the cycloalkyl group can be cyclobutyl or cyclohexyl. The alkyl group and the cycloalkyl group are based on the matching problem with the fluorine ionic liquid. The alkyl group cannot be methyl or ethyl; the cycloalkyl group cannot be the cyclopropyl group. Specifically, due to the compatibility of the host polymer with the fluorine ionic liquid, the carbon-carbon double bond methacrylic acid group can be a saturated hydrocarbon (meth)acrylate, and the C number of the saturated hydrocarbon is at least ≧4 .

In addition, the monomers related to the host polymer in the present invention may contain other copolymerizable monomers, such as acrylic acid, methacrylic acid, ( Carboxyl-containing monomers such as carboxyethyl meth)acrylate and carboxypentyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Sulfonic acid group-containing monomers such as amine propanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloxynaphthalenesulfonic acid; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; and Acrylic amine and acrylonitrile, etc. Specifically, when the host polymer includes structural units derived from the above-mentioned monomers, the physical properties of the host polymer, such as cohesion and heat resistance, will be improved. In fact, by using the above-mentioned monomers, products including the main polymer are less prone to residual degumming during use, and can withstand different high-temperature environments.

The above-mentioned copolymerizable monomers may be used alone to form the structural unit of the host polymer, or two or more copolymerizable monomers may be used at the same time to form the structural unit of the host polymer.

In addition, the monomer used to form the structural unit of the host polymer may also include a multifunctional monomer to perform a high degree of crosslinking reaction in the polymerization reaction. For example, multifunctional monomers can It is hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate.

Similarly, the above-mentioned polyfunctional monomers may be used alone, or two or more types of polyfunctional monomers may be used at the same time. Or, as described above for the copolymerizable monomers, among the monomers used to form the structural units of the host polymer, acrylic monomers or methacrylic monomers may be used alone. By using a multifunctional monomer, the derived host polymer can have improved cohesion and heat resistance.

In this way, the cohesion of the formed main polymer as an adhesive can be effectively improved. When further using high-temperature hardening reactants with different decomposition temperatures, the adhesive sheet provided by the present invention can have a good peeling effect through a high-temperature preparation method, and reduce the content of contaminants remaining on the surface of the product.

In addition, in the conventional technology, in order to increase the cohesive force of the adhesive colloid, a polyisocyanate-based crosslinking agent is also added, which is not limited in the present invention. For example, the polyisocyanate-based crosslinking agent can be toluene diisocyanate (TDI ), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), lysine diisocyanate (LDI) or related derivatives, which have the general formula RN=C=O.

As described above, the host polymer of the present invention may be obtained by polymerization reaction using the above-mentioned monomers alone, or by polymerization reaction using a mixture of two or more monomers. The type of polymerization reaction can be solution polymerization, emulsion polymerization, mass polymerization or suspension polymerization.

After the host polymer is formed through the polymerization reaction, the host polymer may have a weight average molecular weight greater than 200,000. Preferably, the host polymer of the embodiment of the present invention has a The weight average molecular weight is between 800,000 and 3.5 million. For the weight average molecular weight of the host polymer, it can be measured by gel permeation chromatography and calculated. have to).

The host polymer having a weight average molecular weight within the above range may have a lower oligomer content. In this way, after the thermosetting adhesive composition containing the host polymer is peeled from the surface of the adhesive after the thermal curing process, the contaminants remaining on the surface of the adhesive can be greatly reduced. Specifically, based on the above-mentioned selection of monomers related to the host polymer, the host polymer can be made to have a higher molecular weight. Accordingly, the host polymer will have better physical properties, such as resistance to residual degumming and excellent heat resistance. In this way, the low molecular weight substance will not move in the adhesive over time, thereby ensuring the stability of the thermosetting adhesive composition. In contrast, if the molecular weight of the host polymer is low, the low-molecular-weight substances in the adhesive product will have an adverse effect on the thermosetting adhesive composition.

In the embodiment of the present invention, the host polymer, the thermosetting group, the thermosetting agent, and the fluorine ionic liquid must cooperate with each other to achieve the desired effect of the present invention. Specifically, the thermosetting group contained in the thermosetting adhesive composition provided by the embodiment of the present invention is a group that contributes to high-temperature thermosetting, and may be a group that is compatible with the structural unit of the host polymer. The monomer of the polymerized carbon-carbon double bond group" the same group. For example, the thermosetting group may also contain polymerizable carbon-carbon double bond groups.

In addition, the thermosetting group is present in the hardening adhesive composition in the form of a monomer having a thermosetting group or an oligomer having a thermosetting group. In other words, the thermosetting group may exist in the form of a monomer having a polymerizable carbon-carbon double bond group or an oligomer.

In the present invention, the thermosetting group may be located on the side chain of the host polymer through bonding. Alternatively, the thermosetting group may be provided by an oligomer having a thermosetting group that is additionally added. In other words, at least one structural unit of the host polymer can be derived from a monomer having a thermosetting group, and this structural unit is located on the side chain of the host polymer, or it can be used without changing the host polymer. , Additional polymers with thermosetting groups are added. In the embodiment of the present invention, an additionally added oligomer having a thermosetting group is used as the source of the thermosetting group.

The thermosetting group used in the embodiment of the present invention may be derived from a monomer having a thermosetting group, and the monomer having a thermosetting group may be an acrylic group having a polymerizable carbon-carbon double bond or having A methacrylic monomer containing a polymerizable carbon-carbon double bond. Alternatively, the thermosetting group used in the embodiment of the present invention may be derived from the oligomer of the above-mentioned monomer having a thermosetting group. For example, the thermosetting group used in the embodiment of the present invention can be derived from pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetraethylene glycol di(meth)acrylate, trihydroxylate Methylpropane tri(meth)acrylate, 1,6-hexanediol (meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylic acid and polyol ester; ester -Acrylate oligomer; 2-propenyl-3-butenyl cyanurate; or isocyanurate, isocyanurate compound, etc.

In addition, when an oligomer derived from a monomer having a thermosetting group is used to form the thermosetting group in the thermosetting adhesive composition provided by the present invention, in order to make the thermosetting adhesive composition at a high temperature (100~ 200℃) After the reaction, the adhesive force to the adherend is controlled within the desired range. Based on the weight of the main polymer in the thermosetting adhesive composition, the polymerizable carbon in the monomer with the thermosetting group -The content of carbon double bond groups is between 0.5 and 8%, preferably between 1 and 5%, and most preferably between 3 and 3.6%. Based on the above range, you can choose appropriately The content of the thermosetting group in the thermosetting adhesive composition. The position of the thermosetting group can be adjusted according to product requirements.

The thermal hardening agent may be a high-temperature thermal hardening reactant. The high temperature thermal hardening reactant can react under the high temperature process to achieve the effect of reducing the adhesive force of the thermal hardening adhesive composition. Examples of thermosetting agents that can be used in the present invention are listed in Table 1 below, and Table 1 also lists their decomposition temperatures.

Through the use of the thermosetting agent, the thermosetting adhesive composition provided in the embodiment of the present invention can be heated, and the heat source can be used to initiate the polymerization reaction. The heat source used in the present invention comes from the heating and high temperature (100~200℃) sputtering machine provided by the machine, which can be radio waves, electron beams, infrared rays, visible rays, ultraviolet rays, X-rays or gamma rays. However, the heating method of the present invention (that is, the method of providing a heat source) is not limited here, and the heating source may also be provided by means of hot air oven, halogen lamp, microwave heating, stove or steam heat conduction.

In addition, after the high temperature (100~200℃) sputtering process, the thermal hardener can react to reduce the adhesion, and the electronic components can be easily separated from the adhesive sheet. The premise is that the thermal hardener is required. The decomposition temperature is at least <the temperature of the high-temperature sputtering process. For example, if the temperature of the high-temperature sputtering process is 100°C, the thermal hardening is selected as the thermal hardener 1~the thermal hardener 19, and the corresponding decomposition temperature is 66~99°C.

It is worth noting that during the high-temperature heating step, the heating temperature must be higher than the decomposition temperature of the thermal hardener used, and the heating time must last at least 5 minutes.

For example, when the thermal hardener 35 in Table 1 is used for the high-temperature heating step, the heating temperature must be higher than 153° C. and the heating time must be at least 5 minutes. In this way, it can be ensured that the thermosetting adhesive composition is hardened by heating. In addition, based on 100 parts of the host polymer, the content of the thermosetting agent in the thermosetting adhesive composition is between 0.1 and 20 parts by weight, preferably the content of the thermal polymerization initiator is between 0.5 and 10 parts by weight.

The thermosetting antistatic adhesive composition of the present invention may further include a thermal polymerization initiator for initiating the polymerization reaction of the host polymer. The thermal polymerization initiator can be benzoyl peroxide, azobisisobutyronitrile (AIBN), or a mixture thereof.

Based on 100 parts of the host polymer, the content of the thermal polymerization initiator in the thermosetting adhesive composition is between 0.1 and 20 parts by weight, preferably the content of the thermal polymerization initiator is between 0.5 To 10 parts by weight.

The fluorine ionic liquid (minimum decomposition temperature in the product>300℃) in the thermosetting antistatic adhesive composition provided by the present invention can not undergo any cracking or volatilization during the high temperature process, which means that it will pass through the high temperature (100 ~200℃) Sputtering process will not crack or volatilize and contaminate the components. The chemical structure and model of the fluorine ionic liquid (purchased by Mitsubishi Materials Corporation) that can be used in the present invention are listed in Table 2 below, and Table 3 also lists their decomposition temperatures.

Table 2: Models and corresponding chemical structures of fluorine ionic liquids

Table 3: Models of fluorine ionic liquids and corresponding decomposition temperatures

In the embodiment of the present invention, the host polymer, the thermosetting group, the thermosetting agent, and the fluorine ionic liquid must cooperate with each other to achieve the desired effect of the present invention, so the selected fluorine ionic liquid must have aliphatic The number of long carbon chain C is at least ≧3 and the number of S contained in the unit structure of the fluorine ionic liquid is less than 2.

The temperature suitable for the high-temperature sputtering process in the present invention can be in the range of 100 to 200°C. Depending on different machines, different palladium materials and sputtering different metals, the metal layer can be used to prevent EMI.

In addition, plating a metal layer that can prevent EMI on electronic components is not limited to sputtering. For example, evaporation, ion plating, etc. can also be used.

The adhesive sheet provided by the present invention can have different shapes. Specifically, the adhesive sheet It can be a sheet-shaped adhesive material, or a rolled-up adhesive material. In addition, the shape of the adhesive sheet can be adjusted according to the application field, the type of product used for adhesion, or other manufacturing process parameters, and the present invention is not limited herein. The adhesive sheet provided can have different shapes. Specifically, the adhesive sheet may be a sheet-shaped adhesive material, or an adhesive material rolled into a roll. In addition, the shape of the adhesive sheet can be adjusted according to the application field, the type of product used for adhesion, or other manufacturing process parameters, and the present invention is not limited herein.

The polyimide film 10 is used as a thermosetting adhesive composition support, and its thickness can be between 10 and 300 microns (μm), preferably between 12.5 and 200 microns.

In the present invention, the base film must be limited to a polyimide film. Because there are many types of conventionally-known film materials, but due to the high temperature sputtering process (100~200℃), except for polyimide film, other conventional film materials will have problems such as high temperature and easy shrinkage or cracking. happen.

In addition, the imine film can be well-bonded with other layers by surface treatment. For example, the base film may be subjected to physical treatment or chemical treatment, or the base film may be subjected to physical treatment and chemical treatment at the same time. Treatment methods may include light treatment, corona discharge, undercoat treatment, coating treatment, cross-linking treatment, chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionized radiation treatment, and the like.

The adhesive composition in the adhesive sheet provided by the embodiment of the present invention may be formed on the surface of the base film through the coating step, which is the transfer step. For example, the thermal adhesive composition can be directly coated on the surface of the polyimide film. Alternatively, the thermosetting adhesive composition can be first coated on the surface of a temporary carrier, the surface of the temporary carrier is pre-installed with a release agent, and the thermosetting adhesive composition to be coated on the release agent of the temporary carrier After drying and forming, the dried and formed thermosetting adhesive composition is transferred to the surface of the polyimide film.

In the present invention, the thickness of the adhesive composition may be in the range of 1 to 50 micrometers (μm). In practice, in order to ensure the adhesive force including the adhesive sheet, the adhesive composition must have a thickness greater than 1 micron.

In addition to the polyimide film and the adhesive composition, the adhesive sheet provided by the embodiment of the present invention may further include a release layer. The release layer may be disposed on the surface of the adhesive layer, so that the adhesive layer is disposed between the base film and the release layer. The release layer may have a thickness between 10 and 200 microns (μm), and may be formed of paper, polyethylene, polypropylene, and polyethylene terephthalate. The release layer can provide protection and isolation effects to the adhesive layer, so that the adhesive sheet will not be affected by external environmental factors during storage and reduce the adhesive force and other characteristics.

In practice, in order to increase the functionality of the release layer, the release layer can also be given a function of anti-ultraviolet rays, thereby effectively preventing the adhesive layer of the adhesive sheet from reacting under the influence of ultraviolet light in the storage environment. In addition, the release layer can be easily separated from the adhesive layer during use. The surface of the release layer can be subjected to specific surface treatment steps. For example, the surface of the release layer can be modified, such as polysiloxane treatment, long chain Alkylation treatment or peeling treatment such as fluorine treatment.

The adhesive sheet provided by the embodiment of the present invention can be used in the anti-electromagnetic interference (EMI) metal plating process, including sputtering, evaporation and ion plating, etc., but the object (electronic component) is not limited to which industry The application. And the material of the object adhered by the adhesive sheet is not limited. For example, it can be metal, ceramic, glass, semiconductor components, flexible board, rigid board, rigid-flex board, LED and other electronic materials, which are used in the production process of related electronic industries. Adhesive sheet for medium protection or ride.

After the adhesive sheet is attached to the adherend for specific production or manufacturing steps, before the adhesive sheet needs to be removed from the adherend, the adhesive sheet can be heated through the heating step in the production process of the adherend itself. The adhesive layer is heated.

Generally speaking, the heat treatment time for the adhesive sheet provided by the embodiment of the present invention is between 5 and 30 minutes. In practice, the heating time must be at least 5 minutes to ensure that the adhesion reduction rate of the adhesive layer is sufficient to easily separate the adherend from the adhesive sheet in the subsequent steps, and achieve the technical effect of easy pickup.

Next, examples and comparative examples will be used to demonstrate the content and effects of the thermosetting antistatic adhesive sheet provided by the present invention.

A one-liter (1L) round-bottomed flask is equipped with a separatory funnel, a thermometer, a nitrogen introduction tube, a condenser, a vacuum seal, a stirring rod, and a stirring blade. monomer.

The thermal polymerization initiator of the host polymer used AIBN in an amount of 0.3% by weight with respect to the total amount of monomers.

Next, nitrogen was introduced into the above-mentioned experimental apparatus for polymerization, and the temperature of the solution in the experimental apparatus was controlled to 65°C±2°C by means of water-proof heating while stirring, and reacted for 12 hours to obtain the host glue solution of the host polymer.

Mix the high temperature reaction heat hardening reactant (the "thermo hardener"), the thermo hardening group, and the fluorine ionic liquid into the main glue solution obtained above. The following examples and comparative examples show the formula and dosage. It is also necessary to add polyisocyanate-based crosslinking agent and ethyl acetate, and stir evenly to obtain an adhesive solution.

Relative to the total amount of monomers of the main glue, 2% polyisocyanate-based crosslinking agent (toluene diisocyanate, CAS number: 584-84-9, purchased from Sigma-Aldrich) was added.

Use a coater to coat the obtained polymer solution or adhesive solution on the peeling surface of the PET film that has been peeled off by the silicone compound, and dry it in a dryer at 100°C for 30 minutes to obtain a thickness It is a 20μm adhesive layer.

Corona treatment was performed on one side of the polyimide film in advance. The thickness of the base film is 25 μm.

The adhesive layer was attached to the corona-treated surface of the polyimide film with a hand roller, and the adhesive layer was adhered at 50° C. for 72 hours to produce an adhesive sheet. Fix the adhesive sheet on the iron frame, the exposed adhesive sheet in the middle of the iron frame can fix the electronic components in it, and then place it in the sputtering machine to sputter copper metal, and control the temperature of the machine to perform sputtering at 150°C.

A. Surface resistance measurement (Ω):

Surface resistance measuring instrument model: PRS-801; operating specification: refer to ASTM D257; operating method: cut the adhesive sheet into a sample of 10 cm long x 10 cm wide. Place the sample on an insulated flat surface, press the test pen (PRF-922B) vertically on the test surface, press RESET, and then press the TEST button to measure the surface resistance value.

B. The situation of the stripping process:

Under the condition that the component is mounted on the adhesive sheet, after the high-temperature sputtering process, the condition of peeling the electronic component from the adhesive sheet is understood. Use manual methods to peel the adhesive sheet and electronic components out of an opening first, and try to determine whether the adhesive sheet can be removed from the surface of the electronic component to determine the degree of peeling. For example, if the electronic component cannot be attached manually When the adhesive sheet is torn off, it is judged that it is not easy to peel off.

C. The components are contaminated by the adhesive sheet after the peeling process:

When the component is mounted on the adhesive sheet, after the high-temperature sputtering process, the component is peeled off the adhesive sheet, and the surface of the component is observed with a microscope for glue residue (magnification: 400X).

D. After the sputtering process, the adhesion of the adhesive sheet and the object to be affixed:

When the component is mounted via the adhesive sheet, after the high-temperature sputtering process, visually observe the adherence of the adhesive sheet and the object to be attached.

The following contents (%) are calculated based on the total weight of the thermosetting adhesive composition

Example 1:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 0.5% of methyl acrylate; thermosetting agent (32): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Example 2:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of hexyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 0.5% of methyl acrylate; thermosetting agent (32): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Example 3:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 8% of methyl acrylate; thermosetting agent (32): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Example 4:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate and And 2.2g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Example 5:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% EMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 1:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of propyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 0.5% of methyl acrylate; thermosetting agent (32): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 2:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 9% of methyl acrylate; thermosetting agent (32): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 3:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate and And 2.2g of acrylic acid. Thermosetting group: 0.3% of methyl acrylate; thermosetting agent (32): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 4:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIN111. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 5:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of EMIN111. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 6:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: TEATFSI of 1~5%. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 7:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate and And 2.2g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of MTOATFSI. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 8:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% methyl acrylate; thermosetting agent (32): 0.5% 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PET film.

Comparative example 9:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% of methyl acrylate; thermosetting agent (34): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 10:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermosetting group: 4% of methyl acrylate; thermosetting agent (35): 0.5% of 3,3,5,7,7-pentamethyl-1,2,4-trioxepane fluorine Ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparative example 11:

Main polymer: 500 grams (g) of ethyl acetate, 40.5 g of butyl methacrylate, and 2.2 g of acrylic acid. Thermal hardening group: 4% methyl acrylate; thermal hardening agent (36): 0.5% 3,3,5,7,7-Pentamethyl-1,2,4-trioxepane Fluorine ionic liquid: 1~5% of BMIEF41. (Adding 1~5% to observe the surface resistance is the best addition amount); Base film: PI film.

Comparison of Examples and Comparative Examples

The content of the above-mentioned specific embodiments is for describing the present invention in detail, however, these embodiments are for illustration only and are not intended to limit the present invention. Those who are familiar with the art can understand that various changes or modifications made to the present invention without departing from the scope defined by the appended patent application fall into a part of the present invention.

10: Polyimide film

12: Thermosetting antistatic adhesive composition

Claims (4)

A thermosetting antistatic adhesive sheet with a surface resistivity equal to or less than 10 ¹¹ Ω. It is used in a high-temperature sputtering process at 100 to 200°C. It includes: a polyimide film; and a heat The hardening type antistatic adhesive composition is adhered to the polyimide film and includes a host polymer, a thermosetting group, a thermosetting agent, and a fluorine ionic liquid. The host polymer is at least The saturated hydrocarbon C number of a monomer precursor is at least ≧4, the content of the thermosetting group is between 0.5 and 8wt% based on the host polymer, and the decomposition temperature of the thermosetting agent is lower than the high-temperature sputtering process The number of carbon (C) in the aliphatic long carbon chain of the fluorine ionic liquid is at least ≧3, and the number of sulfur (S) contained in the unit structure of the fluorine ionic liquid is less than 2. The thermosetting antistatic adhesive sheet according to claim 1, wherein the at least one monomer precursor of the host polymer includes an acrylic group having a polymerizable carbon-carbon double bond or a polymerizable Carbon-carbon double bond methacryloyl group. The thermosetting antistatic adhesive sheet according to claim 1, wherein the thermosetting group is in the form of a monomer having the thermosetting group or an oligomer having the thermosetting group. The heat-curable antistatic adhesive sheet according to claim 1, wherein the heat-curable antistatic adhesive composition further includes a thermal polymerization initiator that initiates the reaction of the host polymer Agent.

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