TWI743811B - Tape for glass processing - Google Patents

Abstract

The present invention is a tape for glass processing, which provides: a tape for glass processing that can fully undergo heat shrinkage in a short time while maintaining the width of the cut. The glass processing tape (10) of the present invention is characterized by having: an adhesive tape (15) having a substrate film (11) and an adhesive layer (12) formed on at least one side of the substrate film (11) ), the aforementioned adhesive tape (15) is the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured by a thermo-mechanical characteristic testing machine in the MD direction, and In the thermo-mechanical property testing machine in the TD direction, the sum of the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured during the temperature rise is a negative value. It is used for expansion adhesive tapes ( 15) The glass processor of the expansion project.

Description

Tape for glass processing

The present invention relates to the process of cutting the glass into wafer-shaped components, which can be used to fix the glass, and also to the die bonding process or loading process between the wafer and the wafer after the subsequent dicing, or between the wafer and the substrate. It can also be used in the assembly process, and it can also be used in the process of breaking the adhesive layer along the wafer through expansion. It is an extensible glass processing tape.

For cameras or sensors mounted in smartphones, etc., glass with various characteristics of optical characteristics is mounted. Generally speaking, these types of glass are made by vacuum vapor deposition of various materials for the glass that becomes the matrix. After that, after attaching adhesive and stretchable glass processing tape to the glass, the cutting process of breaking the glass into wafer units is implemented, and the expansion process of expanding (expanding) the glass processing tape is picked up. The picking process of the chip, and the picking up of the chip, and then the die bonding process at a specific place.

In the above-mentioned glass cutting process, cutting by a blade has been the mainstream in the past, but the effect of thinning of the glass itself or vapor deposition, such as scratches called grinding, has become a problem, and through this, there is a decrease in yield. The problem.

In order to solve this problem, in recent years, as a method of cutting glass, there have been proposals: using a laser processing device to cut glass without contact, the so-called invisible laser cutting method. For example, Patent Document 1 discloses that as an invisible laser cutting method, an adhesive layer (a die-bonding resin layer) is interposed, passing through the inside of a semiconductor substrate on which a thin sheet is attached, and irradiating a laser with focal light. When light is irradiated, a modified range through multiphoton absorption is formed inside the semiconductor substrate. This modified range is used as the process of cutting the planned part, and when the sheet is expanded, it is cut along the planned cutting part. A method for cutting semiconductor substrates in the process of semiconductor substrates and adhesive layers.

In addition, as another method of cutting a wafer using a laser processing device, for example, Patent Document 2 proposes a process involving mounting an adhesive layer (adhesive film) for die bonding on the back surface of the wafer. With the adhesive layer side of the wafer to which the adhesive layer is attached, the process of attaching a protective adhesive tape that can stretch, and the surface of the wafer with a self-adhesive protective adhesive tape, and irradiating the laser along the dicing path The process of dividing the light into individual chips, the process of expanding the protective adhesive tape to impart tensile force to the adhesive layer, the process of cutting the adhesive layer into individual chips, and the process of attaching the cut adhesive layer to the chip, Dividing method of wafer in the process of detaching from protective adhesive tape.

For example, according to the wafer cutting method described in Patent Document 1 and Patent Document 2, the physical load on the wafer is To be small, it is possible to cut the wafer without generating cutting chips like the current mainstream blade cutting. In addition, since the adhesive layer was broken through expansion, there was no chipping of the adhesive layer. Therefore, it has attracted attention as a superior technology that can replace blade cutting.

The dividing technology described in the above-mentioned documents is mainly composed of wafers, but it can also be applied to glass by changing the laser engine of the device to glass.

However, as described in the above-mentioned Patent Documents 1 and 2, in the method of expanding and breaking the adhesive layer by expansion, the conventional tape for semiconductor processing is used. As the amount of expansion increases, the part pushed up by the expansion ring Then, after the expansion is released, the part is loosened, and there is a problem that the gap between the wafers (hereinafter, "notch width") cannot be maintained.

Therefore, there has been proposed a method of breaking the adhesive layer through expansion, and then releasing the expansion, and then heating the slack portion of the tape for semiconductor processing to shrink it to maintain the width of the cut (for example, Patent Documents 3 and 4). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2003-338467 A [Patent Document 2] JP 2004-273895 A [Patent Document 3] International Publication No. 2016/152957 [Patent Document 4] Japanese Patent Application Publication No. 2015-211081

[The problem to be solved by the invention]

However, as a method of heating the slack and contraction of the tape for semiconductor processing produced by the expansion, generally speaking, it is used to produce the slack annular part pushed up by the expansion ring, by warming a pair of It is a method in which the air nozzle is surrounded, and the warm air is brought into contact with the part to heat and shrink it.

In the tape for semiconductor processing described in Patent Document 3, the thermal shrinkage rate of both the longitudinal direction and the width direction of the tape when heated at 100° C. for 10 seconds becomes 0% or more and 20% or less. However, when heating with a warm air nozzle, the temperature near the surface of the glass processing tape gradually rises, which is a time-consuming problem for removing the slack in all parts of the ring. In addition, when the slit width is narrow, it turns to be used for the division of glass, and the boundary line with the adjacent wafer becomes difficult to distinguish. In the image recognition at the time of picking, there is an identification error of the wafer, and the yield rate of the glass processing process A worsening problem occurs.

In addition, the tape for semiconductor processing described in Patent Document 4 has a shrinkage rate of 0.1% or more at 130°C to 160°C (refer to Claim 1 of Patent Document 4), and the temperature at which shrinkage occurs is high. Therefore, heat shrinkage by warm air requires high temperature and long heating time. The warm air affects the adhesive layer near the outer periphery of the wafer, and the divided adhesive layer is generated. The fear of melting and re-melting. In addition, when the slit width is narrow, it turns to be used for the division of glass, and the boundary line with the adjacent wafer becomes difficult to distinguish. In the image recognition at the time of picking, there is an identification error of the wafer, and the yield rate of the glass processing process A worsening problem occurs.

Therefore, the object of the present invention is to provide glass processing that can fully heat and shrink in a short time, easily distinguish the boundary with adjacent wafers, and can sufficiently maintain the width of the notch to suppress the recognition error of the wafer during the image recognition at the time of picking. adhesive tape. To solve the problem

In order to solve the above problems, the glass processing tape of the present invention has: an adhesive tape having a substrate film and an adhesive layer formed on at least one side of the substrate film. The thermomechanical characteristic testing machine, the average value of the differential value of the thermal deformation rate per 1℃ between 40℃~80℃ measured when the temperature is raised, and the thermomechanical characteristic testing machine passing through the TD direction, when the temperature is raised The sum of the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured is a negative value, and it is used for glass processing including the expansion process of the aforementioned adhesive tape.

In addition, in order to solve the above problems, the glass processing tape of the present invention has: an adhesive tape having a base film and an adhesive layer formed on at least one side of the base film. The base film is made of ion Cross-linked polymer resin, or a mixed resin composition of polypropylene and styrene-butadiene copolymer. The aforementioned adhesive tape is measured by a thermo-mechanical property testing machine passing through the MD direction at a temperature of 40℃~ The average value of the differential value of the thermal deformation rate between 80°C and 1°C, and the heat of each 1°C between 40°C and 80°C measured by the thermo-mechanical characteristic testing machine in the TD direction when the temperature is raised. The sum of the average values of the differential values of the deformation rate is the negative value.

In addition, the above-mentioned glass processing tape is preferably used for full-cutting blade cutting, full-cutting laser cutting, or invisible laser cutting through lasers.

In addition, the adhesive layer of the adhesive tape for glass processing is preferably laminated on the adhesive layer side, and the adhesive layer preferably has a light transmittance of 90% or more with respect to light having a wavelength of 550 nm. Invention effect

For example, according to the glass processing tape of the present invention, it can be fully heated and contracted in a short time, the boundary with the adjacent wafer can be easily distinguished, and the slit width can be sufficiently maintained to the extent that the recognition error of the wafer in the image recognition at the time of picking can be suppressed.

Hereinafter, embodiments of the present invention will be described in detail.

Fig. 1 is a cross-sectional view showing a glass processing tape 10 according to an embodiment of the present invention. The glass processing tape 10 of the present invention has a structure in which when the glass is divided into wafers by expansion, the transparent adhesive layer 13 is divided along the wafer. The glass processing tape 10 has: an adhesive tape 15 formed by a base film 11 and an adhesive layer 12 provided on the base film 11, and a transparent adhesive layer 13 provided on the adhesive layer 12. The structure of pasting the back of the glass on the transparent adhesive layer 13. However, each layer may be pre-cut (cut according to specifications) into a specific shape as a matching process or device. Furthermore, the glass processing tape 10 of the present invention may be cut into one piece of each glass, and a plurality of pieces may be cut into long pieces of one piece of glass and wound into a roll shape. The form can also be. In the following, the structure of each layer will be described.

＜Substrate film＞ When the base film 11 has uniform and isotropic expandability, it is preferable that the glass does not deviate from all directions and can be cut in the expansion process, and its material is not particularly limited. Generally speaking, comparing bridged resins with non-bridged resins, the restoring force for stretching is greater, while the tensile state after the expansion process plus heat shrinkage stress is greater. Along with this, after the expansion process, the slack generated in the tape is removed by heat shrinkage, and the tape is tightened to stably maintain the interval (notch width) between the wafers. Among bridging resins, it is also more desirable to use thermoplastic bridging resins. On the other hand, the non-bridging resin system has a lower restoring force for stretching than the bridging resin. Subsequently, after the expansion process of the low temperature range such as -15℃~0℃, it was once relaxed and returned to normal temperature, and the tape was not easy to shrink during the pick-up process. The point where the agent layers contact each other is superior. Among the non-bridging resins, it is more desirable to use olefin-based non-bridging resins.

As such a thermoplastic bridging resin system, for example, a metal ion bridged ethylene-(meth)acrylic acid binary copolymer or ethylene-(meth)acrylic acid-(meth)acrylic acid alkyl ester as the main polymer is exemplified Ion-crosslinked polymer resin of terpolymer of ingredients. These systems are on the surface of uniform expandability, suitable for expansion engineering, and are particularly suitable for points that produce strong restoring force when heated through bridges. The metal ion system contained in the ionomer resin is not particularly limited, but it can include zinc, sodium, etc., but the zinc ion system is preferably low in elution and low pollution. Among the above-mentioned alkyl (meth)acrylates of the terpolymer, the alkyl group having 1 to 4 carbon atoms has a high elastic modulus, and it is preferable for glass to transmit a strong force. Examples of such alkyl (meth)acrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, and propyl acrylate. , Butyl acrylate and so on.

In addition, as the above-mentioned thermoplastic bridging resin, in addition to the above-mentioned ionomer resin, it is selected from low-density polyethylene having a specific gravity of 0.910 or more to less than 0.930, or ultra-low-density polyethylene having a specific gravity of less than 0.910, and ethylene -For the resin of vinyl acetate copolymer, it is also best to bridge the structure by irradiating energy rays such as electron beams. Such a thermoplastic bridging resin system coexists in the resin from the bridging part and the non-bridging part, and has a certain uniform expansion. In addition, it is best to remove the slack of the tape caused by the expansion process from the situation where a strong restoring force is generated during heating, and the structure of the molecular chain contains almost no chlorine, even after the incineration treatment is used. It becomes an unnecessary tape, and it does not produce chlorinated aromatic hydrocarbons such as dioxin or its insulation, and the environmental burden is also small. By appropriately adjusting the amount of energy rays irradiated to the above-mentioned polyethylene or ethylene-vinyl acetate copolymer, a resin having sufficient uniform expandability can be obtained.

In addition, as the non-bridging resin system, for example, a mixed resin composition of polypropylene and a styrene-butadiene copolymer is exemplified.

As the polypropylene series, for example, a homopolymer of propylene, or a block type or random type propylene-ethylene copolymer can be used. The random type of propylene-ethylene copolymer is preferably less rigid. When the content rate of the ethylene constituent unit in the propylene-ethylene copolymer is 0.1% by weight or more, the rigidity of the tape and the compatibility with the resins in the mixed resin composition are superior. When the rigidity of the tape is appropriate, the cutting performance of the glass is improved, and when the compatibility of resins with each other is high, the amount of extrusion and discharge is easy to stabilize. More preferably, it is 1% by weight or more. In addition, when the content of the ethylene constituent unit in the propylene-ethylene copolymer is 7% by weight or less, it is advantageous that polypropylene becomes a point where it is easy to polymerize stably. More preferably, it is 5% by weight or less.

As the styrene-butadiene copolymer, a hydrogen-added structure can also be adopted. When hydrogen is added to the styrene-butadiene copolymer, the compatibility with propylene is good, and it can prevent embrittlement and discoloration through oxidative degradation caused by double bonding in butadiene. In addition, when the content of the styrene constituent unit in the styrene-butadiene copolymer is 5 wt% or more, it is preferable that the styrene-butadiene copolymer is easily polymerized stably. In addition, the content of 40% by weight or less is superior because of its flexibility and expansibility. It is more desirably 25% by weight or less, and still more desirably 15% by weight or less. As the styrene-butadiene copolymer system, either a block copolymer or a random copolymer may be used. The random copolymer-based styrene phase is uniformly dispersed, and the rigidity can be suppressed from becoming too large, which is ideal for improving the expandability.

When the content of polypropylene in the mixed resin composition is 30% by weight or more, it is preferable to suppress the unevenness of the thickness of the base film. When the thickness is uniform, it is easy to prevent the expansion property from becoming more square. In addition, the stress relaxation property of the base film becomes too large, the distance between the wafers becomes smaller with time, and the adhesive layers contact each other to cause remelting. More preferably, it is 50% by weight or more. In addition, when the polypropylene content is 90% by weight or less, it is easy to appropriately adjust the rigidity of the base film. When the rigidity of the base film becomes too large, the force necessary to expand the base film becomes greater, and the burden on the device becomes greater. However, the separation of the glass or the adhesive layer 13 may not be able to expand sufficiently. Therefore, it is important to make appropriate adjustments. The lower limit of the content of the styrene-butadiene copolymer in the synthetic resin composition is preferably 10% by weight or more, which is easy to adjust to the rigidity of the substrate film suitable for the device. When the upper limit is 70% by weight or less, it is advantageous at the point that thickness unevenness can be suppressed, and 50% by weight or less is more preferable.

However, in the example shown in FIG. 1, the base film 11 is a single layer, but it is not limited to this, and it may be a multiple layer structure in which two or more resins are laminated, and one type of resin layer It can also be stacked in two or more layers. Two or more types of resins, such as unified bridging or non-bridging, are ideal from the point of view of enhancing each characteristic. For the case of combining bridging or non-bridging and layering, it is the point of complementing each shortcoming. As ideal. The thickness of the base film 11 is not specifically defined, but it is easy to stretch during the expansion process of the tape 10 for glass processing, and if it has sufficient strength that does not cause breakage. For example, the degree of 50 to 300 μm is better, and 70 μm to 200 μm is more preferable.

As a manufacturing method of the base film 11 of multiple layers, the conventionally well-known extrusion method, a lamination method, etc. can be used. In the case of using the layering method, a transparent adhesive may be interposed between the layers.

＜Adhesive layer＞ The adhesive layer 12 can be formed by applying an adhesive composition on the base film 11. The adhesive layer 12 that constitutes the glass processing tape 10 of the present invention has retention of defects such as no peeling from the adhesive layer 13 during dicing, and no chip flying, etc., or during pick-up, and adhesion The peeling of the agent layer 13 becomes an easy characteristic.

In the glass processing tape 10 of the present invention, the composition of the adhesive composition constituting the adhesive layer 12 is not particularly limited. However, in order to improve the pick-up after cutting, the energy-ray curable composition is preferred. It is preferable that the peeling from the adhesive layer 13 becomes an easy material. As an example of the form, the adhesive composition contains 60 mol% or more of (meth)acrylate having an alkyl chain with carbon number of 6-12 as a base resin, and has an iodine value of 5~ The composition of 30 energy ray hardenable carbon-carbon double-bonded polymer (A). However, here, energy rays refer to ionizing radiation such as ultraviolet rays or electron beams.

In such a polymer (A), when the introduction amount of the energy-beam-curable carbon-carbon double bond is 5 or more, it is advantageous at the point that the adhesive force reduction effect after energy-beam irradiation becomes higher. More preferably, it is 10 or more. In addition, when the iodine value is 30 or less, the holding force of the wafer after the energy ray irradiation until the pickup is high, and it is advantageous to expand the gap of the wafer during the expansion before the pickup process. When the gap between the wafers can be fully expanded before the picking process, it is ideal because the image recognition of each wafer during picking is easy, and it becomes easy to pick up. In addition, when the introduction amount of the carbon-carbon double bond is an iodine value of 5 or more and 30 or less, it has stability with respect to the polymer (A) itself, and it is ideal because it is easy to manufacture.

Furthermore, when the glass transition temperature of the polymer (A) is -70°C or higher, it is superior in terms of heat resistance to heat accompanying energy ray irradiation, and more preferably -66°C or higher. In addition, if it is 15°C or less, various films are formed with respect to the surface condition, and the effect of preventing wafer scattering after dicing of glass with surface steps is superior, and it is more preferably 0°C or less, and even more ideal. Below -28°C.

The above-mentioned polymer (A) can be made of any structure, but for example, a structure obtained by mixing an acrylic copolymer and a compound having an energy-ray curable carbon-carbon double bond can be used, or it can be made functional -Based acrylic copolymer or methacrylic copolymer with functional group (A1), and a compound having a functional group that can react with its functional group and having an energy-ray-curable carbon-carbon double bond (A2) The resulting composition of the reaction.

Among them, the methacryl-based copolymer (A1) having the above-mentioned functional group is exemplified by a monomer (A1-1) having a carbon-carbon double bond such as alkyl acrylate or alkyl methacrylate. It is a structure obtained by copolymerization with a monomer (A1-2) having a carbon-carbon double bond and having a functional group. Examples of the monomer (A1-1) series include: hexyl propionate having an alkane chain with carbon number of 6-12, n-octyl acrylate, isooctyl acrylate, isooctyl 2-acrylate, ten acrylate Dialkyl esters, decyl acrylate, dodecyl acrylate or monomers with a chain carbon number of 5 or less, n-pentyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, or The same methacrylate etc.

However, in the monomer (A1-1), the component having an alkyl chain of 6 or more carbon atoms can reduce the peeling force between the adhesive layer and the adhesive layer, which is superior in terms of pick-up properties. In addition, the component below 12 has a low elastic modulus at room temperature, and the adhesive layer and the adhesive layer are superior in terms of the adhesive force at the interface. When the adhesive force of the interface between the adhesive layer and the adhesive layer is high, when the tape is expanded and the glass is cut, the deviation of the interface between the adhesive layer and the adhesive layer can be suppressed, and the cutting performance is improved, which is ideal.

In addition, as the monomer (A1-1), the higher the carbon number of the alkane chain is, the lower the glass transition temperature becomes. By appropriate selection, an adhesive composition with a desired glass transition temperature can be prepared. Thinger. In addition, as for the glass transition temperature, for the purpose of improving various properties such as compatibility, it is also possible to formulate low-molecular compounds having carbon-carbon double bonds such as vinyl acetate, styrene, and acrylonitrile. In this case, these low-molecular-weight compounds are formulated in a range of 5% by mass or less of the total mass of the monomer (A1-1).

On the other hand, as the functional group system possessed by the monomer (A1-2), carboxyl group, hydroxyl group, amino group, cyclic anhydride group, epoxy group, isocyanate group, etc. can be mentioned, and as the monomer (A1-2 ) Specific examples include: acrylic acid, methacrylic acid, cinnamic acid, itaconic acid, fumaric acid, phthalic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol mono Acrylic esters, hydroxyethyl methacrylate, N-methylol methacrylamide, N-methylol methacrylamide, allyl alcohol, N-alkylamine ethyl acrylate, N-alkane Base amine ethyl acrylates, acrylamides, methacrylamides, maleic anhydride, itaconic anhydride, fumaric anhydride, phthalic anhydride, glycidyl acrylate, methyl methacrylate Glycidyl acrylate, allyl glycidyl ether, etc.

Furthermore, in compound (A2), when the functional group used in compound (A1) is a carboxyl group or a cyclic acid anhydride group as the functional group used in compound (A1), examples include hydroxyl group, epoxy group, isocyanate group In the case of a hydroxyl group, examples include: cyclic anhydride groups, isocyanate groups, etc., in the case of amino groups, examples include epoxy groups, isocyanate groups, etc., in the case of epoxy groups, examples include Examples include a carboxyl group, a cyclic acid anhydride group, an amino group, and the like. As specific examples, the same configurations as those listed in the specific examples of the monomer (A1-2) can be cited. In addition, as the compound (A2), it is also possible to use a structure in which a part of the isocyanate group of the polyisocyanate compound is urethane-formed with a hydroxyl group or a carboxyl group and a monomer having an energy-ray curable carbon-carbon double bond.

However, when the unreacted functional group remains in the reaction of the compound (A1) and the compound (A2), the desired structure can be produced with respect to characteristics such as acid value or hydroxyl value. When the residual OH group is the hydroxyl value of the polymer (A) becomes 5~100, by reducing the adhesive force after energy ray irradiation, the risk of picking errors can be reduced. In addition, when the acid value of the remaining COOH group of the polymer (A) becomes 0.5-30, the improvement effect after the restoration of the adhesive layer after expanding the glass processing tape of the present invention can be obtained, which is ideal. When the hydroxyl valence of the polymer (A) is 5 or more, the adhesive force reduction effect after energy ray irradiation is superior, and when it is 100 or less, it is at the point of fluidity of the adhesive after energy ray irradiation. And for superiority. In addition, when the acid value is 0.5 or more, it is superior in terms of tape restorability, and when it is 30 or less, it is superior in terms of fluidity of the adhesive.

In the above-mentioned synthesis of polymer (A), as the organic solvent in the case of reaction by solution polymerization, ketone, ester, alcohol, aromatic constitution can be used, but among them, toluene, ethyl acetate , Isopropanol, benzyl ethoxyethanol, diethylene glycol monobutyl ether, acetone, methyl ethyl ketone, etc. Generally, a good solvent for acrylic polymers, a solvent with a boiling point of 60~120℃ is better, and it is used as a polymerization The initiator usually uses radical generators such as α,α'-azobisisobutyronitrile and other azobis series, and organic peroxides such as benzyl peroxide. In this case, a catalyst and a polymerization inhibitor may be used in combination as necessary, and by adjusting the polymerization temperature and the polymerization time, a polymer (A) having a desired molecular weight can be obtained. In addition, for molecular weight adjustment systems, mercaptans are used, and carbon tetrachloride-based solvents are preferred. However, this reaction system is not limited to solution polymerization, and may be another method such as bulk polymerization and suspension polymerization.

From the above, the polymer (A) can be obtained, but in the present invention, when the molecular weight of the polymer (A) is 300,000 or more, it is advantageous in that the cohesive force can be increased. When the cohesive force is high, it has the effect of suppressing the deviation of the interface with the adhesive layer during expansion, and since it is easy to transmit the tensile force to the adhesive layer, it is ideal at the point where the separability of the adhesive layer is improved. When the molecular weight of the polymer (A) is 2 million or less, it is advantageous in terms of suppressing gelation during synthesis and coating. However, the molecular weight in the present invention refers to the mass average molecular weight in terms of polystyrene.

In addition, in the glass processing tape 10 of the present invention, the resin composition constituting the adhesive layer 12 is added to the polymer (A), and the compound (B) may also function as a bridging agent. For example, polyisocyanates, melamine formaldehyde resins, and epoxy resins can be mentioned, and these can be used alone or in combination of two or more types. This compound (B) reacts with the polymer (A) or the substrate film, and through the bridging structure that can lead to the result, the polymer (A) and (B) can be used as the main components after the adhesive composition is applied. The cohesive force of the adhesive.

The polyisocyanate system is not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, 4,4'-diphenylethyl ether diisocyanate, 4,4'-[2,2-bis(4-phenoxyphenyl)propane] diisocyanate and other aromatic isocyanates, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene Diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane toluene diisocyanate, 2,4'-dicyclohexylmethane toluene diisocyanate, lysine diisocyanate, lysine Specifically, for triisocyanate and the like, Corona L (manufactured by Nippon Polyurethane Co., Ltd., trade name) and the like can be used. Specifically as the melamine formaldehyde resin system, NIKALAC MX-45 (manufactured by Sanwa Chemical Co., Ltd., trade name), MELA (manufactured by Hitachi Chemical Co., Ltd., trade name), etc. can be used. As the epoxy resin, TETRAD-X (manufactured by Mitsubishi Chemical Corporation, trade name) or the like can be used. In the present invention, it is particularly preferable to use polyisocyanates.

The addition amount of the compound (B) is superior to 100 parts by mass of the polymer (A) as an adhesive layer of 0.1 parts by mass or more at the point of cohesion. More preferably, it is 0.5 parts by mass or more. In addition, the adhesive layer of 10 parts by mass or less is superior at the point where the gelation is suppressed during the application process, and the workability of the adhesive preparation or coating becomes good. More preferably, it is 5 parts by mass or less.

In addition, in the present invention, the adhesive layer 12 may contain a photopolymerization initiator (C). The photopolymerization initiator (C) contained in the adhesive layer 12 is not particularly limited, and a conventionally known structure can be used. For example, one can cite: benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone, etc. Diphenyl ketones, acetophenones such as acetophenone, diethoxyacetophenone, 2-ethylanthraquinone, anthraquinones such as t-butylanthraquinone, 2-chlorothioxanthone, Benzoin ethyl ether, benzoin isopropyl ether, diphenylethylenedione, 2,4,5-triphenylimidazole dimer (rophene dimer), acridine compounds, etc., these systems can be singly or in combination Use two or more kinds. As the addition amount of the photopolymerization initiator (C), based on 100 parts by mass of the polymer (A), 0.1 parts by mass or more is preferable, and 0.5 parts by mass or more is more preferable. In addition, the upper limit thereof is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

Furthermore, for the energy-ray curable adhesive used in the present invention, an adhesive imparting agent, an adhesive modifier, a surfactant, etc., or other modifiers can be prepared as necessary. In addition, fillers of inorganic compounds may be added as appropriate.

The adhesive layer 12 can be formed using a conventional adhesive layer forming method. For example, it can be formed by applying the above-mentioned adhesive composition to a specific surface of the base film 11, or applying the above-mentioned adhesive composition to a spacer (for example, a mold coated with a release agent). After the adhesive layer 12 is formed on a plastic film or sheet, etc., the adhesive layer 12 is transferred to a specific surface of the substrate to form the adhesive layer 12 on the substrate film 11. However, the adhesive layer 12 may have a single-layer form, or may have a laminated form.

The thickness of the adhesive layer 12 is not particularly limited. When the thickness is 2 μm or more, it is superior in terms of viscosity, and 5 μm or more is more preferable. When it is 15 μm or less, it is excellent for pick-up, and it is more preferably 10 μm or less.

Adhesive tape 15 is the average value of the differential value of the thermal deformation rate per 1°C between 40℃~80℃ measured by the thermo-mechanical characteristics testing machine in the MD (Machine Direction) direction, and the For the thermo-mechanical characteristics testing machine in the TD (Transverse Direction) direction, the sum of the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured during heating is negative, that is, less than 0. The MD direction is the flow direction when the film is formed, and the TD direction is the direction perpendicular to the MD direction.

According to the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured by a thermo-mechanical characteristic testing machine in the MD direction of the adhesive tape 15 when the temperature is raised, and the passing in the TD direction The thermo-mechanical characteristic testing machine can be used for low temperature and short time heating when the sum of the average value of the differential value of the thermal deformation rate per 1 ℃ between 40 ℃ and 80 ℃ measured during the heating is regarded as a negative value. The tape 10 for glass processing is shrunk. Along with this, in the case where a pair of warm air nozzles are used to heat and shrink the part where the slack of the glass processing tape 10 is generated, there is no case in which the expansion amount is reduced while heating and shrinking multiple times. The slack caused by expansion can be removed in a short time, and the width of the incision can be maintained appropriately.

The thermal deformation rate is measured in accordance with JIS K7197:2012 and the amount of deformation through temperature, and can be calculated by the following formula (1). Thermal deformation rate TMA(%)=(deformation amount of sample length/sample length before measurement)×100 (1) However, the amount of deformation is displayed with the expansion direction of the sample as positive and the contraction direction as negative.

The differential value of the thermal deformation rate becomes a curve in the MD direction or a curve in the TD direction in Fig. 7, and the sum of the average value of the differential value in the MD direction and the average value of the differential value in the TD direction is negative. : It means that the adhesive tape is fully contracted between 40℃ and 80℃. In order to make the sum of the average value of the differential value in the MD direction and the average value of the differential value in the TD direction as a negative value, the process of extending the resin film after film formation is added, and the resin that constitutes the adhesive tape 15 is added. For the type, adjust the thickness of the adhesive tape 15, or the extension in the MD direction or the TD direction. As a method of extending the adhesive tape in the TD direction, there are: a method of using a tenter, a method of blow molding (expansion), a method of using an expansion roller, etc., and as a method of extending in the MD direction, the method is Examples include: a method of stretching when the mold is ejected, a method of stretching in a conveying roller, and the like. As a method of obtaining the adhesive tape 15 of the present invention, any method may be adopted.

＜Adhesive layer＞ In the glass processing tape 10 of the present invention, the adhesive layer 13 is a structure in which glass is bonded to the adhesive layer 13 and then diced. When the wafer is picked up, the adhesive layer 13 is peeled off from the adhesive layer 12 and attached to the wafer. In addition, it is used as an adhesive when fixing a chip to a substrate or a lead frame.

The adhesive layer 13 is not particularly limited, but it may be a film-like adhesive generally used for glass. For example, a structure containing a thermoplastic resin and a thermopolymerizable component may be mentioned. The above-mentioned thermoplastic resin used in the adhesive layer 13 of the present invention is a resin having thermoplasticity, or in an uncured state, having thermoplasticity, and a resin that forms a bridge structure after heating is preferable, and is not particularly limited, but as one The morphology system can include: a thermoplastic resin with a weight average molecular weight of 5000 to 200,000 and a glass transition temperature of 0 to 150°C. In addition, as another form, a thermoplastic resin having a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of -50 to 0°C can be cited.

Examples of the former thermoplastic resin series include: polyimide resin, polyimide resin, polyetherimide resin, polyimide imide resin, polyester resin, polyimide resin, Phenoxy resin, polyether resin, polyether sulfide resin, polyphenylene sulfide resin, polyether ketone resin, etc. Among them, polyimide resin is used, phenoxy resin is better, and it is used as the latter's thermoplastic resin. Polymers containing functional groups are preferred.

The polyimide resin system can be obtained by the condensation reaction of tetracarboxylic dianhydride and diamine by a known method. That is, in the organic solvent, use equal mol or slightly equal mol (the order of addition of each component is arbitrary) tetracarboxylic dianhydride and diamine, and add the reaction temperature below 80°C, ideally 0-60°C reaction. As the reaction progresses, the viscosity of the reaction solution slowly rises, and polyimide precursor polyamide acid is formed. When this polyamide acid is heated at a temperature of 50 to 80°C to depolymerize it, its molecular weight can also be adjusted. The polyimide resin system can be obtained by dehydrating and ring-closing the above-mentioned reactant (polyamide acid). The dehydration loop-closure system can be heat-treated by a thermal loop-closure method, and a chemical loop-closure method using a dehydrating agent is performed.

The tetracarboxylic dianhydride used as the raw material of the polyimide resin is not particularly limited. For example, 1,2-(ethylene) bis(trimellitic anhydride), 1,3-(trimethylene) bis (Trimellitic anhydride), 1,4-(tetramethylene) bis(trimellitic anhydride), 1,5-(pentamethylene) bis(trimellitic anhydride), 1,6-(hexamethylene) Methyl)bis(trimellitic anhydride), 1,7-(heptamethylene)bis(trimellitic anhydride), 1,8-(octamethylene)bis(trimellitic anhydride), 1,9 -(Namethylene)bis(trimellitic anhydride), 1,10-(decamethylene)bis(trimellitic anhydride), 1,12-(dodecamethylene)bis(trimellitic anhydride) ), 1,16-(hexamethylene) bis(trimellitic anhydride), 1,18-(octadecemethylene) bis(trimellitic anhydride), pyromellitic dianhydride, 3,3 ',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propionic dianhydride , 2,2-bis(2,3-dicarboxyphenyl)propionic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)acetic acid dianhydride, 1,1-bis(3,4- Dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) ) Sulfonic acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride , 3,4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,2',3'-benzophenone tetracarboxylic dianhydride, 3,3,3',4'-two Benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 1,2 ,4,5-Naphthalenetetracarboxylic acid anhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Anhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5 ,6-Tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,4,3',4'- Biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxylic acid phenyl) dimethyl silan dianhydride, bis(3,4-di Carboxylic acid phenyl) methyl phenyl silane dianhydride, bis (3,4-dicarboxylic acid phenyl) diphenyl silane dianhydride, 1,4-bis (3,4-dicarboxylic acid phenyl dimethyl) Silyl)phthalic anhydride, 1,3-bis(3,4-dicarboxylic acid phenyl)-1,1,3,3-tetramethylcyclohexylpropanol dianhydride, p-phenylene-bis (Trimellitic acid dianhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, decalin-1,4,5,8-pyromellitic dianhydride , 4,8-Dimethyl-1,2,3,5,6,7 -Hexahydronaphthalene-1,2,5,6-pyromellitic dianhydride, cyclopentane-1,2,3,4-pyromellitic dianhydride, pyrrolidine-2,3,4,5- Pyromellitic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis(exo-bicyclo[2,2,1]heptane-2,3-dicarboxylic dianhydride, bicyclo[2.2 .2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis [4-(3,4-Dicarboxyphenyl)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1,4- Bis(2-hydroxyhexafluoroisopropyl)benzenedi(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzenedi(trimellitic anhydride), 5-(2,5- Dioxytetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, etc., and one of these can also be used in combination Or two or more kinds.

(式中，R₁ 及R₂ 係顯示碳原子數1~30之二價的碳化氫基，各自亦可為同一或不同，而R₃ 及R₄ 係顯示一價的碳化氫基，各自亦可為同一或不同，m係1以上的整數)In addition, the diamine as the raw material of polyimine is not particularly limited. For example, o-o-phenylenediamine, m-o-phenylenediamine, p-o-phenylenediamine, 3,3'-diamine diamine can be used. Phenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminediphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, bis(4-amino-3,5-xylyl)methane, bis(4-amine-3,5-diisopropylphenyl)methane, 3,3 '-Diaminodiphenyldifluoromethane, 3,4'-Diaminodiphenyldifluoromethane, 4,4'-Diaminodiphenyldifluoromethane, 3,3'-Diaminodifluoromethane Benzene, 3,4'-diamine diphenyl sulfide, 4,4'-diamine diphenyl sulfide, 3,3'-disulfide diphenylamine, 3,4'-disulfide diphenylamine, 4,4'- Disulfide phenylamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(3-amine Phenyl) propane, 2,2'-(3,4'-diaminobiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl) Hexafluoropropane, 2,2-(3,4'-diaminobiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminobenzene) Oxy)toluene, 1,4-bis(3-aminophenoxy)toluene, 1,4-bis(4-aminophenoxy)toluene, 3,3'-(1,4-phenylene(1 -Methylethylene)) bisaniline, 3,4'-(1,4-phenylene (1-methylethylene)) bisaniline, 4,4'-(1,4-phenylene (1-methylethylene)) bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy) Phenyl) propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane , Bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(4-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy)benzene Aromatic diamine groups such as sulfonic acid, bis(4-(4-aminophenoxy)phenyl)sulfonic acid, 3,5-diaminobenzoic acid, 1,2-ethylenediamine, 1, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane , 1,9-diaminononane, 1,10-diaminodecane, 1,11-aminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, in the following Silicon diamine shown in general formula (1), 1,3-bis(aminomethyl)cyclohexane, JEFFAMINE D-230, D-400, D-2000, D-4000, ED manufactured by Santekunokemikaru Co., Ltd. -600, ED-900, ED-2001, EDR-148 and other polyoxyalkylene diamines, etc. The aliphatic diamine group, etc., can also be used in combination of one or more of these. The glass transition temperature of the polyimide resin is preferably 0 to 200°C, and the weight average molecular weight is 10,000 to 200,000.

(In the formula, R ₁ and R ₂ show a divalent hydrocarbon group with 1 to 30 carbon atoms, and each may be the same or different, and R ₃ and R ₄ show a monovalent hydrocarbon group, and each is also Can be the same or different, m is an integer greater than 1)

The phenoxy resin, which is one of the above-mentioned other ideal thermoplastic resins, is preferably obtained by reacting various bisphenols with epichlorohydrin, or by reacting liquid epoxy resins with bisphenols. , And the bisphenol series may include: bisphenol A, bisphenol AF, bisphenol AD, bisphenol F, and bisphenol S. Phenoxy resins have a similar structure to epoxy resins, and have good compatibility with epoxy resins, and are suitable for imparting good adhesion to adhesive films.

Examples of the phenoxy resin system used in the present invention include resins having repeating units shown in the following general formula (2).

In the above general formula (2), the X system shows a single bond or a divalent linking group. Examples of the divalent linking group system include an alkylene group, a phenylene group, -O-, -S-, -SO-, or -SO ₂ -. Here, the alkyl group is preferably an alkylene group having 1 to 10 carbon atoms, and -C(R ₁ )(R ₂ )- is more preferable. R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and the alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl , Isopropyl, isooctyl, 2-ethylhexyl, 1,3,3-trimethylbutyl, etc. In addition, the alkyl group may be substituted with a halogen atom, and for example, a trifluoromethyl group may be mentioned. X is an alkylene group, preferably -O-, -S-, fluorenyl or -SO ₂ -, and more preferably an alkylene group, -SO ₂ -. Among them, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH ₂ -, -SO ₂ -are preferred, and -C(CH ₃ ) ₂ -, -CH(CH ₃ )-,- CH ₂ -is better, and -C(CH ₃ ) ₂ -is particularly desirable.

If the phenoxy resin shown in the above general formula (2) has repeating units, X in the above general formula (2) is a resin with multiple different repeating units, or X is composed of only the same repeating unit Can. In the present invention, X is preferably a resin composed only of the same repeating unit.

In addition, when the phenoxy resin shown in the above general formula (2) contains a polar substitution group such as a hydroxyl group and a carboxyl group, the compatibility with the thermally polymerizable component is improved, and uniform appearance or characteristics can be imparted. .

When the mass average molecular weight of the phenoxy resin is 5000 or more, it is ideal from the point of film formation. It is more desirably 10,000 or more, and still more desirably 30,000 or more. In addition, when the mass average molecular weight is 150,000 or less, the fluidity during heating and pressing or the compatibility with other resins are preferable. More preferably, it is 100,000 or less. In addition, when the glass transition temperature is -50°C or higher, it is desirable from the point of film formability, more desirably 0°C or higher, and still more desirably 50°C or higher. When the glass transition temperature is 150°C, the adhesive strength of the adhesive layer 13 during cutting is superior, and it is more desirably 120°C or less, and even more desirably 110°C or less.

On the other hand, as the functional group system in the polymer containing the above-mentioned functional group, for example, an oxypropylene group, an acrylic group, a butylene group, a hydroxyl group, a carboxyl group, an isocyanurate group, an amine group can be mentioned. Among them, an oxypropylene group is preferred.

Examples of the high-molecular-weight component system containing the above-mentioned functional group include (meth)acrylic copolymers of functional groups such as oxypropylene group, hydroxyl group, and carboxyl group.

As the above-mentioned (meth)acrylic copolymer system, for example, (meth)acrylate copolymer, acrylic rubber, etc. can be used, and acrylate rubber is preferred. Acrylic rubber is a rubber composed mainly of copolymers of butyl acrylate and acrylonitrile, or copolymers of ethyl acrylate and acrylonitrile, etc., with acrylate as the main component.

As the functional group, in the case of containing an oxypropylene group, the oxypropylene group preferably contains repeating units in an amount of 0.5 to 6.0% by weight, more preferably 0.5 to 5.0% by weight, and particularly preferably 0.8 to 5.0% by weight. The oxypropylene group-containing repeating unit refers to the constituent monomer of the (meth)acrylic copolymer containing the oxypropylene group, and specifically, it is glycidyl acrylate or glycidyl methacrylate. When the amount of repeating units contained in the oxypropylene group is within this range, the adhesive force can be ensured and gelation can be prevented.

As glycidyl acrylate and glycidyl methacrylate, the above-mentioned (meth)acrylic acid copolymer constitutes a single system such as ethyl (meth)acrylate and butyl (meth)acrylate. Etc., these systems can also be used alone or in combination of two or more types. However, in the present invention, ethyl (meth)acrylate means: showing ethacrylate and/or ethyl methacrylate. The mixing ratio in the case of combining the functional monomers for use may be determined in consideration of the glass transition temperature of the (meth)acrylic copolymer. When the glass transition temperature is -50°C or higher, it is excellent in film formation and can control excess viscosity at room temperature, which is ideal. When the viscosity at room temperature is excessive, the handling of the adhesive layer becomes difficult. It is more desirably -20°C or higher, and still more desirably 0°C or higher. In addition, when the glass transition temperature is 30°C or lower, the adhesive strength of the adhesive layer at the time of cutting is superior, and it is more preferably 20°C or lower.

In the case of polymerizing the above-mentioned monomers to produce high molecular weight components containing functional monomers, the polymerization method is not particularly limited. For example, methods such as bead polymerization, solution polymerization, etc. can be used, and bead polymerization is preferred.

In the present invention, when the weight average molecular weight of the high molecular weight component containing the functional monomer is 100,000 or more, it is superior in terms of film formability, more preferably 200,000 or more, and still more preferably 500,000 or more. In addition, when the weight average molecular weight is adjusted to 2,000,000 or less, it is advantageous at the point where the heating fluidity of the adhesive layer at the time of wafer bonding is improved. When the heating fluidity of the adhesive layer during wafer bonding is improved, the adhesion between the adhesive layer and the adherend becomes good, and the adhesive force can be improved. In addition, the unevenness of the adherend is easily buried and voids are suppressed. It is more desirably 1,000,000 or less, and more desirably 800,000 or less, and when it is 500,000 or less, greater effects can be obtained.

In addition, the thermally polymerizable component is not particularly limited, such as a structure polymerized by heat. For example, examples include: having an oxypropylene group, an acrylic group, an isobutylene group, a hydroxyl group, a carboxyl group, and an isocyanurate group. , Amine group, amide group and other functional group compounds and excitation materials, these systems can also be used alone or in combination of two or more types, but when considering the heat resistance of the adhesive layer, it should be combined with hardeners and accelerators at the same time. It is preferable to contain a thermosetting resin that is hardened by heat and affects the work of the connection. Examples of thermosetting resins include epoxy resins, acrylic resins, silicone resins, phenol resins, thermosetting polyimide resins, polyurethanes, melamine resins, urea resins, etc., especially It is best to use epoxy resin when an adhesive layer with excellent heat resistance, workability, and reliability can be obtained.

The above-mentioned epoxy resin is not particularly limited if it has a structure that is used for curing, and it is not particularly limited. Bifunctional epoxy resins such as bisphenol A epoxy, phenol novolac epoxy or cresol novolac can be used. Phenolic epoxy resins such as epoxy resins, etc. In addition, polyfunctional epoxy resins, glycidylamine type epoxy resins, heterocyclic epoxy resins, alicyclic epoxy resins, and other commonly known structures can be applied.

Examples of the above-mentioned bisphenol A epoxy resin system include: Mitsubishi Chemical Co., Ltd. EPIKOTE series (EPIKOTE807, EPIKOTE815, EPIKOTE825, EPIKOTE827, EPIKOTE828, EPIKOTE834, EPIKOTE1001, EPIKOTE1004, EPIKOTE1007, EPIKOTE1009), manufactured by Dow Chemical, DER-330, DER-301, DER-361, and manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., YD8125, YDF8170, etc. Examples of the above-mentioned phenol novolac epoxy resins include: EPIKOTE 152 and EPIKOTE 154 manufactured by Mitsubishi Chemical Corporation, EPPN-201 manufactured by Nippon Kayaku Co., Ltd., DEN-438 manufactured by Dow Chemical, etc. Examples of the above-mentioned o-cresol phenolic epoxy resin system include: EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 manufactured by Nippon Kayaku Co., Ltd., or Nippon Steel & Sumikin Chemical Co., Ltd., YDCN701, YDCN702, YDCN703, YDCN704, etc. Examples of the above-mentioned multifunctional epoxy resin system include: Epon1031S manufactured by Mitsubishi Chemical Corporation, Araldite 0163 manufactured by Ciba Chemical Co., Ltd., Denacol EX-611 and EX-614 manufactured by Nagase ChemteX Co., Ltd. , EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, etc. Examples of the above-mentioned amine epoxy resin systems include: EPIKOTE604 manufactured by Mitsubishi Chemical Co., Ltd., YH-434 manufactured by Toto Kasei Co., Ltd., TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., and Sumitomo ELM-120 manufactured by Chemical Industry Co., Ltd., etc. Examples of the above-mentioned heterocyclic-containing epoxy resin system include Araldite PT810 manufactured by Ciba Seiki Co., Ltd., ERL4234, ERL4299, ERL4221, ERL4206 manufactured by UCC Corporation, and the like. These epoxy resins can also be used alone or in combination of two or more types.

In order to harden the above-mentioned thermosetting resin, additives may be suitably added. As such an additive system, for example, a hardener, a hardening accelerator, a catalyst, etc. can be cited, and when a catalyst is added, an auxiliary catalyst can be used as necessary.

In the case where epoxy resin is used for the above-mentioned thermosetting resin, it is preferable to use an epoxy resin hardener or a hardening accelerator, and it is more preferable to use these in combination. Examples of hardeners include: phenol resins, dicyandiamide, boron trifluoride complexes, organic hydrazine compounds, amines, polyamide resins, imidazole compounds, urea or thiourea compounds, and polythiols Compound, polysulfide resin with sulfur and hydrogen-based terminal, acid anhydride, light and ultraviolet hardener. These systems can be used individually or in combination of two or more. Among them, as boron trifluoride complexes, there can be mentioned: boron trifluoride-amine complexes with various amine compounds (ideal first-order amine compounds), and as organic hydrazine compounds, they can be polymerized: Phthalic hydrazine.

Examples of phenol resins include: phenol phenol resins, phenol aralkyl resins, cresol novolac resins, tert-butyl phenol phenol resins, nonyl phenol phenol resins and other phenolic phenol resins, and resol phenol resins. Phenol resin, polyoxystyrene such as polyoxystyrene, etc. Among them, phenol-based compounds having at least two phenolic hydroxyl groups in the molecule are preferred.

Examples of phenolic compounds having at least two phenolic hydroxyl groups in the above-mentioned molecule include: phenol phenol resin, cresol novolak resin, t-butyl phenol phenol resin, cyclopentadiene cresol phenol resin , Cyclopentadiene phenol phenol resin, xylene-based modified phenol phenol resin, naphthol phenol resin, triphenol phenol resin, tetraphenol phenol resin, bisphenol A phenol resin, poly-p-vinyl phenol resin, phenol aromatic Alkyl resin etc. Furthermore, among these phenol resins, phenol phenol resins and phenol aralkyl resins are particularly desirable, which can improve connection reliability.

Examples of amines include: chain aliphatic amines (diethylenetriamine, triethylenetetramine, hexamethylenediamine, N,N-dimethylpropylamine, benzyldimethylamine, 2(dimethylamino)phenol , 2,4,6-Tris(dimethylaminomethyl)phenol, m-xylylenediamine, etc.), cyclic aliphatic amines (N-aminoethylpiperazine, bis(3-methyl-4- Aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, antioxidants (MDA), isophorone diamine, 1,3-bis (aminomethyl) cyclohexane, etc.), polycyclic amines (piper Oxazine, N,N-dimethylpiperazine, trimethylenediamine, melamine, guanamine, etc.), aromatic amines (m-phenylenediamine, 4,4'-diaminodiphenylmethane, diamine, 4 , 4'-Diaminodiphenyl sulfide, etc., polyamide resin (polyamide amine is preferred, the condensate of dimer acid and polyamine), imidazole compound (2-phenyl-4,5-dimethylol Imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-n-heptadecylimidazole, 1-cyanoethyl-2-undecylimidazole, trimellitate, epoxy ･Imidazole addendum, etc.), urea or sulfurized urea compounds (N,N-dialkyl urea compounds, N,N-dialkyl sulfide urea compounds, etc.), polythiol compounds, polysulfides with sulfur-based terminals Resins, acid anhydrides (tetrahydrophthalic anhydride, etc.), light and ultraviolet hardeners (diphenyl iodide, hexafluorophosphoric acid, triphenyl sulfonium hexafluorophosphate, etc.).

The hardening accelerator is not particularly limited if it is a composition for hardening a thermosetting resin, for example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dicarboxylic acid, triphenyl phosphorus, tetraphenyl Boron tetraphenylphosphonium, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo[5.4.0]undecene-7-tetraphenylborate, etc. Examples of imidazoles include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2-phenyl-4,5-dimethylolimidazole, etc.

The content of the curing agent for epoxy resin or the curing accelerator in the adhesive layer is not particularly limited, and the optimum content varies depending on the type of curing agent or curing accelerator.

The blending ratio of the epoxy resin and the phenol resin is, for example, the epoxy group in the epoxy resin component is 0.5 to 2.0 equivalent per equivalent of the epoxy group in the phenol resin. More preferably, it is 0.8 to 1.2 equivalents. That is, when the blending ratio of the two exceeds the aforementioned range, a sufficient curing reaction cannot proceed, and the characteristics of the adhesive layer are likely to deteriorate. Other thermosetting resins and curing agents are based on one embodiment. For 100 parts by mass of the thermosetting resin, the curing agent is 0.5-20 parts by mass, and in other embodiments, the curing agent is 1-10. Mass parts. The content of the hardening accelerator is preferably less than the content of the hardening agent. For 100 parts by mass of the thermosetting resin, the hardening accelerator is preferably 0.001~1.5 parts by mass, and 0.01~0.95 parts by mass is more. good. By adjusting to the above-mentioned range, it can assist the progress of sufficient hardening reaction. The content of the catalyst is preferably 0.001 to 1.5 parts by mass for 100 parts by mass of the thermosetting resin, and more preferably 0.01 to 1.0 parts by mass.

In addition, the adhesive layer 13 of the present invention can be suitably formulated with a filler according to its use. As a result, it is possible to improve the cutting properties of the adhesive layer in the uncured state, improve the handling properties, adjust the melt viscosity, impart thixotropy, and moreover, impart the thermal conductivity of the adhesive layer in the cured state. Follow-up lifters. The filler used in the present invention is preferably an inorganic filler. The inorganic filler is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate can be used. Whiskers, boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, antimony oxide, etc. In addition, these systems may be used alone or in mixture of two or more types.

In addition, among the above-mentioned inorganic fillers, aluminum oxide, aluminum nitride, boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. are preferably used from the viewpoint of improving thermal conductivity. In addition, from the point of adjusting the melt viscosity or imparting thixotropy, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, and crystallinity are used. Silicon oxide, amorphous silicon dioxide, etc. are preferred. In addition, from the viewpoint of improving the cutting performance, aluminum oxide is used, preferably silicon dioxide.

The adhesive layer of the present invention, as the above-mentioned filler, may contain two or more types of fillers with different average particle diameters. In this case, compared to the case of using a single filler, in the raw material mixture before thinning, it is easy to prevent the viscosity increase when the content of the filler is high or the viscosity decreases when the content of the filler is low. It is easy to obtain good film forming properties, it is the best to suppress the fluidity of the uncured adhesive layer, and at the same time, it is easy to obtain superior adhesive force for the cured adhesive layer.

In addition, the average particle size of the adhesive layer system filler of the present invention is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the average particle size of the filler is 2.0 μm or less, thinning of the film becomes easy. Here, the film refers to the thickness below 20μm. In addition, when it is 0.01 μm or more, the dispersibility is good. Furthermore, from the viewpoint of preventing the viscosity increase or decrease of the raw material mixture before filming, the fluidity of the uncured adhesive layer is controlled to the best, and the adhesive force after curing of the adhesive layer is improved. The first filler whose diameter is in the range of 0.1 to 1.0 μm, and the second filler whose average primary particle diameter is in the range of 0.005 to 0.03 μm are preferable. Contains: The average particle size is in the range of 0.1~1.0μm, and more than 99% of the particles are distributed in the first filler with the particle size of 0.1~1.0μm, and the average particle size of the primary particle size is in the range of 0.005 Within the range of ~0.03μm, and more than 99% of the particles are distributed in the second filler with a particle size of 0.005~0.1μm. The average particle diameter in the present invention means that 50% by volume of particles have a D50 value of the cumulative volume distribution curve with a diameter smaller than this value. In the present invention, the average particle diameter or D50 value is measured by a laser diffraction method, for example, using Malvern Mastersizer 2000 manufactured by Malvern Instruments. In this technique, the size of the particles in the dispersion is measured by the diffraction of laser light based on any application of Fraunhofer or Mie theory. In the present invention, using the Mie theory or the modified Mie theory for non-spherical particles, the average particle size or D50 value is measured with respect to the incident laser light at a scattering of 0.02 to 135°.

In the present invention, in one aspect, the entire adhesive composition constituting the adhesive layer 13 contains 10-40% by mass of a thermoplastic resin having a weight average molecular weight of 5000-200,000, and 10-40% by mass % Of thermally polymerizable ingredients and 30~75% by mass of fillers are also possible. In this embodiment, the content of the filler may be 30-60% by mass, or 40-60% by mass. In addition, the mass average molecular weight of the thermoplastic resin may be 5000 to 150,000, and may be 10,000 to 100,000. In other forms, the entire adhesive composition constituting the adhesive layer 13 contains 10 to 20% by mass of a thermoplastic resin with a weight average molecular weight of 200,000 to 2,000,000, and 20 to 50% by mass of thermally polymerizable resin. Ingredients, and 30~75% by mass fillers are also possible. In this embodiment, the content of the filler may be 30-60% by mass, or 30-50% by mass. In addition, the mass average molecular weight of the thermoplastic resin may be 200,000 to 1,000,000, and may be 200,000 to 800,000. By adjusting the blending ratio, the storage elastic modulus and fluidity after curing of the adhesive layer 13 can be optimized, and the heat resistance at high temperature also tends to be sufficiently obtained.

The adhesive layer 13 preferably has a light transmittance of 90% or more for light having a wavelength of 550 nm. In the case of a device in which glass is laminated on top of the image sensor with an adhesive layer, when the light transmittance is less than 90%, there is a possibility that the sensor may not operate properly. The light transmittance is generally adjusted by the blending composition of the adhesive layer, especially by selecting the base resin and filler, which can have both installation reliability and high transmittance. It can be adjusted by reducing the particle size of the filler, suppressing the scattering of light, and increasing the transmittance. As the resin with high transmittance, for example, epoxy resin or silicone resin is desirably used. In order to coexist with mounting reliability, bisphenol-type epoxy resin is particularly desirably used, but it is not limited to this.

The light transmittance can be measured by using a spectrophotometer (manufactured by Hitachi High-Technologies, spectrophotometer U-4100 solid sample measurement system) to determine the amount of transmitted light. Specifically, an adhesive layer with a thickness of 20 μm was attached to the glass, and the light penetrated in the normal direction to the glass surface, and the light transmittance of the glass at 550 nm at 25° C. was obtained. Specifically, it is calculated by the following formula (2). The light transmittance of the adhesive layer I(%)=I1/I0 (2) I1 (%): The light transmittance of the glass containing the adhesive layer I0(%): Light transmittance of glass

In the glass processing tape 10 of the present invention, the adhesive layer 13 has a structure in which a thin film is formed in advance (hereinafter referred to as an adhesive film), and it may be directly or indirectly laminated and formed on the base film 11. The temperature during lamination is set as the range of 10~100℃, plus the linear load of 0.01~10N/m is better. However, such an adhesive film may also be a structure in which the adhesive layer 13 is formed on the release film. In this case, the release film may be peeled off after lamination, or it may be used directly as a cover film of the glass processing tape 10 It is also possible to peel off when bonding the glass.

The aforementioned adhesive film may be laminated on the entire surface of the adhesive layer 12, but it may be laminated on the adhesive layer 12 with an adhesive film that has been previously laminated and cut into the shape of the glass (cut according to specifications). In this way, the lamination of the adhesive film for glass, as shown in FIG. 3, there is an adhesive layer 13 for the part where the glass W is bonded, and there is no adhesive layer 13 for the part where the ring frame 20 is bonded. However, only the adhesive layer 12 is present. Generally speaking, since the adhesive layer 13 is not easy to peel off from the adherend, by using the adhesive film cut according to the specifications, the ring frame 20 can be attached to the adhesive layer 12. After use, the tape It is not easy to produce the effect of the paste remaining on the ring frame 20 during peeling.

＜Use＞ The tape 10 for glass processing of this invention is a structure used for the processing method of the glass which contains the expansion process which breaks the adhesive layer 13 by expansion at least. In addition, other processes or the order of the processes are not particularly limited. For example, it can be best used in the following glass processing methods (A) ~ (C).

Glass processing method (A) Including: (a) The process of attaching the adhesive film to the glass in the state of heating the glass at 70~80°C, and pasting the adhesive layer of the adhesive layer of the tape for glass body processing, And (b) the process of irradiating laser light on the predetermined divided part of the aforementioned glass to form a modified range through multiphoton absorption in the interior of the glass, And (c) the process of separating the glass and the adhesive film along the breaking line while expanding the tape for semi-glass processing to obtain a plurality of wafers with adhesive films, And (d) the process of removing the slack generated in the aforementioned expansion process by heating and shrinking the part that does not overlap the aforementioned wafer of the aforementioned glass processing tape, and maintaining the distance between the wafers, And (e) The glass processing method of the process of picking up the aforementioned wafer with the aforementioned adhesive layer from the adhesive layer of the glass processing tape. The processing method of this glass adopts the method of invisible laser cutting.

Glass processing method (B) Including: (a) The process of applying the adhesive film attached to the adhesive layer of the glass processing tape to the glass while heating the glass at 70~80°C, And (b) The process of irradiating laser light along the breaking line from the surface of the aforementioned glass to break into individual wafers, And (c) the process of separating the adhesive film in response to the wafer during the expansion of the glass processing tape to obtain a plurality of wafers with adhesive films, And (d) the process of removing the slack generated in the aforementioned expansion process by heating and shrinking the part that does not overlap the aforementioned wafer of the aforementioned glass processing tape, and maintaining the distance between the wafers, And (e) The glass processing method of the process of picking up the aforementioned wafer with the aforementioned adhesive layer from the adhesive layer of the glass processing tape. The processing method of this glass adopts full-cut laser cutting method.

Glass processing method (C) Including: (a) The process of applying the adhesive film attached to the adhesive layer of the glass processing tape to the glass while heating the wafer at 70~80°C, And (b) the process of cutting the aforementioned glass along the breaking line with a dicing knife, and breaking it into individual wafers, And (c) the process of separating the adhesive film in response to the wafer during the expansion of the glass processing tape to obtain a plurality of wafers with adhesive films, And (d) the process of removing the slack generated in the aforementioned expansion process by heating and shrinking the part that does not overlap the aforementioned wafer of the aforementioned glass processing tape, and maintaining the distance between the wafers, And (e) The glass processing method of the process of picking up the aforementioned wafer with the aforementioned adhesive layer from the adhesive layer of the glass processing tape. The processing method of this glass adopts a full-cut blade cutting method.

＜How to use＞ The tape 10 for glass processing of the present invention will be described with reference to FIGS. 2 to 5 with reference to the method of using the tape when the above-mentioned glass processing method (A) is applied.

As shown in FIG. 2, after placing the glass W on the heating stage 25 of the wafer mounter with the front side as the lower side, the glass processing tape 10 is attached to the back of the glass W. The glass processing tape 10 used here is a laminated film that is pre-cut (cut according to specifications) into an adhesive film corresponding to the shape of the glass W to be bonded, and is exposed on the surface bonded to the glass W The adhesive layer 12 is exposed around the area where the adhesive layer 13 is located. The part where the adhesive layer 13 of the glass processing tape 10 is exposed and the back surface of the glass W are bonded together, and the part where the adhesive layer 12 around the adhesive layer 13 is exposed and the ring frame 20 are bonded together. At this time, the heating stage 25 is set to 70-80 degreeC, and heat bonding is implemented through this. However, in the present embodiment, the present embodiment has: an adhesive tape 15 formed by a base film 11 and an adhesive layer 12 provided on the base film 11, and an adhesive layer provided on the adhesive layer 12 The glass processing tape 10 of 13 can also be used as an adhesive tape and a film-like adhesive. In this case, first, a film-like adhesive is attached to form an adhesive layer on the back of the glass, and then the adhesive layer of the adhesive tape is attached to this adhesive layer. At this time, as the adhesive tape, the adhesive tape 15 through the present invention is used.

Next, the glass W to which the glass processing tape 10 is attached is carried out from above the heating stage 25. As shown in FIG. The modification range is 32.

Next, as shown in FIG. 4(a), the glass W and the ring frame 20 are bonded to the tape 10 for glass processing, with the base film 11 side as the bottom, and placed on the platform 21 of the expansion device.

Next, as shown in FIG. 4(b), in the state where the annular frame 20 is fixed, the push-up member 22 in the shape of a hollow cylinder of the expansion device is raised to expand (expand) the tape 10 for glass processing. As the expansion condition, the expansion speed is, for example, 5 to 500 mm/sec, and the expansion amount (push-up amount) is, for example, 5 to 25 mm. In this way, when the glass processing tape 10 is stretched in the radial direction of the glass W, the glass W is divided into 34 units of wafers with the aforementioned modified range 32 as a starting point. At this time, the adhesive layer 13 is attached to the back surface of the glass W, suppressing extension (deformation) through expansion without causing breakage, but in the position between the wafers 34, the tension caused by the expansion of the tape is concentrated. fracture. Subsequently, as shown in FIG. 4(c), at the same time as the glass W, the adhesive layer 13 is also broken. In this way, a plurality of wafers 34 with the adhesive layer 13 can be obtained.

Next, as shown in FIG. 5, the push-up member 22 is returned to its original position, the slack of the glass processing tape 10 generated in the previous expansion process is removed, and the process of maintaining the gap between the wafers 34 stably is performed. In this process, for example, in the area where the wafer 34 of the glass processing tape 10 exists, and the ring-shaped heating shrinkage area 28 between the ring frame 20, a warm air nozzle 29 is used to contact 40~120℃ The warm air heats and shrinks the base film 11, so that the glass processing tape 10 is in a state of being attached to the pins. Afterwards, the adhesive layer 12 is subjected to energy ray hardening treatment or thermal hardening treatment, etc., and after weakening the adhesive force to the adhesive layer 13 of the adhesive layer 12, the wafer 34 is picked up.

However, the glass processing tape 10 of this embodiment has a structure provided with the adhesive layer 13 on the adhesive layer 12, but the adhesive layer 13 may not be provided and the structure may be sufficient. In this case, the glass is laminated on the adhesive layer 12 and used to only break the glass. When used as a tape for glass processing, the adhesive layer 13 is used as the adhesive film produced in the same way as the adhesive layer 13 The glass is attached to the adhesive layer 12 together, and the glass and the adhesive film may be broken. <Example> Next, in order to make the effect of the present invention clearer, examples and comparative examples will be described in detail, but the present invention is not limited to these examples.

[Production of glass processing tape] (1) Production of base film <Base film A> Zinc ion polymerization of ethylene-methacrylic acid-methacrylate copolymer synthesized by radical polymerization at 230°C (Methacrylic acid content 15%, methacrylate content 5%, softening point 72°C, melting point 90°C, density 0.96g/cm ³ , zinc ion content 5% by mass) resin beads, use extruded The machine is formed into a long film with a thickness of 150μm. After that, the long film was stretched to a thickness of 90 μm in the TD direction to produce a base film A.

＜Substrate film B＞ The thickness of the long film was set to 180 μm, and the long film was stretched to a thickness of 90 μm except for the TD direction, and the base film B was produced in the same manner as the base film A.

＜Substrate film C＞ The thickness of the long film was set to 215 μm, and the long film was stretched to a thickness of 90 μm except for the TD direction, and the base film C was produced in the same manner as the base film A.

<Base film D> A zinc ion polymer of ethylene-methacrylic acid-isobutyl methacrylate copolymer synthesized by radical polymerization at 230°C (methacrylic acid content 11%, methacrylic acid isobutyl ester) butyl content of 9%, a softening point of 64 deg.] C, a melting point of 83 deg.] C, density of 0.95g / cm ^3, a zinc ion content of 4% by mass) of the resin beads, and formed into a thickness of 150μm long film using an extruder. After that, the long film was stretched to a thickness of 90 μm in the TD direction to produce a base film D.

＜Substrate Film E＞ Melt at 200°C and mix hydrogen-added styrene-based thermoplastic synthetic rubber and polypropylene (PP) resin beads with a mixing ratio of 52:48, and use an extruder to form a long film with a thickness of 150μm. After that, the long film was stretched in the TD direction into a thickness of 90 μm to produce a base film E.

＜Substrate film F＞ Melt at 200°C and mix with hydrogen-added styrene-based thermoplastic synthetic rubber and polypropylene (PP) resin beads at a mixing ratio of 64:36, and use an extruder to form a long film with a thickness of 150μm. After that, the long film was stretched to a thickness of 90 μm in the TD direction to produce a base film F.

＜Base film G＞ The thickness of the long film was 150 μm, and the long film was stretched to a thickness of 90 μm other than the MD direction, and the base film G was produced in the same manner as the base film A.

＜Substrate film H＞ The thickness of the long film was 150 μm, and the long film was stretched to a thickness of 90 μm other than the MD direction, and the base film H was produced in the same manner as the base film D.

＜Substrate Film I＞ The thickness of the long film was set to 90 μm, and the stretching treatment of the long film was performed, and the base film I was produced in the same manner as the base film A.

＜Substrate film J＞ The thickness of the long film was set to 90 μm, and the stretching treatment of the long film was performed, and the base film J was produced in the same manner as the base film D.

＜Substrate film K＞ The thickness of the long film was set to 90 μm, and the stretching treatment of the long film was performed, and the base film K was produced in the same manner as the base film E.

＜Base film L＞ The thickness of the long film was set to 90 μm, and the stretching treatment of the long film was performed, and the base film L was produced in the same manner as the base film F.

＜Base film M＞ The thickness of the long film was 110 μm, and the long film was stretched to a thickness of 90 μm except for the TD direction, and the base film M was produced in the same manner as the base film A.

＜Base film N＞ The thickness of the long film was 120 μm, and the long film was stretched to a thickness of 90 μm except for the TD direction, and the base film N was produced in the same manner as the base film A.

(2) Preparation of acrylic copolymer As an acrylic copolymer (A1) having a functional group, it is composed of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and methacrylic acid, and the ratio of preparing 2-ethylhexyl acrylate is 60 moles. Ear%, a copolymer with a mass average molecular weight of 700,000. Next, the iodine value became 25 and 2-isocyanoethyl methacrylate was added to prepare an acrylic copolymer having a glass transition temperature of -50°C, a hydroxyl value of 10 mgKOH/g, and an acid value of 5 mgKOH/g.

(3-1) Preparation of Adhesive Composition A Add 100 parts by mass of epoxy resin "1256" (manufactured by Mitsubishi Chemical Corporation, bisphenol A phenoxy resin, epoxy equivalent 7500), and epoxy resin "828" (trade name, manufactured by Mitsubishi Chemical Corporation, Bisphenol A liquid epoxy resin, epoxy equivalent 220, specific gravity 1.17) 100 parts by mass, hardener "DICY7" (manufactured by Mitsubishi Chemical Corporation, dicyandiamide) 4 parts by mass, and "hardening accelerator" "Curezol 2PZ" (trade name, 2-phenyl-4,5-dimethylolimidazole, manufactured by Shikoku Chemical Co., Ltd.) 0.4 parts by mass, and MEK was added, and the mixture was stirred and mixed until it became uniform. Furthermore, these were filtered with a 100 mesh filter, and then vacuum degassed to obtain the varnish of the adhesive composition.

(3-2) Preparation of adhesive composition B 40 parts by mass of epoxy resin "1002" (manufactured by Mitsubishi Chemical Co., Ltd., solid bisphenol A epoxy resin, epoxy equivalent 600), epoxy resin "806" (trade name of Mitsubishi Chemical Co., Ltd., double Phenol F type epoxy resin, epoxy equivalent 160, specific gravity 1.20) 100 parts by mass, hardener "Dyhard100SF" (trade name, dicyandiamide manufactured by Degussa) 5 parts by mass, silica filler "SO-C2" ( ADMAFINE Co., Ltd. product name, average particle size 0.5μm) 200 parts by mass, and silica filler "Aerosil R972" (Japan Aerosil Co., Ltd. product name, average primary particle size 0.016μm) 3 mass Add MEK to the resulting composition and stir and mix to make a uniform composition. In addition, 100 parts by mass of phenoxy resin "PKHH" (trade name manufactured by INCHEM, mass average molecular weight 52,000, glass transition temperature 92°C), and "KBM-802" (Shin-Etsu Chemical Co., Ltd. product name, mercaptopropyltrimethoxysilane) 0.6 parts by mass, and "CUREZOL 2PHZ-PW" as a hardening accelerator (Shikoku Chemical Co., Ltd. product name, 2-phenyl- 4,5-dihydroxymethylimidazole, decomposition temperature 230°C) 0.5 parts by mass, stirring and mixing until it becomes uniform. Furthermore, these were filtered with a 100 mesh filter, and then vacuum degassed to obtain the varnish of the adhesive composition.

<Example 1> For 100 parts by mass of the above-mentioned acrylic copolymer, 5 parts by mass of coronate L (manufactured by Japan Polyurethane) is added as polyisocyanate, and 3 parts by mass of Esacure KIP 150 (Lamberti Co., Ltd.) is added as a photopolymerization initiator. The mixture prepared) was dissolved in ethyl acetate and stirred to prepare an adhesive composition. In the release liner made of the polyethylene terephthalate film of the release treatment, the adhesive composition is coated to a thickness of 10μm after drying, and then dried at 110°C for 3 minutes , Laminate with the base film to produce an adhesive sheet that forms an adhesive layer on the base film.

Next, apply the above-mentioned adhesive composition A to a release liner made of a polyethylene terephthalate film that has been demolded to a thickness of 20μm after drying, and then apply it at 110°C. Dry for 5 minutes to produce an adhesive film that forms an adhesive layer on the release liner.

The adhesive sheet, for the ring frame, can be attached to cover the opening, and cut into the shape of Figure 3, etc. In addition, the adhesive film is cut into the shape shown in Figure 3, etc., which can cover the back of the glass. In addition, the adhesive layer side of the adhesive sheet and the adhesive layer side of the adhesive film are bonded together as shown in FIG. 3 and so on to form a part where the adhesive layer 12 is exposed around the adhesive film to produce glass processing adhesive tape.

<Examples 2 to 8, Comparative Examples 1 to 6> The glass processing tapes of Examples 2 to 8 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1 except for the substrate thin mold described in Table 1 and the adhesive composition.

The adhesive tapes of the glass processing tapes related to the Examples and Comparative Examples were cut to have a length of 24 mm (the direction of measuring the amount of deformation) and a width of 5 mm (the direction orthogonal to the direction of measuring the amount of deformation), and sample pieces were prepared. For the obtained sample piece, using a thermomechanical property testing machine (manufactured by Rigaku Co., Ltd., trade name: TMA8310), the tensile load method was used to measure the temperature through the two directions of MD and TD under the following measurement conditions. Deformed. (Measurement conditions) Measuring temperature: -60~100℃ Heating rate: 5℃/min Measured load: 19.6mN Ambient gas: nitrogen environment (100ml/min) Sampling: 0.5s Distance between suction plates: 20mm

In addition, the thermal deformation rate is calculated by the following formula (1), the integral value calculated by the sum of the thermal deformation rates per 1°C between 40°C and 80°C in each MD direction and TD direction is calculated, and the sum is calculated . The results are shown in Tables 1,2. Thermal deformation rate TMA(%)=(displacement of sample length/sample length before measurement)×100 (1)

[Assessment of chip identification errors] By the method shown below, for each of the glass processing tapes of the foregoing Examples and the foregoing Comparative Examples, the glass was broken into wafers, and the wafer identification errors were evaluated.

Implement (a) the process of irradiating laser light on the predetermined part of the glass to form a modified range through multiphoton absorption inside the glass, And (b) The process of bonding the adhesive layer of the glass processing tape to the glass while heating the glass at 70~80°C, And (c) the process of separating the glass and the adhesive layer along the breaking line while expanding the glass processing tape to obtain a plurality of wafers with adhesive films, And (d) by heating the part that does not overlap the aforementioned wafer of the aforementioned glass processing tape (the area where the wafer exists and the ring-shaped area between the ring frame), and the contraction is removed, except for the expansion in (c) The slack generated in the process, the process to maintain the interval between the wafers, And (e) the process of picking up the aforementioned wafer with the aforementioned adhesive layer from the adhesive layer of the glass processing tape.

However, in the process (b), the breaking lines of the glass are added to the MD and TD directions of the base film to bond the glass to the glass processing tape.

In the process (c), using DDS2300 manufactured by Disco Co., Ltd., the dicing ring frame attached to the tape for glass processing is pressed down through the expansion ring of DDS2300 manufactured by Disco Co., Ltd., and the glass processing tape The part of the outer circumference of the glass bonding part that does not overlap the glass is pressed down on the circular push-up member to implement expansion. As the conditions of the (c) process, the expansion speed was set to 300 mm/sec, and the expansion height was set to 10 mm, and the expansion amount was adjusted. Here, the amount of expansion refers to the amount of change in the relative positions of the ring frame and the push-up member before and after pressing down. The wafer size is assumed to be an angle of 1×1mm.

(d) The process is performed from room temperature at an expansion speed of 1 mm/sec and an expansion height of 10 mm. After the expansion is performed again, the heat shrinking treatment is performed under the following conditions. [Condition 1] Heater setting temperature: 220℃ Hot air volume: 40L/min The distance between the heater and the glass processing tape: 20mm Heater rotation speed: 7°/sec [Condition 2] Heater setting temperature: 220℃ Hot air volume: 40L/min The distance between the heater and the glass processing tape: 20mm Heater rotation speed: 5°/sec

For the glass processing tapes of Examples 1 to 8 and Comparative Examples 1 to 6, (after the above-mentioned (g) process, pick up is performed, and when the boundary with the adjacent wafer cannot be distinguished, the wafer cannot be correctly identified and cannot be picked up For chips, the frequency of occurrence is evaluated as a chip identification error. In both conditions 1 and 2 of the above (g) process, the frequency of occurrence of chip identification errors is 0%. As a good product, it is evaluated as "◎", and In condition 2, a composition with a chip identification error frequency of less than 1% is regarded as a good product, and is evaluated as "○". In a condition 2, a composition with a chip identification error frequency of 1% or more and less than 3% is regarded as a permissible product. , Which is evaluated as "△", condition 1, and condition 2, where the frequency of chip identification errors is 3% or more, as a defective product, it is evaluated as "×". The results are shown in Tables 1 and 2. However, during the evaluation, as shown in Fig. 6, there is no missing corner in the MD direction of the adhesive tape, and the periphery of the chip 50a at the rightmost end in Fig. 6 is the same as that for the absence of missing corners in the MD direction of the adhesive tape. Chipped corners, at the periphery of the leftmost chip 50b in Fig. 6, for the periphery of the chip 51 at the two ends without a chipped corner in the TD direction of the adhesive tape, and the periphery of the chip 52 located in the center, pick up 100 chips each for evaluation .

[Determination of the transmittance of the adhesive layer] The transmittance of the adhesive layer of the foregoing Examples and the foregoing Comparative Example was measured by the method shown below. After bonding the adhesive layer with a thickness of 20 μm formed on the release liner to the glass, the release liner was peeled off to prepare a glass sample containing the adhesive layer. For glass containing glass and adhesive layer, as for the glass surface, as light penetrates to the normal direction, a spectrophotometer (manufactured by Hitachi High-Technologies, spectrophotometer U-4100 solid sample measurement system) is used. The light transmittance of the glass at 550 nm at 25°C was measured, and the transmittance of the adhesive layer was calculated by the following formula (2). The results are shown in Tables 1,2. The light transmittance of the adhesive layer I(%)=I1/I0 (2) I1 (%): The light transmittance of the glass containing the adhesive layer I0(%): Light transmittance of glass

As shown in Table 1, the glass processing tapes of Examples 1 to 8 were measured by a thermo-mechanical property testing machine in the MD direction of the adhesive tape. The sum of the average value of the differential value of the deformation rate and the average value of the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermo-mechanical characteristics tester in the TD direction during the temperature rise is Because of the negative value, it is easy to distinguish the boundary with the adjacent chip. In the image recognition at the time of picking, the frequency of chip recognition errors is low, which is a good result.

On the other hand, the glass processing tapes of Comparative Examples 1 to 6 are as shown in Table 2. It is measured by a thermo-mechanical property testing machine in the MD direction of the adhesive tape at the temperature of 40°C to 80°C. The average value of the differential value of the thermal deformation rate at 1°C, and the average of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermo-mechanical characteristic testing machine in the TD direction when the temperature is raised. Because the sum of the values is not a negative value, the frequency of chip identification errors is high, which becomes a poor result.

10: Tape for glass processing 11: Substrate film 12: Adhesive layer 13: Adhesive layer 22: Push on the component 28: Heating shrinkage range 29: Warm air nozzle

Fig. 1 is a cross-sectional view schematically showing the structure of a tape for glass processing according to an embodiment of the present invention. [Fig. 2] is a cross-sectional view for explaining the process of bonding glass and the ring frame to the glass processing tape according to the embodiment of the present invention. [Figure 3] is a cross-sectional view showing how the modified range of glass is formed by laser processing. [Fig. 4] (a) is a cross-sectional view showing a state in which the glass processing tape according to the embodiment of the present invention is mounted on the expansion device. (b) is a cross-sectional view showing the process of breaking the glass into wafers through the expansion of the glass processing tape. (c) is a cross-sectional view showing the expanded glass processing tape, adhesive layer, and wafer. [Figure 5] is a cross-sectional view for explaining the heat shrinkage process. [Fig. 6] An explanatory diagram showing the measurement locations of the incision width in the evaluation of Examples and Comparative Examples. [Figure 7] An example of the measurement result of the thermal deformation rate.

10: Tape for glass processing

11: Substrate film

12: Adhesive layer

13: Adhesive layer

15: Adhesive tape

Claims (4)

An adhesive tape for glass processing, which has: an adhesive tape having a substrate film and an adhesive layer formed on at least one side of the substrate film; The average value of the differential value of the thermal deformation rate measured between 40°C and 80°C per 1°C, and the average value of the differential value between 40°C and 80°C measured by the thermomechanical characteristic tester in the TD direction when the temperature is raised. The sum of the average value of the differential value of the thermal deformation rate in ℃ is a negative value; it is used for glass processing including the expansion process of the aforementioned adhesive tape. An adhesive tape for glass processing, comprising: an adhesive tape having a substrate film and an adhesive layer formed on at least one side of the substrate film; the substrate film is made of ionomer resin, or polypropylene and It is made of mixed resin composition of styrene-butadiene copolymer; the thermal deformation rate per 1°C between 40°C and 80°C in the MD direction of the aforementioned adhesive tape measured by the thermomechanical characteristics tester at the temperature rise The sum of the average value of the differential value of the TD direction and the average value of the differential value of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermomechanical characteristic testing machine during the heating process is a negative value. For example, the glass processing tape of claim 1 or claim 2, which is used for blade cutting for full cutting, laser cutting, or invisible laser cutting by laser. Such as the glass processing tape of claim 1 or claim 2, wherein the adhesive layer is laminated on the side of the adhesive layer; the light transmittance of the adhesive layer for light having a wavelength of 550 nm is 90% or more.

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