TWI755743B - Tape for glass processing - Google Patents

Abstract

The present invention relates to an adhesive tape for glass processing, which provides the adhesive tape for glass processing which can sufficiently heat and shrink in a short time and can maintain the width of the slit. The glass processing tape (10) of the present invention is characterized by having an adhesive tape (15) having a base film (11) and an adhesive layer (12) formed on at least one side of the base film (11). ), the above-mentioned adhesive tape (15) is the integral value calculated by the sum of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermomechanical property testing machine in the MD direction during the temperature rise, The sum of the integral value calculated from the sum of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermomechanical property testing machine in the TD direction is a negative value, which is used for including expansion. Glass processor for expansion work of adhesive tape (15).

Description

Tape for glass processing

The present invention relates to the dicing process of dividing glass into wafer-like components, which can be used for fixing glass, and also in the die bonding process or loading process between wafer and wafer or between wafer and substrate after subsequent dicing It can also be used in the process of mounting, and can also be used in the process of dividing the adhesive layer along the wafer by expansion. It is an expandable tape for glass processing.

In cameras or sensors mounted on smartphones, etc., glass with various optical properties is mounted. These glass systems are generally prepared by vacuum-depositing various materials or the like for the glass serving as the mother body. After that, after attaching the adhesive and stretchable tape for glass processing to these glasses, a dicing process for dividing the glass into wafer units is performed, and an expansion process for expanding (expanding) the tape for glass processing is performed, and the divided glass is picked up. The pick-up process of the chip, and the picked-up chip is followed by a die bonding process at a specific place.

In the above-mentioned glass cutting process, cutting through a blade has been the mainstream in the past, but the influence of thinning and vapor deposition on the glass itself, such as scratches called grinding, have become problems, and this has caused a decrease in productivity. the problem.

In order to solve such a problem, in recent years, as a cutting method of glass, a so-called invisible laser cutting method has been proposed that can cut glass without contact using a laser processing apparatus. For example, Patent Document 1 discloses that, as an invisible laser dicing method, an adhesive layer (die-bonding resin layer) is interposed, and a laser is irradiated with a focus light through the inside of a semiconductor substrate on which a sheet is attached. When light is emitted, a modified region through multiphoton absorption is formed inside the semiconductor substrate, and this modified region is used as a process for cutting the planned part, and when the sheet is expanded, it is cut along the planned cutting part. A method of cutting a semiconductor substrate in the process of a semiconductor substrate and an adhesive layer.

In addition, as another wafer cutting method using a laser processing apparatus, for example, Patent Document 2 proposes a process including a process of mounting an adhesive layer (adhesive film) for die bonding on the back surface of the wafer, and the process of laminating the protective adhesive tape which may be stretched on the adhesive layer side of the wafer to which the adhesive layer is attached, and irradiating the surface of the wafer with the self-adhesive protective adhesive tape and irradiating the laser along the dicing line Light, the process of dividing into individual wafers, and the process of expanding the protective adhesive tape to impart tensile force to the adhesive layer, cutting the adhesive layer into each wafer, and attaching the wafer with the cut adhesive layer, Wafer singulation method for the process of self-protective adhesive tape detachment.

According to the wafer cutting methods described in Patent Document 1 and Patent Document 2, the physical load on the wafer is caused by the non-contact cutting of the wafer through the irradiation of laser light and the expansion of the tape. Because of its small size, the wafer can be cut without generating the chips of the wafer as in the case of the current mainstream cutting edge cutting. In addition, since the adhesive layer was divided by expansion, chips of the adhesive layer were not generated. Therefore, it is attracting attention as a superior technology that can replace blade cutting.

The singulation techniques described in the above-mentioned documents mainly target wafers, but it can also be applied to glass by changing the laser engine of the device to be used for glass.

However, as described in the above-mentioned Patent Documents 1 and 2, in the method of dividing the adhesive layer by expanding by expanding, the conventional tape for semiconductor processing is used, and the portion pushed up by the expanding ring is used as the amount of expansion increases. Then, after the expansion is released, the portion becomes slack, 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 maintaining the slit width by dividing the adhesive layer by expansion, releasing the expansion, and then shrinking the slack by heating the slack portion of the tape for semiconductor processing (for example, Patent Documents 3 and 4). [Prior Art Literature] [Patent Literature]

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

[The problem to be solved by the invention]

However, as a method of heating and shrinking the slack and shrinkage of the tape for semiconductor processing due to expansion, generally, a ring-shaped portion where the slack is pushed up by the expansion ring is used, and a pair of them are warmed. A method in which the air nozzle is surrounded, and warm air is applied to the part to heat and shrink it.

In the tape for semiconductor processing described in the above-mentioned 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 is 0% or more and 20% or less. However, when heating is performed by surrounding the hot air nozzle, since the temperature in the vicinity of the surface of the tape for glass processing gradually rises, it takes time to remove all the slack in the annular shape. In addition, the retention of the slit width is not sufficient, and the adhesive layers are in contact with each other and re-bonded, which is used in the case of glass division, and there is a problem that the yield of the glass processing process is deteriorated.

In addition, the shrinkage rate of the tape system for semiconductor processing described in the above-mentioned Patent Document 4 at 130° C. to 160° C. is 0.1% or more (refer to Claim 1 of the Patent Document 4 specification), and the temperature at which shrinkage occurs is high. Therefore, in the case of heating and shrinking by warm air, high temperature and long heating time are required. However, the warm air affects the adhesive layer near the outer periphery of the wafer, and the divided adhesive layer occurs. The risk of melting and then melting again.

Therefore, the objective of this invention is to provide the tape for glass processing which can fully heat shrink in a short time, and can maintain a slit width sufficiently to prevent the adhesive layers from coming into contact with each other and rebonding. means of solving problems

In order to solve the above-mentioned problems, the glass processing tape according to 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, wherein the adhesive tape is oriented in the MD direction through a The thermomechanical properties testing machine, the integral value calculated from the sum of the thermal deformation rate per 1 °C between 40 °C and 80 °C measured during the temperature rise, and the thermomechanical properties testing machine in the TD direction. The sum of the integral values calculated from the sum of the thermal deformation rates per 1°C between 40°C and 80°C measured at the time of temperature rise is a negative value, and it is characterized by a glass processor used for the expansion process including the expansion of the adhesive tape. .

In addition, in order to solve the above problems, the tape for glass processing according to the present invention is an adhesive tape having a base film and an adhesive layer formed on at least one side of the base film, wherein the base film is made of ionic Cross-linked polymer resin, or a mixed resin composition of polypropylene film and styrene-butadiene copolymer, the above-mentioned adhesive tape is measured by a thermomechanical property tester in the MD direction at a temperature of 40 The integral value calculated from the sum of the thermal deformation rate per 1°C between ℃ and 80°C, and the value of each temperature between 40°C and 80°C measured by the thermomechanical property testing machine in the TD direction at the time of heating. The characteristic is that the sum of the integral values calculated from the sum of the thermal deformation rates at 1°C is a negative value.

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

Moreover, it is preferable that the said adhesive bond layer is laminated|stacked on the said adhesive bond layer side, and the light transmittance of the said adhesive bond layer is 90% or more with respect to the light which has a wavelength of 550nm. Invention effect

According to the adhesive tape for glass processing according to the present invention, heat shrinkage can be sufficiently performed in a short time, and the slit width can be kept sufficiently to prevent the adhesive layers from coming into contact with each other and rebonding.

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

FIG. 1 : is sectional drawing which shows the tape 10 for glass processing which concerns on embodiment of this invention. In the glass processing tape 10 of the present invention, when glass is divided into wafers by expansion, the transparent adhesive layer 13 is divided along the wafers. The glass processing tape 10 includes an adhesive tape 15 formed of 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. A structure in which the back surface of the glass is bonded to 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 tape 10 for glass processing of the present invention may be in the form of being cut into one piece of glass, and a plurality of long sheets cut into one piece of glass may be formed and wound into a roll shape. Form can also be. Hereinafter, the configuration of each layer will be described.

<Substrate film> As long as the base film 11 has uniform and isotropic expandability, it is desirable that the glass does not deviate from the point where the glass can be cut in all directions in the expansion process, and its material is not particularly limited. Generally speaking, compared with non-bridging resins, bridging resins have greater restoring force for stretching, and greater shrinkage stress during tensile state after expansion process plus heat. Then, after the expansion process, the slack caused by the tape is removed by heating and shrinking, and the tape is taut to keep the gap (cut width) between the wafers stably. Among the bridging resins, thermoplastic bridging resins are more desirably used. On the other hand, the non-bridging resin is smaller in restoring force to stretching than the bridging resin. Subsequently, after the expansion process in the low temperature range such as -15°C ~ 0°C, it was once relaxed, and returned to normal temperature, and then proceeded to the pick-up process. The tape during the loading process is not easy to shrink. The point where the adhesive layers are in contact with each other is preferred. Among the non-bridging resins, it is also more desirable to use an olefin-based non-bridging resin.

Examples of such thermoplastic bridging resins include metal ions bridged with ethylene-(meth)acrylic acid binary copolymers or ethylene-(meth)acrylic acid-(meth)acrylic acid alkyl esters as the main polymer. The terpolymer of components is an ionomer resin. These systems are suitable for expansion work on a uniformly extensible surface, and are particularly suitable for a point where a strong restoring force acts when heated through a bridge. The metal ion contained in the above-mentioned ionomer resin is not particularly limited, and examples thereof include zinc, sodium, and the like, but zinc ions are preferred from the viewpoint of low solubility and low contamination. Among the alkyl (meth)acrylates of the above-mentioned terpolymers, the alkyl group having 1 to 4 carbon atoms has a high elastic modulus, and it is preferable to transmit a strong force to the glass. Examples of such alkyl (meth)acrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, and propyl acrylate , Butyl acrylate, etc.

In addition, as the above-mentioned thermoplastic bridging resin, in addition to the above-mentioned ionomer resin, for low-density polyethylene with a specific gravity of 0.910 or more to less than 0.930, or an ultra-low density polyethylene with a specific gravity of less than 0.910, and ethylene -The resin of a vinyl acetate copolymer, the structure which bridge|bridged by irradiating the energy ray, such as an electron beam, is also optimal. Such thermoplastic bridging resin is a case where the bridging part and the non-bridging part coexist in the resin, and it has a certain uniform expansion property. In addition, since the strong restoring force is produced during heating, it is also the best for removing the slack of the tape caused by the expansion process, and since there is almost no chlorine in the structure of the molecular chain, even after incineration treatment and use Since it becomes unnecessary tape and does not generate dioxin or its insulating chlorinated aromatic hydrocarbons, the environmental burden is also small. Resin having sufficient uniform expansibility can be obtained by appropriately adjusting the amount of energy ray irradiated to the above-mentioned polyethylene or ethylene-vinyl acetate copolymer.

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

As the polypropylene system, 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 low in rigidity. When the content rate of the ethylene structural 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 high, which is excellent. When the rigidity of the tape is appropriate, the cutting property of glass is improved, and when the compatibility between resins is high, the extrusion discharge volume is easily stabilized. More preferably, it is 1% by weight or more. In addition, when the content rate of the ethylene structural unit in the propylene-ethylene copolymer is 7% by weight or less, the polypropylene is advantageous in that it is easy to polymerize stably. More preferably, it is 5 wt % or less.

As the styrene-butadiene copolymer system, a structure in which hydrogen is added can also be used. When hydrogen is added to the styrene-butadiene copolymer, compatibility with propylene is good, and embrittlement and discoloration through oxidative deterioration caused by double bonding in butadiene can be prevented. In addition, when the content rate of the styrene structural unit in the styrene-butadiene copolymer is 5% by weight or more, it is desirable that the styrene-butadiene copolymer is easily polymerized stably. Moreover, in 40 weight% or less, it is the point of a soft expandability, and it is excellent. More preferably, it is 25% by weight or less, and still more preferably 15% by weight or less. As a styrene-butadiene copolymer system, either a block type copolymer or a random type 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 expansibility.

When the content rate of polypropylene in the mixed resin composition is 30% by weight or more, it is desirable to suppress uneven thickness of the base film. When the thickness is uniform, it is easy to prevent the expansibility from being easily equalized, and the stress relaxation property of the base film becomes too large, the distance between wafers decreases with time, and the adhesive layers come into contact with each other to cause remelting. More preferably, it is 50% by weight or more. Moreover, when the content rate of polypropylene is 90 weight% or less, it becomes easy to adjust suitably the rigidity of a base film. When the rigidity of the base film becomes too large, the force necessary to expand the base film becomes larger, and the burden on the device becomes larger, and the glass or the adhesive layer 13 cannot be sufficiently expanded due to the splitting. Therefore, it is important to adjust the situation appropriately. The lower limit of the content of the styrene-butadiene copolymer in the synthetic resin composition is preferably 10% by weight or more, and it is easy to adjust the rigidity of the base film suitable for the device. When the upper limit is 70 wt % or less, it is superior in that thickness unevenness can be suppressed, and 50 wt % 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 a plural-layer structure in which two or more types of resins are laminated may be used, and one type of resin layer may be It can be stacked in 2 or more layers. Two or more resin systems, such as unified bridging or non-bridging properties, are ideal from the viewpoint of finding that each characteristic is more enhanced, and in the case of combining bridging properties or non-bridging properties and laminating, it is based on the point of complementing each disadvantage. for ideal. The thickness of the base film 11 is not particularly specified, but it is easy to stretch in the expansion process of the tape 10 for glass processing, and should have sufficient strength as long as it does not break. For example, 50 to 300 μm is preferable, and 70 to 200 μm is more preferable.

As a manufacturing method of the base film 11 of a plurality of layers, a conventionally known extrusion method, a lamination method, or the like can be used. In the case of using the lamination method, a transparent adhesive may be interposed between the layers.

<Adhesive layer> The adhesive layer 12 can be formed by coating the adhesive composition on the base film 11 . The adhesive layer 12 constituting the glass processing tape 10 of the present invention has a retention property that does not cause peeling from the adhesive layer 13 during dicing, and does not cause defects such as wafer flying, or it is The peeling of the agent layer 13 is easy.

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, but in order to improve the pick-up after dicing, the composition of energy ray curability is preferably It is preferable that the peeling from the adhesive layer 13 is easy. As one of the forms, the adhesive composition contains, as a base resin, 60 mol% or more of an alkyl chain (meth)acrylate having a carbon number of 6 to 12 and having an iodine value of 5 to 50. The composition of the energy ray hardening carbon-carbon double bond polymer (A) of 30. Here, however, the energy rays refer to rays such as ultraviolet rays, or ionizing radiation such as electron beams.

In such a polymer (A), when the introduction amount of the energy ray-curable carbon-carbon double bond is 5 or more iodine number, it is advantageous in that the effect of reducing the adhesive force after energy ray irradiation becomes high. More ideally, 10 or more. In addition, when the iodine value is 30 or less, the holding force of the wafer after the energy beam irradiation until the pick-up is high, and during expansion before the pick-up process, it is easy to widen the gap between the wafers, which is advantageous. When the gap between the wafers can be sufficiently widened before the pick-up process, the image recognition of each wafer at the time of pick-up is easy and the pick-up becomes easy, which is ideal. In addition, when the introduction amount of carbon-carbon double bond is 5 or more and 30 or less iodine value, it is preferable because the polymer (A) itself is stable and production is easy.

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 is more preferably -66°C or higher. In addition, if it is 15° C. or lower, various films are formed on the surface state, and there is an effect of preventing wafer scattering after dicing of glass having a surface level difference. below -28°C.

The above-mentioned polymer (A) can be composed of any product, but for example, a composition obtained by mixing an acrylic copolymer and a compound having an energy ray hardening carbon-carbon double bond can be used, or a functional acrylic-based copolymers or methacrylic-based copolymers with functional groups (A1), and compounds with functional groups that can react with their functional groups and energy ray hardening carbon-carbon double bonds (A2) The resulting composition of the reaction.

Among them, the methacrylic-based copolymer (A1) having the above-mentioned functional group is exemplified by a monomer (A1-1) having a carbon-carbon double bond such as an alkyl acrylate or an alkyl methacrylate, It is a composition obtained by copolymerizing a monomer (A1-2) with a carbon-carbon double bond and a functional group. Examples of the monomer (A1-1) system include: hexyl propyl acetate having an alkane chain having a carbon number of 6 to 12, n-octyl acrylate, isooctyl acrylate, isooctyl 2-acrylate, ten-octyl acrylate Dialkyl acrylate, decyl acrylate, dodecyl acrylate or monomers with alkane chain carbon number less than 5, n-amyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, or The same methacrylate etc. as these.

However, in the monomer (A1-1), the component having 6 or more carbon atoms in the alkane chain is superior in terms of pick-up properties because the peeling force between the adhesive layer and the adhesive layer can be reduced. In addition, the component of 12 or less has a low modulus of elasticity at room temperature, and is superior in the point of the adhesive force at the interface between the adhesive layer and the adhesive layer. When the adhesive force at the interface between the adhesive layer and the adhesive layer is high, when the tape is expanded to cut the glass, the interface between the adhesive layer and the adhesive layer can be prevented from deviating, and the cutting property can be improved, which is ideal.

In addition, as the monomer (A1-1), since the glass transition temperature system becomes lower as the monomer having a larger carbon number in the alkane chain is used, an adhesive composition having a desired glass transition temperature can be prepared by appropriately selecting it. thing. In addition, other than the glass transition temperature, low molecular weight compounds having carbon-carbon double bonds such as vinyl acetate, styrene, and acrylonitrile can also be prepared for the purpose of improving various properties such as compatibility. In this case, these low molecular weight compounds are prepared in a range of 5 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), a carboxyl group, a hydroxyl group, an amine group, a cyclic acid anhydride group, an epoxy group, an isocyanate group, etc. are 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 monoacrylate Acrylates, Hydroxyethyl Methacrylate, N-Methylol Acrylamide, N-Methylol Methacrylamide, Allyl Alcohol, N-Alkylamine Ethyl Acrylate, N-alkane Ethyl amine ethyl methyl acrylate, acrylamide, methacrylamide, maleic anhydride, itaconic anhydride, fumaric anhydride, phthalic anhydride, glycidyl acrylate, methyl methacrylate glycidyl acrylate, allyl glycidyl ether, etc.

Furthermore, in the compound (A2), as the functional group used in the case where the functional group possessed by the compound (A1) is a carboxyl group or a cyclic acid anhydride group, a hydroxyl group, an epoxy group, and an isocyanate group are exemplified. etc., in the case of a hydroxyl group, a cyclic acid anhydride group, an isocyanate group, etc. are mentioned, in the case of an amine group, an epoxy group, an isocyanate group, etc. are mentioned, and in the case of an epoxy group, a Ex: a carboxyl group, a cyclic acid anhydride group, an amine group, etc., as a specific example, the structure similar to the structure mentioned in the specific example of a monomer (A1-2) is mentioned. In addition, as the compound (A2), a part of the isocyanate group of the polyisocyanate compound may be urethane-ized with a hydroxyl group or a carboxyl group and a monomer having an energy ray-curable carbon-carbon double bond.

However, in the reaction between the compound (A1) and the compound (A2), when a functional group which is not reacted remains, a desired structure can be produced with regard to properties such as an acid value or a hydroxyl value. When the residual OH group is the hydroxyl valence of the polymer (A) of 5 to 100, the risk of picking errors can be further reduced by reducing the adhesive force after energy ray irradiation. In addition, when the acid value of the polymer (A) as the residual COOH group is 0.5 to 30, the improvement effect after the recovery of the adhesive layer after expanding the tape for glass processing of the present invention can be obtained, which is ideal. When the hydroxyl valence of the polymer (A) is 5 or more, it is superior at the point of the effect of reducing the adhesive force after energy ray irradiation, and when it is 100 or less, the point of the fluidity of the adhesive after energy ray irradiation for superiority. In addition, when the acid value is 0.5 or more, it is excellent in the point of recovery of the tape, and when it is 30 or less, it is excellent in the point of the fluidity of the adhesive.

In the synthesis of the above-mentioned polymer (A), as the organic solvent when the reaction is carried out by solution polymerization, ketone-based, ester-based, alcohol-based, and aromatic-based organic solvents can be used. Among them, toluene and ethyl acetate are used. , isopropanol, benzyl ethoxyethanol, diethylene glycol monobutyl ether, acetone, methyl ethyl ketone, etc. are generally good solvents for acrylic polymers. As the starting agent, free generators such as azobis-series such as α,α'-azobisisobutyronitrile, and organic peroxide-series such as benzyl peroxide are generally used. At this time, a catalyst and a polymerization inhibitor can be used in combination as necessary, and a polymer (A) having a desired molecular weight can be obtained by adjusting the polymerization temperature and the polymerization time. In addition, it is preferable to use a mercaptan and a carbon tetrachloride-based solvent for molecular weight adjustment. 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 improved. 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 the tensile force is easily transmitted to the adhesive layer, it is ideal at the point where the splitability of the adhesive layer is improved. When the molecular weight of the polymer (A) is set to be 2 million or less, it is excellent at the point of suppressing gelation at the time of synthesis and coating. However, the molecular weight in the present invention refers to the mass average molecular weight in terms of polystyrene.

Further, in the glass processing tape 10 of the present invention, the resin composition constituting the adhesive layer 12 may be added to the polymer (A), and may further include a compound (B) acting as a bridge agent. For example, polyisocyanates, a melamine formaldehyde resin, and an epoxy resin are mentioned, and these can be used individually or in combination of 2 or more types. The compound (B) reacts with the polymer (A) or the substrate film, and through the bridging structure that can lead to the result, after the adhesive composition is applied, the polymers (A) and (B) can be promoted as the main components the cohesive force of the adhesive.

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

The amount of the compound (B) added is preferably 0.1 part by mass or more at the point of cohesion with respect to 100 parts by mass of the polymer (A). More preferably, it is 0.5 mass part or more. In addition, 10 parts by mass or less of the adhesive layer is excellent at the point of suppressing abrupt gelation at the time of coating, and workability such as preparation of the adhesive and coating becomes good. More preferably, it is 5 parts by mass or less.

In addition, in the present invention, the photopolymerization initiator (C) may be contained in the adhesive layer 12 . The photopolymerization initiator (C) contained in the adhesive layer 12 is not particularly limited, and a conventionally known structure can be used. For example, benzophenone, 4,4'- dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone, etc. are mentioned. Diphenylketones, acetophenones, acetophenones such as diethoxyacetophenone, 2-ethylanthraquinone, anthraquinones such as t-butylanthraquinone, 2-chlorothioxanthone, Benzoin ethyl ether, benzoin isopropyl ether, benzoin ethylenedione, 2,4,5-triphenylimidazole dimer (rophene dimer), acridine-based compounds, etc., these systems can be used alone or in combination Use 2 or more types. The addition amount of the photopolymerization initiator (C) is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more, with respect to 100 parts by mass of the polymer (A). In addition, the upper limit 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, etc. can be prepared as necessary. In addition, an inorganic compound filler may be appropriately added.

The adhesive layer 12 can be formed by a conventional method of forming an adhesive layer. 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, one coated with a release agent). After forming the adhesive layer 12 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 the form of a single layer, and may also have the form of lamination.

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

The adhesive tape 15 is the integral value calculated by the sum of the thermal deformation rate per 1°C between 40°C and 80°C measured during the temperature rise through a thermomechanical property tester in the MD (Machine Direction) direction, and The sum of the integral values calculated by the sum of the thermal deformation rates per 1°C between 40°C and 80°C measured at the time of heating through a thermomechanical property testing machine in the direction of TD (Transverse Direction) is a negative value. 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 integral value calculated by the sum of the thermal deformation rate per 1°C between 40°C and 80°C measured at the time of temperature rise through the thermomechanical property tester in the MD direction of the adhesive tape 15, and through the TD Directional thermomechanical property testing machine, when the sum of the integral value calculated from the sum of the thermal deformation rate per 1°C measured between 40°C and 80°C during the temperature rise is regarded as a negative value, it can be tested at a low temperature and for a short time. Heating shrinks the tape 10 for glass processing. Then, in the case of adopting the method of heating and shrinking a pair of warm air nozzles around the portion where the slack of the glass processing tape 10 has occurred, there is no case where the expansion amount is reduced and the heating and shrinking is performed multiple times. The slack produced by expansion can be removed in a short time, and the appropriate incision width can be maintained.

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

The integrated value of the thermal deformation rate corresponds to the area surrounded by the curve in the MD direction or the curve in the TD direction and the x-axis in Fig. 7, and the sum of the integrated value in the MD direction and the integrated value in the TD direction is included. The sum of the areas of the symbols. Therefore, when the sum becomes a negative value, it means that between 40°C and 80°C, the adhesive tape generally shows the action of shrinkage. In order to make the sum of the integral value in the MD direction and the integral value in the TD direction as a negative value, a process of extending the resin film after film formation is added, and the adhesive tape 15 is adjusted according to the type of resin constituting the adhesive tape 15. The thickness, or the extension in the MD direction or the TD direction is sufficient. As a method of extending the adhesive tape in the TD direction, a method of using a tenter, a method of forming (expanding) by blowing, a method of using an expansion roller, etc., and the method of extending in the MD direction are exemplified. Examples include a method of stretching at the time of die discharge, a method of stretching with a conveying roller, and the like. Any method may be adopted as a method of obtaining the adhesive tape 15 of the present invention.

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

The adhesive layer 13 is not particularly limited, but may be a film-like adhesive generally used for glass, and examples thereof include a configuration containing a thermoplastic resin and a thermopolymerizable component. The above-mentioned thermoplastic resin used in the adhesive layer 13 of the present invention is a resin having thermoplasticity, or a resin having thermoplasticity in an uncured state, and a resin that forms a bridge structure after heating is preferably, and is not particularly limited, but as a The form system includes thermoplastic resins having a weight average molecular weight of 5,000 to 200,000 and a glass transition temperature of 0 to 150°C. Moreover, as another form, the thermoplastic resin whose weight average molecular weight is 100,000-1,000,000 and glass transition temperature -50-20 degreeC is mentioned.

Examples of the former thermoplastic resins include polyimide resins, polyimide resins, polyetherimide resins, polyimide resins, polyester resins, polyimide resins, Phenoxy resins, polysiloxane resins, polyether silt resins, polyphenylene sulfide resins, polyetherketone resins, etc. Among them, polyimide resins are used, phenoxy resins are preferred, and the latter thermoplastic resins are used Polymers containing functional groups are preferred.

The polyimide resin can be obtained by a known method by subjecting tetracarboxylic dianhydride and diamine to condensation reaction. That is, in an organic solvent, equimolar or almost equimolar (the order of addition of each component is arbitrary) tetracarboxylic dianhydride and diamine are used, and the reaction temperature is 80°C or lower, ideally 0 to 60°C to add reaction. As the reaction progresses, the viscosity of the reaction solution gradually increases, and a polyamide acid, which is a precursor of polyimide, is generated. When this polyamic acid is depolymerized by heating at a temperature of 50 to 80° C., its molecular weight can be adjusted. The polyimide resin can be obtained by dehydration and ring closure of the above-mentioned reactant (polyamide). The dehydration closed-loop system can be carried out by a thermal closed-loop method of heat treatment and a chemical loop-closed method using a dehydrating agent.

The tetracarboxylic dianhydride used as the raw material of the polyimide resin is not particularly limited, and for example, 1,2-(ethylene)bis(trimellitic anhydride), 1,3-(trimethylene)bis can be used. (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 -(nonamethylene)bis(trimellitic anhydride), 1,10-(decamethylene)bis(trimellitic anhydride), 1,12-(dodecamethylene)bis(trimellitic anhydride) ), 1,16-(hexamethylene)bis(trimellitic anhydride), 1,18-(octadecamethylene)bis(trimellitic anhydride), pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propionic acid 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-perylene tetracarboxylic 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'-bis Benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic anhydride, 1,2 ,4,5-Naphthalenetetracarboxylic 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-dicarboxyphenyl) dimethylsilane dianhydride, bis(3,4-di Carboxylic acid phenyl) methylphenyl silane dianhydride, bis(3,4-dicarboxylate phenyl) diphenyl silane dianhydride, 1,4-bis(3,4-dicarboxylate phenyl dimethyl anhydride) Silyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethylcyclohexylpropanol dianhydride, p-phenylene-bis (Mellitic 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 acid 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(mellitic 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 these can also be used in combination 1 type or 2 or more types.

(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 system as the raw material of polyimide is not particularly limited, for example, o-o-phenylenediamine, m-o-phenylenediamine, p-o-phenylenediamine, 3,3'-diaminediamine can be used Phenyl ether, 3,4'-diaminediphenyl ether, 4,4'-diaminediphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, bis(4-amino-3,5-xylyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, 3,3 '-Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminedifluoromethane phenylene, 3,4'-diaminediphenylene, 4,4'-diaminediphenylene, 3,3'-dithiodiphenylamine, 3,4'-dithiodiphenylamine, 4,4'- Dithiodianiline, 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)) dianiline, 3,4'-(1,4-phenylene(1-methylethylene)) dianiline, 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) sulfonic acid, bis(4-(4-aminophenoxy)phenyl)sulfonic acid, 3,5-diaminobenzoic acid and other aromatic diamine groups, 1,2-ethylenediamine, 1,2-ethylenediamine, 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 bisamine represented by 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. may use these 1 type or 2 or more types together. The glass transition temperature of the above-mentioned polyimide resin is preferably 0 to 200° C., and the weight average molecular weight is preferably 10,000 to 200,000.

(In the formula, R ₁ and R ₂ represent a divalent hydrocarbon group with 1 to 30 carbon atoms, and each of them may be the same or different, while R ₃ and R ₄ represent a monovalent hydrocarbon group, each of which is also may be the same or different, and m is an integer of 1 or more).

The phenoxy resin, which is one of the other desirable thermoplastic resins mentioned above, is preferably a resin obtained by a method of reacting various bisphenols with epichlorohydrin, or a method of reacting a liquid epoxy resin with bisphenol. , and bisphenols include bisphenol A, bisphenol AF, bisphenol AD, bisphenol F, and bisphenol S. The phenoxy resin has a structure similar to that of the epoxy resin, has good compatibility with the epoxy resin, and is suitable for imparting good adhesiveness to the adhesive film.

As a phenoxy resin system used for this invention, the resin which has the repeating unit shown by the following general formula (2) is mentioned, for example.

In the above general formula (2), X represents a single bond or a bivalent linking group. As a divalent linking group system, an alkyl group, a phenylene group, -O-, -S-, -SO- or _-SO2- is mentioned. Here, the alkyl group is preferably an alkyl 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 straight-chain or branched alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, and an n-propyl group. , isopropyl, isooctyl, 2-ethylhexyl, 1,3,3-trimethylbutyl, etc. Moreover, this alkyl group may be substituted by a halogen atom, and, for example, a trifluoromethyl group is mentioned. X is an alkylene group, -O-, -S-, fluorenyl or -SO ₂ - is preferred, and an alkylene group, -SO ₂ - is more preferred. 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, -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 having a plurality of different repeating units, or X is only composed of the same repeating unit. Can. In the present invention, X is preferably only a resin composed of the same repeating unit.

In addition, when the phenoxy resin represented by the above general formula (2) contains polar substituents such as hydroxyl groups and carboxyl groups, the compatibility with thermally polymerizable components is improved, and uniform appearance and properties can be imparted .

When the mass average molecular weight of the phenoxy resin is 5,000 or more, it is desirable in terms of film formability. More preferably, it is 10,000 or more, and still more preferably 30,000 or more. In addition, when the mass-average molecular weight is 150,000 or less, it is desirable in terms of fluidity at the time of hot pressing and compatibility with other resins. More ideally, it is less than 100,000. In addition, when the glass transition temperature is -50°C or higher, it is desirable in terms 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 force of the adhesive layer 13 at the time of dicing is excellent, more preferably 120°C or lower, and still more preferably 110°C or lower.

On the other hand, as the functional group in the polymer containing the above functional group, for example, an oxypropylene group, an acrylyl group, a butenyl group, a hydroxyl group, a carboxyl group, an isocyanurate group, an amine group can be mentioned. group, amide group, etc., among which, oxypropylene group is preferred.

As a high molecular weight component system containing the said functional group, the (meth)acrylic acid copolymer etc. of functional groups, such as an oxypropylene group, a hydroxyl group, and a carboxyl group, are mentioned, for example.

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

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

As glycidyl acrylate, the constituent monomer system of the above-mentioned (meth)acrylic copolymer other than glycidyl methacrylate, for example, ethyl (meth)acrylate and butyl (meth)acrylate are mentioned. etc., these systems can also be used individually or in combination of 2 or more types. However, in the present invention, ethyl (meth)acrylate means: showing ethyl acrylate and/or ethyl methacrylate. The mixing ratio in the case of using a functional monomer in combination can 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 ideal at a point where the film-forming properties are excellent and the excess viscosity at normal temperature can be controlled. When the adhesive force at room temperature is excessive, it becomes difficult to handle the adhesive layer. More preferably, it is -20 degreeC or more, and still more preferably, it is 0 degreeC or more. Moreover, when glass transition temperature is 30 degrees C or less, it is excellent in the point of the adhesive force of the adhesive layer at the time of dicing, and it is more preferable that it is 20 degrees C or less.

When polymerizing the above-mentioned monomers to produce a high molecular weight component containing functional monomers, the polymerization method is not particularly limited. For example, methods such as bead polymerization and solution polymerization can be used, among which bead polymerization is preferable.

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 in that the heating fluidity of the adhesive layer at the time of wafer bonding is improved. When the heating fluidity of the adhesive layer at the time of die bonding is improved, the adhesion between the adhesive layer and the adherend becomes good, the adhesive force can be improved, and the irregularities of the adherend are easily embedded to suppress voids. It is more desirable to be 1,000,000 or less, and more desirable to be 800,000 or less, and when it is 500,000 or less, a larger effect can be obtained.

In addition, there is no particular limitation on the structure of the thermally polymerizable component which is polymerized by heat, for example, those having an oxypropylene group, an acrylyl group, an isobutylene group, a hydroxyl group, a carboxyl group, and an isocyanurate group can be mentioned. , 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, together with hardener, accelerator It is preferable to contain a thermosetting resin which is hardened by heat and affects the bonding effect. Examples of thermosetting resins include epoxy resins, acrylic resins, polysiloxane resins, phenol resins, thermosetting polyimide resins, polyurethanes, melamine resins, urea resins, and the like, particularly Since an adhesive layer excellent in heat resistance, workability, and reliability can be obtained, epoxy resin is optimal.

The above-mentioned epoxy resin is not particularly limited if it has an adhesive function for curing, and bifunctional epoxy resins such as bisphenol A epoxy resin, phenol novolac epoxy resin, or cresol novolac epoxy resin can be used. Novolac epoxy resin, etc., such as epoxy resin. In addition, generally known structures such as polyfunctional epoxy resins, glycidylamine epoxy resins, heterocyclic epoxy resins, and alicyclic epoxy resins can be applied.

Examples of the above-mentioned bisphenol A-type epoxy resins include: EPIKOTE series (EPIKOTE807, EPIKOTE815, EPIKOTE825, EPIKOTE827, EPIKOTE828, EPIKOTE834, EPIKOTE1001, EPIKOTE1004, EPIKOTE1007, EPIKOTE1009) manufactured by Mitsubishi Chemical Corporation, manufactured by Dow Chemical Corporation, DER-330, DER-301, DER-361, and Nippon Steel & Sumitomo Metal 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 Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., DEN-438 manufactured by Dow Chemical Co., Ltd., and the like. Examples of the above-mentioned o-cresol novolac epoxy resins include: EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 manufactured by Nippon Kayaku Co., Ltd., or Nippon Steel & Sumitomo Metal Chemical Co., Ltd., YDCN701, YDCN702, YDCN703, YDCN704, etc. Examples of the above-mentioned polyfunctional epoxy resins include: Epon1031S manufactured by Mitsubishi Chemical Co., Ltd., Araldite 0163 manufactured by Ciba Refinery Co., Ltd., Denacol EX-611, 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-type epoxy resins include: EPIKOTE604 manufactured by Mitsubishi Chemical Co., Ltd., YH-434 manufactured by Todo Chemical Co., Ltd., TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., Sumitomo ELM-120 manufactured by Chemical Industry Co., Ltd., etc. Examples of the above-mentioned heterocycle-containing epoxy resins include Araldite PT810 manufactured by Ciba Refinery Co., Ltd., and ERL4234, ERL4299, ERL4221, and ERL4206 manufactured by UCC Corporation. These epoxy resins may be used alone or in combination of two or more.

In order to harden the said thermosetting resin, an additive can be suitably added. As such an additive system, a hardener, a hardening accelerator, a catalyst etc. are mentioned, for example, When adding a catalyst, a cocatalyst can be used as needed.

When an 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 together. Examples of the curing agent include phenol resins, dicyandiamide, boron trifluoride complexes, organic hydrazine compounds, amines, polyamide resins, imidazole compounds, urea or thiourea compounds, and polythiol Compound, polysulfide resin with sulfhydryl-based terminal, acid anhydride, light/ultraviolet hardener. These systems can be used alone or in combination of two or more. Among them, the boron trifluoride complex system includes: boron trifluoride-amine complex compound with various amine compounds (ideally a first-order amine compound), and the organic hydrazine compound system includes: Phthalohydrazine.

Examples of phenol resins include phenol novolac resins, phenol aralkyl resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins, and other novolac-type phenol resins, and resol novolac resins. Phenol resin, polyoxystyrene such as polyoxystyrene, etc. Among them, phenolic 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 molecules include phenol novolac resins, cresol novolac resins, t-butylphenol novolac resins, and cyclopentadiene cresol novolac resins. , Cyclopentadiene phenol novolac resin, xylene denatured phenol novolac resin, naphthol novolac resin, trisphenol novolac resin, tetraphenol novolac resin, bisphenol A novolac resin, poly-p-vinylphenol resin, phenol aromatic Alkyl resin, etc. Furthermore, among these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferable, and can improve connection reliability.

Examples of the amines include: chain aliphatic amines (diethylenetriamine, triethylenetetramine, hexamethylenediamine, N,N-dimethylpropylamine, benzyldimethylamine, 2(dimethylamino)phenol) , 2,4,6-tris(dimethylaminomethyl)phenol, m-m-xylylenediamine, etc.), cyclic aliphatic amines (N-aminoethylpiperazine, bis(3-methyl-4- Aminocyclohexyl)methane, bis(4-aminocyclohexyl)methane, antioxidant (MDA), isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, etc.), polycyclic amine (piperidine) oxazine, N,N-dimethylpiperazine, triethylenediamine, melamine, guanamine, etc.), aromatic amines (m-phenylenediamine, 4,4'-diaminodiphenylmethane, diamine, 4 ,4'-diaminodiphenylene, etc., polyamide resin (polyamide amine is preferred, 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 adducts, etc.), urea or urea sulfide compounds (N,N-dialkyl urea compounds, N,N-dialkyl urea sulfide compounds, etc.), polythiol compounds, polysulfides with sulfhydryl-based terminals Resin, acid anhydride (tetrahydrophthalic anhydride, etc.), light/ultraviolet curing agent (diphenyl iodide, hexafluorophosphoric acid, triphenyl perylene hexafluorophosphate, etc.).

The above-mentioned curing accelerator is not particularly limited, such as a structure for curing a thermosetting resin, and examples thereof include imidazoles, dicyandiamide derivatives, dicarboxylic acid diacids, phosphorus triphenylide, and tetraphenyl groups. 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 in the adhesive layer of the epoxy resin curing agent or curing accelerator is not particularly limited, and the optimum content varies depending on the type of the curing agent or curing accelerator.

The blending ratio of the epoxy resin and the phenol resin is, for example, optimal if the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per 1 equivalent of epoxy groups in the epoxy resin components. More preferably, it is 0.8 to 1.2 equivalents. That is, when the mixing ratio of the two is outside the aforementioned range, a sufficient curing reaction cannot proceed, and the properties of the adhesive layer are easily deteriorated. Other thermosetting resins and curing agents In one embodiment, the curing agent is 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermosetting resin, and in other embodiments, the curing agent is 1 to 10 parts by mass parts by mass. The content of the hardening accelerator is preferably less than that of the hardener, and for 100 parts by mass of the thermosetting resin, the hardening accelerator is preferably 0.001 to 1.5 parts by mass, and 0.01 to 0.95 parts by mass is more good. By adjusting it within the aforementioned range, the progress of a sufficient hardening reaction can be assisted. The content of the catalyst is preferably 0.001 to 1.5 parts by mass, and more preferably 0.01 to 1.0 parts by mass, with respect to 100 parts by mass of the thermosetting resin.

In addition, the filler of the adhesive layer 13 of the present invention can be appropriately prepared according to the application. Through this, 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 further, impart thermal conductivity to the adhesive layer in the hardened state, A follower of strength. 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, and aluminum borate can be used. Whisker, boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, antimony oxide, etc. In addition, these systems may be used alone or in a mixture of two or more.

In addition, among the above-mentioned inorganic fillers, it is preferable to use aluminum oxide, aluminum nitride, boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. from the viewpoint of improving thermal conductivity. In addition, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline di- Silicon oxide, amorphous silicon dioxide, etc. are preferred. In addition, it is preferable to use aluminum oxide and silicon dioxide from the viewpoint of improving the cutting property.

The adhesive layer of the present invention may contain, as the filler, two or more fillers having different average particle diameters. In this case, compared with the case of using a single filler, in the raw material mixture before film formation, it becomes easier to prevent the viscosity from increasing when the filler content is high or the viscosity from decreasing when the filler content is low. It is easy to obtain a good film formability, and the fluidity of the uncured adhesive layer can be suppressed to be the best, and at the same time, it is easy to obtain an excellent adhesive force for the cured adhesive layer.

In addition, the average particle diameter of the adhesive layer-based filler of the present invention is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the average particle diameter of the filler is 2.0 μm or less, thinning of the film becomes easy. Here, the thin film means a thickness of 20 μm or less. In addition, when it is 0.01 μm or more, the dispersibility is good. Furthermore, from the viewpoint of preventing the viscosity increase or viscosity decrease of the raw material mixture before thinning, optimizing the fluidity of the uncured adhesive layer, and improving the adhesive force after curing the adhesive layer, it contains an average particle size. Preferably, the diameter of the first filler is in the range of 0.1 to 1.0 μm, and the average particle diameter of the primary particle diameter of the second filler is in the range of 0.005 to 0.03 μm. 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 range of particle size 0.1~1.0μm. The first filler, 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 mean particle size in the present invention means that 50% of the particles by volume have the D50 value of the cumulative volume distribution curve of the 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 determined by diffraction of laser light according to the application of either Fraunhofer and Fiddle or Mie theories. 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 scatter of 0.02-135° with respect to the incident laser light.

In the present invention, in one aspect, the entire adhesive composition constituting the adhesive layer 13 contains 10 to 40 mass % of the thermoplastic resin having a weight average molecular weight of 5,000 to 200,000, and 10 to 40 mass % of the thermoplastic resin. % of thermally polymerizable components, and 30 to 75% by mass of filler. In this embodiment, the content of the filler may be 30 to 60 mass %, or 40 to 60 mass %. In addition, the mass average molecular weight of the thermoplastic resin may be 5,000 to 150,000, or 10,000 to 100,000. In another form, the entire adhesive composition constituting the adhesive layer 13 contains 10 to 20 mass % of a thermoplastic resin having a weight-average molecular weight of 200,000 to 2,000,000, and 20 to 50 mass % of a thermopolymerizable resin. ingredients, and 30 to 75% by mass of filler. In this embodiment, the content of the filler may be 30 to 60 mass %, or 30 to 50 mass %. In addition, the mass average molecular weight of the thermoplastic resin may be 200,000 to 1,000,000, or 200,000 to 800,000. By adjusting the mixing ratio, the storage elastic modulus and fluidity of the adhesive layer 13 after curing 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 with a structure in which glass is laminated on the upper part of the image sensor by an adhesive layer, when the light transmittance is less than 90%, there is a possibility that the sensor does not operate reliably. Generally speaking, the light transmittance can be adjusted by the composition of the adhesive layer. In particular, when the base resin and filler are selected, mounting reliability and high transmittance can be coexisted. It can be adjusted by reducing the particle size of the filler, suppressing the scattering of light, and improving the transmittance. As the resin with high transparency, for example, epoxy resin or polysiloxane resin is preferably used, and bisphenol-type epoxy resin is particularly preferably used in order to coexist with mounting reliability, but it is not limited thereto.

The light transmittance can be obtained by measuring the amount of transmitted light using a spectrophotometer (manufactured by Hitachi High-Technologies, Inc., Spectrophotometer U-4100 Solid Sample Measurement System). Specifically, an adhesive layer with a thickness of 20 μm was bonded to glass, and the light transmittance with respect to the glass of 550 nm at 25° C. was obtained as that light penetrated in the normal direction to the glass surface. Specifically, it is calculated by the following formula (2). The light transmittance of the adhesive layer I(%)= I1/I0 (2) I1(%): Light transmittance of glass containing adhesive layer I0(%): Light transmittance of glass

In the glass processing tape 10 of the present invention, the adhesive agent layer 13 may be formed into a thin film in advance (hereinafter, referred to as an adhesive film), and may be directly or indirectly laminated on the base film 11 . The temperature at the time of lamination is in the range of 10~100℃, and the linear load of 0.01~10N/m is added. However, such an adhesive film may have a structure in which the adhesive layer 13 is formed on the release film, and in this case, the release film may be peeled off after lamination, or it may be used as a cover film of the glass processing tape 10 as it is. , and can be peeled off when laminating glass.

The aforementioned adhesive film may be laminated on the entire surface of the adhesive layer 12 , but the adhesive layer 12 may also be laminated on the adhesive layer 12 by laminating the adhesive film previously bonded and cut to suit the shape of the glass (cutting according to specifications). In this way, in the case of laminating the adhesive film for glass, as shown in FIG. 3 , the adhesive layer 13 is provided for the portion where the glass W is bonded, and the adhesive layer 13 is not provided for the portion where the annular frame 20 is bonded. Instead, only the adhesive layer 12 is present. Generally speaking, since the adhesive layer 13 is not easily peeled off from the object to be attached, by using an adhesive film cut according to specifications, the annular frame 20 can be attached to the adhesive layer 12, and the adhesive tape after use can be obtained. The effect of paste residue on the ring frame 20 is not easily produced during peeling.

＜Use＞ The adhesive tape 10 for glass processing of this invention is used for the glass processing method including the expansion process which divides the adhesive agent layer 13 at least by expansion. Accordingly, other processes or the order of the processes are not particularly limited. For example, it can be used optimally in the following glass processing methods (A) to (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 to 80°C, the adhesive film attached to the adhesive layer of the tape for glass body processing, and (b) the process of irradiating laser light to a predetermined portion of the glass to form a modified range through multiphoton absorption inside the glass, and (c) the process of dividing the glass and the adhesive film along the dividing line when expanding the tape for semi-glass processing to obtain a plurality of wafers with adhesive films, and (d) a process of removing the slack generated in the expansion process by heating and shrinking the portion not overlapping the wafer of the glass processing tape, and maintaining the gap between the wafers, And (e) the glass processing method of the process of picking up the above-mentioned wafer with the above-mentioned 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 attaching the adhesive film of the adhesive layer of the adhesive tape for glass processing to the glass in a state of heating the glass at 70 to 80°C, and (b) the process of irradiating laser light along the breaking line from the surface of the aforementioned glass to separate wafers, and (c) through the process of dividing the adhesive film according to the wafer when the tape for glass processing is expanded to obtain a plurality of wafers with the adhesive film, and (d) a process of removing the slack generated in the expansion process by heating and shrinking the portion not overlapping the wafer of the glass processing tape, and maintaining the gap between the wafers, And (e) the glass processing method of the process of picking up the above-mentioned wafer with the above-mentioned adhesive layer from the adhesive layer of the glass processing tape. The processing method of this glass adopts the full-cut laser cutting method.

Glass processing method (C) Including: (a) the process of laminating the adhesive film of the adhesive layer of the glass processing tape to the glass in the state of heating the wafer at 70~80°C, and (b) the process of cutting the above-mentioned glass along the breaking line using a dicing blade, and breaking it into individual wafers, and (c) through the process of dividing the adhesive film according to the wafer when the tape for glass processing is expanded to obtain a plurality of wafers with the adhesive film, and (d) a process of removing the slack generated in the expansion process by heating and shrinking the portion not overlapping the wafer of the glass processing tape, and maintaining the gap between the wafers, And (e) the glass processing method of the process of picking up the above-mentioned wafer with the above-mentioned adhesive layer from the adhesive layer of the glass processing tape. The processing method of this glass adopts the method of full-cut blade cutting.

＜How to use＞ The adhesive tape 10 for glass processing of this invention is demonstrated simultaneously with reference to FIGS. 2-5 about the usage method of the adhesive tape in the case of applying the said glass processing method (A).

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

Next, the glass W to which the glass processing tape 10 is bonded is unloaded from above the heating stage 25, and 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 glass processing tape 10 , and the base film 11 side is placed downward on the platform 21 of the expansion device.

Next, as shown in FIG. 4( b ), in a state where the annular frame 20 is fixed, the hollow cylindrical push-up member 22 in the expansion device is raised to expand (expand) the glass processing tape 10 . As the expansion condition, the expansion speed is, for example, 5 to 500 mm/sec, and the expansion amount (pull-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 wafer 34 units 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, and the extension (deformation) through expansion is suppressed without causing breakage, but in the position between the wafers 34, the tension through the expansion of the tape is concentrated and generated fracture. Subsequently, as shown in FIG. 4( c ), simultaneously with the glass W, the adhesive layer 13 is also divided. Through this, a plurality of wafers 34 with the adhesive layer 13 attached thereto can be obtained.

Next, as shown in FIG. 5 , the push-up member 22 is returned to the 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 is performed stably. In this process, for example, in the region where the wafer 34 of the glass processing tape 10 exists, and the annular heat shrinking region 28 between the annular frame 20, the warm air nozzle 29 is used, and the contact is 40 to 120° C. The warm air heats and shrinks the base film 11, and the adhesive tape 10 for glass processing is in a state of being attached to the pins. After that, the adhesive layer 12 is subjected to energy ray hardening treatment, thermal hardening treatment, or the like to weaken the adhesive force to the adhesive layer 13 of the adhesive layer 12 , and then the wafer 34 is picked up.

However, although the adhesive tape 10 for glass processing of this embodiment has the structure provided with the adhesive layer 13 on the adhesive layer 12, the structure without providing the adhesive layer 13 may be sufficient. In this case, the glass may be laminated on the adhesive layer 12 to be used only for cutting the glass, but when it is used as a tape for glass processing, the same as the adhesive layer 13 is used as the produced adhesive film, and the The glass is attached on the adhesive layer 12 together, and the glass and the adhesive film can be separated. <Example> Next, in order to clarify the effect of this invention, an Example and a comparative example are demonstrated in detail, but this invention is not limited to these Examples.

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

<Base film B> The base film B was prepared in the same manner as the base film A by setting the thickness of the long film to be 180 μm, and extending the long film to a thickness of 90 μm other than the TD direction.

<Substrate film C> The base film C was prepared in the same manner as the base film A, with the thickness of the long film being 215 μm, and then extending the long film so as to have a thickness of 90 μm other than the TD direction.

<Substrate film D> Zinc ion polymer of ethylene-methacrylic acid-isobutyl methacrylate copolymer synthesized by radical polymerization method (methacrylic acid content 11%, isobutyl methacrylate) was melted at 230°C. Resin beads having a butyl ester content of 9%, a softening point of 64° C., a melting point of 83° C., a density of 0.95 g/cm ³ , and a zinc ion content of 4 mass %) were formed into a long film with a thickness of 150 μm using an extruder. Then, the base film D was produced from what was stretched in the TD direction so that the long film had a thickness of 90 μm.

<Substrate film E> The resin beads of styrene thermoplastic synthetic rubber and polypropylene (PP) were mixed with hydrogen at a mixing ratio of 52:48, melted at 200° C., and formed into a long film with a thickness of 150 μm using an extruder. Then, the base film E was produced from what was stretched in the TD direction so that the long film had a thickness of 90 μm.

<Substrate film F> The resin beads of styrene thermoplastic synthetic rubber and polypropylene (PP) were mixed with hydrogen at a mixing ratio of 64:36, melted at 200° C., and formed into a long film with a thickness of 150 μm using an extruder. Then, the base film F was produced from what was drawn in the TD direction so that the long film had a thickness of 90 μm.

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

<Substrate film H> The base film H was prepared in the same manner as the base film D by setting the thickness of the long film to be 150 μm, and extending the long film to a thickness of 90 μm except in the MD direction.

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

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

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

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

<Substrate film M> The base film M was prepared in the same manner as the base film A, with the thickness of the long film being 110 μm, and then extending the long film so as to have a thickness of 90 μm other than the TD direction.

<Substrate film N> The base film N was prepared in the same manner as the base film A, with the thickness of the long film being 120 μm, and the long film being stretched to a thickness of 90 μm other than in the TD direction.

(2) Preparation of acrylic copolymer The functional group-containing acrylic copolymer (A1) is composed of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methacrylic acid, and the ratio of preparing 2-ethylhexyl acrylate is 60 mol Ear%, the mass average molecular weight of the copolymer of 700,000. Next, isocyanoethyl 2-methacrylate was added so that the iodine value was 25, and 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 was prepared.

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

(3-2) Preparation of Adhesive Composition B In epoxy resin "1002" (manufactured by Mitsubishi Chemical Co., Ltd., solid bisphenol A epoxy resin, epoxy equivalent 600) 40 parts by mass, epoxy resin "806" (manufactured by Mitsubishi Chemical Co., Ltd. trade name, double Phenol F type epoxy resin, epoxy equivalent 160, specific gravity 1.20) 100 parts by mass, hardener "Dyhard100SF" (trade name made by Degussa, dicyandiamide) 5 mass parts, silica filler "SO-C2" ( ADMAFINE Co., Ltd. trade name, average particle size 0.5 μm) 200 parts by mass, and silica filler “Aerosil R972” (Japan Aerosil Co., Ltd. trade name, average particle size of primary particle size 0.016 μm) 3 mass Add MEK, stir and mix to make a homogeneous composition. In addition, 100 parts by mass of a phenoxy resin "PKHH" (trade name, manufactured by INCHEM Co., Ltd., mass average molecular weight 52,000, glass transition temperature 92°C), and "KBM-802" (Shin-Etsu Chemical Co., Ltd.) were added as a coupling agent. 0.6 parts by mass of mercaptopropyltrimethoxysilane, and "CUREZOL 2PHZ-PW" (trade name, manufactured by Shikoku Chemical Co., Ltd., 2-phenyl-4,5- 0.5 mass part of dihydroxymethylimidazole, decomposition temperature 230 degreeC), and it stirred and mixed until it became uniform. Furthermore, these were filtered with the filter of 100 meshes, and the varnish of the adhesive composition was obtained by vacuum defoaming.

<Example 1> To 100 parts by mass of the above-mentioned acrylic copolymer, 5 parts by mass of coronate L (manufactured by Nippon Polyurethane) was added as a polyisocyanate, and 3 parts by mass of Esacure KIP 150 (Lamberti) was added as a photopolymerization initiator. A mixture of the company) was dissolved in ethyl acetate and stirred to prepare an adhesive composition. A release liner made of a release-treated polyethylene terephthalate film was coated with the adhesive composition so that the thickness after drying was 10 μm, and then dried at 110°C for 3 minutes. , and lamination with the base film to make an adhesive sheet that forms an adhesive layer on the base film.

Next, on the release liner made of the polyethylene terephthalate film that was released from the mold, the above-mentioned adhesive composition A was coated so that the thickness after drying was 20 μm, and then the temperature was 110° C. After drying for 5 minutes, an adhesive film for forming an adhesive layer on a release liner was produced.

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

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

The adhesive tapes related to the glass processing tapes of Examples and Comparative Examples were cut so as to have a length of 24 mm (the direction in which the deformation amount was measured) and a width of 5 mm (the direction perpendicular to the direction of the deformation amount measurement) to prepare a test piece. The obtained test piece was measured by the tensile load method using a thermomechanical property tester (manufactured by Rigaku Co., Ltd., trade name: TMA8310) under the following measurement conditions through the temperature between the two directions of MD and TD. deformed. (measurement conditions) Measuring temperature: -60~100℃ Heating rate: 5℃/min Measurement load: 19.6mN Ambient gas: nitrogen environment (100ml/min) Sampling: 0.5s Distance between suction cups: 20mm

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

[Evaluation of the retention of incision width] By the method shown below, with respect to each tape for glass processing of the said Example and the said comparative example, glass was divided|segmented into wafer, and the retention property of a slit width was evaluated.

(a) The process of irradiating laser light to a predetermined part of the glass to form a modified range through multiphoton absorption inside the glass, and (b) the process of laminating the adhesive layer of the above-mentioned glass processing tape to the above-mentioned glass in the state of heating the above-mentioned glass to 70~80℃, and (c) the process of dividing the glass and the adhesive layer along the dividing line when the tape for glass processing is expanded to obtain a plurality of wafers with adhesive films, and (d) by heating and shrinking the portion that does not overlap with the wafer of the glass processing tape (the region where the wafer exists and the annular region between the annular frame), the expansion in (c) is removed. The slack that occurs in the process, the process of maintaining the spacing between the wafers, and (e) the process of picking up the wafer with the adhesive layer attached from the adhesive layer of the glass processing tape.

However, in the process of (b), the breaking line of the glass is added to the MD direction and the TD direction of the base film, and the glass is bonded to the tape for glass processing.

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

(d) In the process, the expansion rate was 1 mm/sec and the expansion height was 10 mm at room temperature, and after expansion was performed again, the thermal shrinkage treatment was performed under the following conditions. [Condition 1] Heater set temperature: 220℃ Hot air volume: 40L/min Distance between heater and glass processing tape: 20mm Heater rotation speed: 7°/sec [Condition 2] Heater set temperature: 220℃ Hot air volume: 40L/min Distance between heater and 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 step (d), as shown in FIG. 6 , in the MD direction of the adhesive tape, it was measured from the right side of FIG. 6 without a missing corner. The notch width X between the wafers next to the center in the MD direction of the most extreme wafer 50a (the notch width in the MD direction), and the notch width Y between the wafers from the center in the TD direction of the wafer 50a (the notch width in the TD direction) ). Similarly, in the MD direction of the adhesive tape, the notch width in the MD direction and the notch width in the TD direction were also measured from the leftmost wafer 50b in FIG. In addition, in the TD direction of the adhesive tape, the notch width in the MD direction and the notch width in the TD direction were also measured for the wafer 51 at the extreme end with no corner cut and the wafer 52 at the center. The average value of the notch widths in the MD direction at the above-mentioned five points and the average value of the notch widths in the TD direction at the above-mentioned five points were calculated. And the average value of 5 points of slit widths in the MD direction and the average value of five points of slit widths in the TD direction, whichever is smaller, were used as the minimum slit width. In both conditions 1 and 2 of the above-mentioned process (g), the structure with the minimum notch width of 7 μm or more was evaluated as a good product, and the structure with the minimum notch width of 7 μm or more in Condition 2 was evaluated as a good product , evaluated as "○", in condition 2, the configuration with the minimum incision width of 5 μm or more was evaluated as “△” as an acceptable product, and the configuration in both conditions 1 and 2, the minimum incision width was less than 5 μm, as a defective product, evaluated "X". The results are shown in Tables 1 and 2.

[Measurement of Transmittance of Adhesive Layer] The transmittance was measured by the method shown below about the adhesive layer of the said Example and the said comparative example. 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. The glass containing the glass and the adhesive layer was measured by a spectrophotometer (a spectrophotometer U-4100 type solid sample measurement system, manufactured by Hitachi High-Technologies, Inc.) as a way of entering the glass surface in the normal direction. The light transmittance of the glass at 25° C. of 550 nm was measured, and the transmittance of the adhesive layer was calculated by the following formula (2). The results are shown in Tables 1 and 2. The light transmittance of the adhesive layer I(%)=I1/I0 (2) I1(%): Light transmittance of glass containing adhesive layer I0(%): Light transmittance of glass

As shown in Table 1, the tapes for glass processing related to Examples 1 to 8 were measured by a thermomechanical property tester in the MD direction of the adhesive tape at a temperature of 40°C to 80°C per 1°C. The integral value calculated from the sum of the thermal deformation rates and the integral value calculated from the sum of the thermal deformation rates per 1°C between 40°C and 80°C measured by a thermomechanical property testing machine in the TD direction during the temperature rise Because the sum of , is negative, it is a result of excellent retention of the kerf width. Thereby, it can suppress that the adhesive agent layers contact each other and generate|occur|produce rebonding.

On the other hand, the adhesive tapes for glass processing of Comparative Examples 1 to 6 are as shown in Table 2, and are measured at a temperature between 40°C and 80°C by a thermomechanical property tester in the MD direction of the adhesive tape. The integral value calculated from the sum of the thermal deformation rates per 1°C and the sum of the thermal deformation rates per 1°C between 40°C and 80°C measured by a thermomechanical property tester in the TD direction at the time of temperature rise Since the sum of the calculated integral values is not a negative value, it is a result that the retention of the notch width is not good.

10: Tape for glass processing 11: substrate film 12: Adhesive layer 13: Adhesive layer 22: Push on the components 28: heating shrinkage range 29: Warm air nozzle

It is sectional drawing which shows typically the structure of the adhesive tape for glass processing concerning embodiment of this invention. 2 is a cross-sectional view for explaining the process of laminating glass and a ring frame to the glass processing tape according to the embodiment of the present invention. FIG. 3 is a cross-sectional view showing a state in which a modified range is formed in glass by laser processing. [ Fig. 4] (a) is a cross-sectional view showing a state in which the tape for glass processing according to the embodiment of the present invention is mounted on an expansion device. (b) is a cross-sectional view showing the process of dividing glass into wafers through expansion of the tape for glass processing. (c) is a cross-sectional view showing the glass processing tape after expansion, the adhesive layer, and the wafer. Fig. 5 is a cross-sectional view for explaining the heat shrinking process. [ Fig. 6] Fig. 6 is an explanatory diagram showing a measurement location of the notch width in the evaluation of Examples and Comparative Examples. Fig. 7 is 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 (3)

An adhesive tape for glass processing, comprising: an adhesive tape having a base film and an adhesive layer formed on at least one side of the base film; the MD direction of the above-mentioned adhesive tape is caused by a thermomechanical property tester when heating up The integral value calculated from the sum of the thermal deformation rate per 1°C measured between 40°C and 80°C, and the reason for the TD direction through the thermomechanical property testing machine. The sum of the integral values calculated from the sum of the thermal deformation rate per 1°C between the two is a negative value; for the processing of the glass used in the expansion process including the expansion of the above-mentioned adhesive tape: Laminate the adhesive layer on the side of the above-mentioned adhesive layer; the above-mentioned The adhesive layer has a light transmittance of 90% or more for light having a wavelength of 550 nm. An adhesive tape for glass processing, comprising: 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 ionomer resin, or polypropylene and It is composed of a mixed resin composition of styrene-butadiene copolymer; the MD direction of the above-mentioned adhesive tape system is measured by a thermomechanical property tester at the temperature of 40°C to 80°C for every 1°C. The integral value calculated from the sum of the thermal deformation rates and the integral calculated from the sum of the thermal deformation rates per 1°C between 40°C and 80°C measured by the thermomechanical property testing machine at the time of heating up in the TD direction. The sum of the values is negative. As claimed in claim 1 or claim 2, the tape for glass processing is used for full cutting blade cutting, laser cutting, or invisible laser cutting via laser.

Images