CN112368108B

CN112368108B - Adhesive tape for glass processing

Info

Publication number: CN112368108B
Application number: CN202080003846.4A
Authority: CN
Inventors: 松原侑弘; 横井启时
Original assignee: Furukawa Electric Co Ltd
Current assignee: Furukawa Electric Co Ltd
Priority date: 2019-05-29
Filing date: 2020-03-04
Publication date: 2022-11-04
Anticipated expiration: 2040-03-04
Also published as: SG11202100512QA; TWI755743B; JP7060547B2; JP2020194903A; WO2020240962A1; KR20210015888A; TW202043401A; CN112368108A; PH12021550125A1; KR102505582B1

Abstract

The invention provides an adhesive tape for glass processing, which can be sufficiently heated and shrunk in a short time and can keep the width of a cut. The adhesive tape (10) for glass processing is characterized by comprising an adhesive tape (15), wherein the adhesive tape (15) comprises a base film (11) and an adhesive layer (12) formed on at least one surface side of the base film (11), the sum of an integral value in the MD direction calculated from the sum of thermal deformation rates per 1 ℃ between 40 ℃ and 80 ℃ measured by a thermomechanical property tester at the time of temperature rise and an integral value in the TD direction calculated from the sum of thermal deformation rates per 1 ℃ between 40 ℃ and 80 ℃ measured by a thermomechanical property tester at the time of temperature rise is a negative value, and the adhesive tape (10) for glass processing comprising a step of expanding the adhesive tape (15) is used for glass processing.

Description

Adhesive tape for glass processing

Technical Field

The present invention relates to an expandable glass processing tape which can be used in a dicing step for dividing glass into chip-like elements, in a step of fixing the glass, in a die bonding step or a mounting step for bonding chips after dicing or between the chips and a substrate, and in a step of dividing an adhesive layer along the chips by expansion.

Background

A camera or a sensor mounted in a smartphone or the like is mounted with glass having various characteristic optical characteristics. These glasses are generally produced by vacuum deposition or the like of various materials for a glass to be a base material. After the adhesive and stretchable glass processing tape is attached to the glass, a dicing step of dividing the glass into chip units, an expanding step of expanding (expanding) the glass processing tape, a picking up step of picking up the divided chips, and a pasting step of bonding the picked-up chips to a specific position are performed.

In the glass cutting step, cutting by a blade has been a main stream in the past, but due to the influence of thinning and vapor deposition of glass itself, breakage called chipping and the like become problems, and thus there is a problem that productivity is lowered.

In order to solve such a problem, in recent years, as a glass cutting method, a so-called stealth dicing method has been proposed, in which glass can be cut in a non-contact manner using a laser processing apparatus. For example, patent document 1 discloses a method for cutting a semiconductor substrate, which includes the following steps: a step of condensing a focal light in a semiconductor substrate to which a sheet is attached by interposing an adhesive layer (a chip resin layer), irradiating the inside with a laser beam, thereby forming a modified region by multiphoton absorption in the semiconductor substrate, and using the modified region as a portion to be cut; and a step of cutting the semiconductor substrate and the adhesive layer along the portion to be cut by expanding the sheet.

As another method for cutting a wafer using a laser processing apparatus, for example, patent document 2 proposes a wafer dividing method including the steps of: a step of mounting an adhesive layer (adhesive film) for bonding on the back surface of the wafer; a step of bonding an extensible protective adhesive tape to the adhesive layer side of the wafer to which the adhesive layer is bonded; irradiating a laser beam from the surface of the wafer bonded with the protective adhesive tape along the dicing streets to divide the wafer into chips; a step of expanding the protective adhesive tape to apply a tensile force to the adhesive layer and cutting the adhesive layer for each chip; and a step of detaching the chip to which the cut adhesive layer is attached from the protective adhesive tape.

According to the method for cutting a wafer described in patent document 1 and patent document 2, since the wafer is cut in a non-contact manner by irradiation of laser light and expansion of the tape, the physical load on the wafer is small, and the wafer can be cut without generating chips of the wafer as in the case of blade dicing which is currently the mainstream. Further, since the adhesive layer is divided by the expansion, no cutting chips of the adhesive layer are generated. Therefore, the present invention has been attracting attention as an excellent technique that can replace blade cutting.

The separation techniques described in these documents are mainly applied to wafers, but can be applied to glass by changing the laser engine of the apparatus to glass.

However, as described in patent documents 1 and 2, when the conventional adhesive tape for semiconductor processing is used in the method of expanding and dividing the adhesive layer by spreading, there are the following problems: as the expansion amount increases, the portion pushed up by the expansion ring expands, and after the expansion is released, the portion relaxes, and the space between chips (hereinafter referred to as "notch width") cannot be maintained.

Therefore, the following methods are proposed: after the adhesive layer is divided by expansion and the expansion is released, the slack portion of the tape for semiconductor processing is heated and contracted to maintain the notch width (for example, patent document 3,4).

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication 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 laid-open publication No. 2015-211081

Disclosure of Invention

Problems to be solved by the invention

However, as a method of shrinking the slack of the semiconductor processing tape caused by the expansion by heating, the following method is generally used: the pair of warm air nozzle rings are wound around an annular portion that is pushed up by an expanded ring to be loosened, and warm air is blown to the portion and heated to contract the portion.

In the adhesive tape for semiconductor processing described in patent document 3, the thermal shrinkage rate of the adhesive tape in both the longitudinal direction and the width direction when heated at 100 ℃ for 10 seconds is 0% or more and 20% or less. However, when heating is performed by surrounding the warm air nozzle, the temperature in the vicinity of the surface of the tape for glass processing gradually rises, and therefore, there is a problem that it takes time to remove the slack in all the annular positions. Further, the holding property of the notch width is insufficient, and when the adhesive layers are brought into contact with each other and re-joined and transferred to the division of the glass, there is a problem that the yield of the glass processing step is deteriorated.

The semiconductor processing tape described in patent document 4 has a shrinkage rate of 0.1% or more at 130 to 160 ℃ (see claim 1 of the specification of patent document 4), and the temperature at which shrinkage occurs is high. Therefore, when the thermal contraction is performed by warm air, a high temperature and a long heating time are required, and the warm air affects the adhesive layer near the outer periphery of the wafer, and the divided adhesive layer may melt and re-fuse.

Accordingly, an object of the present invention is to provide a glass processing tape which can be sufficiently shrunk by heating in a short time and can sufficiently maintain a slit width to a degree that prevents adhesive layers from coming into contact with each other and being re-bonded.

Means for solving the problems

In order to solve the above problems, the present invention provides an adhesive tape for glass processing, the adhesive tape comprising a base film and an adhesive layer formed on at least one surface of the base film, wherein a sum of an integral value in an MD direction calculated from a sum of thermal deformation rates per 1 ℃ between 40 ℃ and 80 ℃ measured at a time of temperature rise by a thermomechanical property tester and a sum of an integral value in a TD direction calculated from a sum of thermal deformation rates per 1 ℃ between 40 ℃ and 80 ℃ measured at a time of temperature rise by a thermomechanical property tester is a negative value, and the adhesive tape for glass processing is used for processing glass including an expansion step of expanding the adhesive tape.

In order to solve the above problems, the present invention provides a glass-processing tape comprising an adhesive tape having a base film and an adhesive layer formed on at least one surface side of the base film, wherein the base film is formed from an ionomer resin or a mixed resin composition of a polypropylene film and a styrene-butadiene copolymer, and wherein the sum of an integral value in the MD direction calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by a thermomechanical property tester at the time of temperature rise and an integral value in the TD direction calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by a thermomechanical property tester at the time of temperature rise is a negative value.

The glass processing tape is preferably used for full-cut blade cutting, full-cut laser cutting, or stealth cutting using a laser.

The glass processing tape preferably has an adhesive layer laminated on the adhesive layer side, and the adhesive layer has a light transmittance of 90% or more with respect to light having a wavelength of 550 nm.

Effects of the invention

According to the adhesive tape for glass processing of the present invention, it is possible to sufficiently perform heat shrinkage in a short time and to sufficiently maintain the width of the cut to such an extent that re-bonding of the adhesive layers due to contact with each other can be suppressed.

Drawings

Fig. 1 is a cross-sectional view schematically showing the structure of a glass processing tape according to an embodiment of the present invention.

Fig. 2 is a sectional view for explaining a process of bonding 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 mode of forming a modified region 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 the expanding device. (b) The cross-sectional view is a view showing a process of dividing glass into chips by expanding a glass processing tape. (c) The cross-sectional view shows the glass processing tape, the adhesive layer and the chip after expansion.

Fig. 5 is a sectional view for explaining a heat shrinking process.

FIG. 6 is an explanatory view showing the measurement points of the incision width in the evaluation of examples and comparative examples.

Fig. 7 shows an example of the measurement result of the thermal deformation rate.

Detailed Description

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

Fig. 1 is a sectional view showing a glass processing tape 10 according to an embodiment of the present invention. When the glass processing tape 10 of the present invention is expanded to divide glass into chips, the transparent adhesive layer 13 is divided along the chips. The glass-processing tape 10 includes: the pressure-sensitive adhesive tape 15 includes a base film 11 and a pressure-sensitive adhesive layer 12 provided on the base film 11, and a transparent pressure-sensitive adhesive layer 13 provided on the pressure-sensitive adhesive layer 12, and the back surface of glass is bonded to the transparent pressure-sensitive adhesive layer 13. Each layer may be cut (precut) into a predetermined shape in advance in accordance with a use process or an apparatus. Further, the glass-processing tape 10 of the present invention may be cut into 1 glass sheet, or a long sheet of a plurality of glass-processing tapes cut into 1 glass sheet may be wound into a roll. The structure of each layer will be described below.

< substrate film >

When the base film 11 has uniform and isotropic stretchability, it is preferable that the glass can be cut without variation in all directions in the stretching step, and the material thereof is not particularly limited. In general, a crosslinked resin has a larger restoring force to stretching than a non-crosslinked resin, and a larger shrinkage stress when heated in a stretched state after an expansion step. Therefore, it is excellent in that the slack generated in the tape is removed by heat shrinkage after the expanding step, and the tape is stretched to stably maintain the interval (slit width) between the chips. Among the crosslinked resins, a thermoplastic crosslinked resin is more preferably used. On the other hand, the non-crosslinked resin has a smaller restoring force to stretching than the crosslinked resin. Therefore, the tape is temporarily loosened after the expanding step in a low temperature region of-15 to 0 ℃, and is less likely to shrink when returning to normal temperature and proceeding to the picking-up step and the mounting step, and therefore, is excellent in preventing the adhesive layers adhering to the chips from coming into contact with each other. Among the non-crosslinked resins, an olefin-based non-crosslinked resin is more preferably used.

Examples of such thermoplastic crosslinked resins include: an ionomer resin obtained by crosslinking a terpolymer containing an ethylene- (meth) acrylic acid copolymer or an ethylene- (meth) acrylic acid-alkyl (meth) acrylate as a main polymer component with a metal ion. They are particularly suitable in the following respects: is suitable for the expanding step in terms of uniform expandability, and exhibits strong restoring force when heated by crosslinking. The metal ions contained in the ionomer resin are not particularly limited, and examples thereof include zinc, sodium, and the like, and zinc ions are preferable in terms of low elution and low contamination. Among the alkyl (meth) acrylates of the terpolymer, an alkyl group having 1 to 4 carbon atoms is preferable in that it has a high elastic modulus and can transmit a strong force to glass. Examples of such alkyl (meth) acrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like.

In addition, as the thermoplastic crosslinked resin, in addition to the ionomer resin, a resin obtained by crosslinking a resin selected from the group consisting of low density polyethylene having a specific gravity of 0.910 or more and less than 0.930, ultra low density polyethylene having a specific gravity of less than 0.910, and an ethylene-vinyl acetate copolymer by irradiation with an energy ray such as an electron beam is also suitable. Such a thermoplastic crosslinked resin has a certain uniform expansion property because crosslinked sites and non-crosslinked sites coexist in the resin. Further, since the adhesive tape exerts a strong restoring force during heating, it is suitable for removing slack of the adhesive tape generated in the expanding step, and since there is little chlorine in the molecular chain structure, even if the adhesive tape which becomes unnecessary after use is incinerated, chlorinated aromatic hydrocarbons such as dioxin and the like are not generated, and thus the environmental burden is small. By appropriately adjusting the amount of energy rays to be irradiated to the polyethylene or ethylene-vinyl acetate copolymer, a resin having a sufficiently uniform expandability can be obtained.

Examples of the non-crosslinked resin include: a mixed resin composition of polypropylene and a styrene-butadiene copolymer.

As polypropylene, for example, there can be used: homopolymers of propylene, or block-type or random-type propylene-ethylene copolymers. The random type propylene-ethylene copolymer is preferably small in rigidity. When the content of the ethylene structural unit in the propylene-ethylene copolymer is 0.1% by weight or more, the adhesive tape is excellent in rigidity and compatibility between resins in the mixed resin composition. When the rigidity of the tape is appropriate, the glass-cutting property is improved, and the compatibility between resins is high, the extrusion discharge amount is easily stabilized. More preferably 1% by weight or more. When the content of the ethylene structural unit in the propylene-ethylene copolymer is 7% by weight or less, the polypropylene is excellent in that stable polymerization of the polypropylene is easy. More preferably 5% by weight or less.

As the styrene-butadiene copolymer, a hydrogenated styrene-butadiene copolymer may also be used. When the styrene-butadiene copolymer is hydrogenated, the compatibility with propylene is good, and embrittlement and discoloration due to oxidative deterioration caused by double bonds in butadiene can be prevented. When the content of the styrene structural unit in the styrene-butadiene copolymer is 5% by weight or more, the styrene-butadiene copolymer is preferably easily stably polymerized. When the content is 40% by weight or less, the flexibility is preferable in terms of the stretchability. More preferably 25% by weight or less, and still more preferably 15% by weight or less. As the styrene-butadiene copolymer, any of a block type copolymer and a random type copolymer can be used. The random copolymer is preferred because the styrene phase is uniformly dispersed, and excessive increase in rigidity and improvement in expandability can be suppressed.

When the content of polypropylene in the mixed resin composition is 30% by weight or more, it is excellent in that unevenness in thickness of the base material film can be suppressed. When the thickness is uniform, the expansion properties are easily isotropic, and it is easy to prevent the stress relaxation property of the base film from becoming too large, the distance between chips from becoming small with time, and the adhesive layers from coming into contact with each other and re-fusing. More preferably 50% by weight or more. When the content of polypropylene is 90 wt% or less, the rigidity of the base film can be easily adjusted appropriately. If the rigidity of the base film is too high, the force required to expand the base film increases, which increases the burden on the apparatus and may make it impossible to sufficiently expand the glass or adhesive layer 13, and therefore, appropriate adjustment is important. The lower limit of the content of the styrene-butadiene copolymer in the mixed resin composition is preferably 10% by weight or more, and can be easily adjusted to be suitable for the rigidity of the substrate film of the device. An upper limit of 70 wt% or less is excellent in that unevenness in thickness can be suppressed, and 50 wt% or less is more preferable.

In the example shown in fig. 1, the base film 11 is a single layer, but is not limited thereto, and may have a multilayer structure in which 2 or more resins are laminated, or 1 resin may be laminated in 2 or more layers. If the total of 2 or more resins is crosslinkable or non-crosslinkable, it is preferable from the viewpoint of further enhancing and developing the respective properties, and when they are laminated in combination of crosslinkable or non-crosslinkable properties, it is preferable to complement the respective disadvantages. The thickness of the base film 11 is not particularly limited, and the base film is easy to stretch in the expanding step of the glass processing tape 10 and has sufficient strength so as not to break. For example, it may be about 50 to 300. Mu.m, and more preferably 70 to 200. Mu.m.

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

< adhesive layer >

The adhesive layer 12 can be formed by applying an adhesive composition to the substrate film 11. The pressure-sensitive adhesive layer 12 constituting the glass processing tape 10 of the present invention may have such a property that it is easily peeled from the pressure-sensitive adhesive layer 13 at the time of picking up, and has such a holding property that defects such as peeling from the pressure-sensitive adhesive layer 13 and chip scattering do not occur at the time of dicing.

In the glass-processing tape 10 of the present invention, the configuration of the adhesive composition constituting the adhesive layer 12 is not particularly limited, but in order to improve the pickup after dicing, an energy ray-curable adhesive composition is preferable, and a material which is easily peeled from the adhesive layer 13 after curing is preferable. As one mode, there can be exemplified: the adhesive composition contains, as a matrix resin, a polymer (A) containing 60 mol% or more of a (meth) acrylate having an alkyl chain with 6 to 12 carbon atoms and having an energy-ray-curable carbon-carbon double bond with an iodine value of 5 to 30. Here, the energy ray refers to a light ray such as an ultraviolet ray or an ionizing radiation such as an electron beam.

In the polymer (a), when the amount of introduction of the energy ray-curable carbon-carbon double bond is 5 or more in terms of iodine value, the effect of reducing the adhesive force after the irradiation with the energy ray is excellent. More preferably 10 or more. Further, when the iodine value is 30 or less, the holding force of the chip after the energy ray irradiation until the pickup is performed is high, and it is preferable that the gap between the chips is easily enlarged when the expansion is performed immediately before the pickup step. When the gap between the chips can be sufficiently enlarged before the pickup step, it is preferable that the image of each chip at the time of pickup be easily recognized and picked up. Further, when the amount of carbon-carbon double bonds introduced is 5 or more and 30 or less in terms of iodine value, the polymer (a) itself is stable and easy to produce, and therefore, it is preferable.

Further, the polymer (A) has a glass transition temperature of-70 ℃ or higher, and is excellent in heat resistance to heat accompanying energy ray irradiation, and more preferably-66 ℃ or higher. Further, if the temperature is 15 ℃ or lower, various films are formed in a surface state, and the chip scattering prevention effect after dicing of glass having a surface level difference is excellent, more preferably 0 ℃ or lower, and still more preferably-28 ℃ or lower.

The polymer (a) mentioned above may be produced by any means, and for example: a product obtained by mixing an acrylic copolymer with a compound having an energy ray-curable carbon-carbon double bond; an acrylic copolymer having a functional group or a methacrylic copolymer having a functional group (A1) is reacted with a compound having a functional group reactive with the functional group and having an energy ray-curable carbon-carbon double bond (A2).

Among them, as the above methacrylic copolymer (A1) having a functional group, there can be exemplified: a product obtained by copolymerizing a monomer (A1-1) having a carbon-carbon double bond such as an alkyl acrylate or an alkyl methacrylate with a monomer (A1-2) having a functional group and a carbon-carbon double bond. Examples of the monomer (A1-1) include: hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, decyl acrylate, lauryl acrylate having an alkyl chain of 6 to 12 carbon atoms; or amyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, and methyl acrylate, which are monomers having an alkyl chain of 5 or less carbon atoms; or the same methacrylic acid esters as those described above.

In the monomer (A1-1), the component having an alkyl chain of 6 or more carbon atoms can reduce the peel force between the pressure-sensitive adhesive layer and the adhesive layer, and therefore is excellent in the pickup property. Further, the components of 12 or less have a low elastic modulus at room temperature, and are excellent in terms of adhesion at the interface between the pressure-sensitive adhesive layer and the adhesive layer. When the adhesive force at the interface between the adhesive layer and the adhesive layer is high, the interface between the adhesive layer and the adhesive layer is suppressed from being deviated when the tape is stretched to cut the glass, and the cuttability is improved, which is preferable.

Further, since the glass transition temperature is lower when a monomer having a larger carbon number in the alkyl chain is used as the monomer (A1-1), a binder composition having a desired glass transition temperature can be produced by appropriately selecting the monomer. In addition, low molecular weight compounds having a carbon-carbon double bond such as vinyl acetate, styrene, and acrylonitrile may be blended for the purpose of improving various performances such as compatibility, in addition to the glass transition temperature. In this case, these low-molecular compounds are blended in a range of 5 mass% or less of the total mass of the monomer (A1-1).

On the other hand, examples of the functional group of the monomer (A1-2) include: examples of the monomer (A1-2) include carboxyl group, hydroxyl group, amine group, cyclic acid anhydride group, epoxy group, isocyanate group, and the like: acrylic acid, methacrylic acid, cinnamic acid, itaconic acid, fumaric acid, phthalic acid, 2-hydroxyalkyl acrylates, 2-hydroxyalkyl methacrylates, ethylene glycol monoacrylates, ethylene glycol monomethacrylates, N-methylolacrylamide, N-methylolmethacrylamide, allyl alcohol, N-alkylaminoethyl acrylates, N-alkylaminoethyl methacrylates, acrylamides, methacrylamides, maleic anhydride, itaconic anhydride, fumaric anhydride, phthalic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and the like.

Further, in the case where the functional group of the compound (A1) used in the compound (A2) is a carboxyl group or a cyclic acid anhydride group, examples thereof include: examples of the hydroxyl group include a hydroxyl group, an epoxy group, and an isocyanate group, and when the hydroxyl group is a hydroxyl group: when the cyclic acid anhydride group, isocyanate group, etc. are amino groups, examples thereof include: when the epoxy group is an epoxy group, examples thereof include: specific examples of the carboxyl group, the cyclic acid anhydride group and the amino group include the same compounds as those listed as specific examples of the monomer (A1-2). Further, as the compound (A2), a compound obtained by urethanizing a part of the isocyanate groups of the polyisocyanate compound with a monomer having a hydroxyl group, a carboxyl group, and an energy ray-curable carbon-carbon double bond may be used.

In the reaction of the compound (A1) and the compound (A2), a desired compound can be produced with respect to characteristics such as an acid value and a hydroxyl value by leaving unreacted functional groups. When the OH groups remain so that the hydroxyl value of the polymer (a) is 5 to 100, the adhesive force after irradiation with energy rays can be reduced, thereby further reducing the risk of pickup errors. In addition, when the COOH group remains so that the acid value of the polymer (a) is 0.5 to 30, the effect of improving the recovery of the pressure-sensitive adhesive layer after the expansion of the glass processing tape of the present invention can be obtained, which is preferable. When the hydroxyl value of the polymer (a) is 5 or more, the adhesive strength after energy ray irradiation is excellent in terms of the effect of reducing the adhesive strength, and when the hydroxyl value is 100 or less, the adhesive strength after energy ray irradiation is excellent in terms of the fluidity. When the acid value is 0.5 or more, the adhesive tape is excellent in terms of recovery from adhesive tape, and when the acid value is 30 or less, the adhesive tape is excellent in terms of fluidity.

In the synthesis of the polymer (a), as the organic solvent in the case of performing the reaction by solution polymerization, ketone-based, ester-based, alcohol-based, and aromatic-based organic solvents can be used, and among them, a solvent having a boiling point of 60 to 120 ℃ and being a good solvent for general acrylic polymers such as toluene, ethyl acetate, isopropyl alcohol, benzyl cellosolve, ethyl cellosolve, acetone, and methyl ethyl ketone is preferable, and as the polymerization initiator, a radical generator such as azo-based, e.g., α' -azobisisobutyronitrile, and organic peroxide-based, e.g., benzoyl peroxide, is used. In this case, if necessary, a catalyst and a polymerization inhibitor may be used in combination, and the polymerization temperature and the polymerization time may be adjusted to obtain the polymer (A) having a desired molecular weight. In addition, as for the adjustment of the molecular weight, a thiol or carbon tetrachloride solvent is preferably used. The reaction is not limited to solution polymerization, and may be another method such as bulk polymerization or suspension polymerization.

The polymer (a) can be obtained as described above, and in the present invention, when the molecular weight of the polymer (a) is 30 ten thousand or more, the polymer (a) is excellent in that the cohesive force can be improved. When the cohesive force is high, there is an effect of suppressing the deviation at the interface with the adhesive layer at the time of expansion, and the adhesive layer easily conducts a tensile force, so that it is preferable in terms of improving the separability of the adhesive layer. When the molecular weight of the polymer (a) is 200 ten thousand or less, the polymer (a) is excellent in suppressing gelation during synthesis and coating. The molecular weight in the present invention means a mass average molecular weight in terms of polystyrene.

In the glass processing tape 10 of the present invention, the resin composition constituting the pressure-sensitive adhesive layer 12 may further include a compound (B) that functions as a crosslinking agent in addition to the polymer (a). Examples thereof include: polyisocyanates, melamine-formaldehyde resins, and epoxy resins, which may be used alone or in combination of 2 or more. The compound (B) reacts with the polymer (a) or the base material film to form a crosslinked structure, and the cohesive force of the adhesive containing the polymers (a) and (B) as main components can be increased after the adhesive composition is applied.

The polyisocyanate is not particularly limited, and examples thereof include: examples of the isocyanate include aromatic isocyanates such as 4,4' -diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4' -diphenylether diisocyanate, 4,4' - [2,2-bis (4-phenoxyphenyl) propane ] diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, isophorone diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, 2,4' -dicyclohexylmethane diisocyanate, lysine diisocyanate, and lysine triisocyanate, and specifically, coronate L (product name, manufactured by Polyurethane corporation, japan) can be used. Specific examples of the melamine-formaldehyde resin include NIKALAC MX-45 (trade name, manufactured by Sanko Chemical Co., ltd.), MELAN (trade name, manufactured by Hitachi Chemical Co., ltd.), and the like. As the epoxy resin, TETRAD-X (trade name, manufactured by Mitsubishi chemical corporation) or the like can be used. In the present invention, polyisocyanates are particularly preferably used.

The pressure-sensitive adhesive layer in which the amount of the compound (B) added is 0.1 part by mass or more per 100 parts by mass of the polymer (a) is excellent in cohesive force. More preferably 0.5 parts by mass or more. In addition, the adhesive layer of 10 parts by mass or less is excellent in suppressing rapid gelation at the time of application, and the workability of mixing and applying the adhesive is good. More preferably 5 parts by mass or less.

In the present invention, the adhesive layer 12 may contain a photopolymerization initiator (C). The photopolymerization initiator (C) contained in the pressure-sensitive adhesive layer 12 is not particularly limited, and conventionally known photopolymerization initiators can be used. Examples thereof include: benzophenones such as benzophenone, 4,4' -dimethylaminobenzophenone, 4,4' -diethylaminobenzophenone, 4,4' -dichlorobenzophenone, and the like; acetophenones such as acetophenone and diethoxyacetophenone, anthraquinones such as 2-ethylanthraquinone and tert-butylanthraquinone; 2-chlorothioxanthone, benzoin ethyl ether, benzoin isopropyl ether, benzil, 2,4,5-triarylimidazole dimer (powderine dimer), acridine compounds, and the like, and they may be used singly or in combination of 2 or more. The amount of the photopolymerization initiator (C) added is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, per 100 parts by mass of the polymer (a). The upper limit is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

Further, a tackifier, an adhesion regulator, a surfactant, or the like, or another modifier may be added to the energy ray-curable adhesive used in the present invention, as necessary. Further, an inorganic compound filler may be appropriately added.

The pressure-sensitive adhesive layer 12 can be formed by a conventional method for forming a pressure-sensitive adhesive layer. For example, the pressure-sensitive adhesive layer 12 can be formed on the substrate film 11 by a method of applying the pressure-sensitive adhesive composition to a predetermined surface of the substrate film 11, or a method of applying the pressure-sensitive adhesive composition to a spacer (for example, a plastic film or sheet coated with a release agent) to form the pressure-sensitive adhesive layer 12, and then transferring the pressure-sensitive adhesive layer 12 to a predetermined surface of the substrate. The pressure-sensitive adhesive layer 12 may have a single-layer form or a laminated form.

The thickness of the pressure-sensitive adhesive layer 12 is not particularly limited, but is preferably 2 μm or more, more preferably 5 μm or more, in view of the adhesive strength. When the particle diameter is 15 μm or less, the pick-up property is excellent, and more preferably 10 μm or less.

The adhesive tape 15 has a negative value, i.e., less than 0, which is the sum of an integrated value in the MD (Machine Direction) Direction calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by a thermomechanical property tester at the time of temperature rise and an integrated value in the TD (perpendicular Direction) Direction calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by a thermomechanical property tester at the time of temperature rise. The MD direction is a flow direction when a film is formed, and the TD direction is a direction perpendicular to the MD direction.

The glass-processing tape 10 can be shrunk by heating at a low temperature for a short time by a negative value of the sum of the integral value calculated from the sum of the thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by the thermomechanical property tester at the time of temperature rise in the MD direction of the adhesive tape 15 and the integral value calculated from the sum of the thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by the thermomechanical property tester at the time of temperature rise in the TD direction. Therefore, even when a method is employed in which a pair of warm air nozzle rings are wound around a portion of the tape for glass processing 10 where slack has occurred to perform thermal contraction, there is no need to perform thermal contraction several times while reducing the amount of expansion, and the slack caused by expansion can be removed in a short time to maintain an appropriate notch width.

The thermal deformation rate may be in accordance with JIS K7197:2012, the amount of deformation due to temperature is measured and calculated by the following formula (1).

Thermal deformation rate TMA (%) = (deformation amount of sample length/sample length before measurement) × 100 (1)

The deformation amounts are shown with the expansion direction of the sample being positive and the contraction direction being negative.

The integrated value of the thermal deformation rate corresponds to the area enclosed by the MD direction curve or the TD direction curve and the x axis in fig. 7, and the sum of the MD direction integrated value and the TD direction integrated value is the sum of the areas including the signs. Therefore, a negative value of sum means that the adhesive tape as a whole shows a shrinking behavior between 40 ℃ and 80 ℃.

In order to make the sum of the MD-direction integrated value and the TD-direction integrated value negative, a step of stretching the resin film after film formation may be added, and the thickness of the adhesive tape 15, and the MD-direction or TD-direction stretching amount may be adjusted according to the type of resin constituting the adhesive tape 15. Examples of methods for extending the adhesive tape in the TD direction include: methods of stretching in the MD include a method using a tenter, a method based on blow molding (inflation), a method using an expanding roll, and the like, and examples of the method of stretching in the MD include: a method of stretching the die at the time of discharge, a method of stretching the die at a conveying roller, and the like. As a method for obtaining the adhesive tape 15 of the present invention, any method can be adopted.

< adhesive layer >

In the glass processing tape 10 of the present invention, the adhesive layer 13 is peeled from the adhesive layer 12 and attached to the chip when the chip is picked up after glass is bonded and cut. And, it is used as an adhesive when fixing the chip to the substrate or the lead frame.

The adhesive layer 13 is not particularly limited, and may be a film-like adhesive generally used for glass, and examples thereof include: an adhesive layer containing a thermoplastic resin and a thermopolymerizing component. The thermoplastic resin used in adhesive layer 13 of the present invention is preferably a resin having thermoplasticity or a resin having thermoplasticity in an uncured state and forming a crosslinked structure after heating, and is not particularly limited, and one embodiment thereof includes a thermoplastic resin having a weight average molecular weight of 5000 to 200,000 and a glass transition temperature of 0 to 150 ℃. In addition, as other embodiments, there may be mentioned: a thermoplastic resin having a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of-50 to 20 ℃.

Examples of the former thermoplastic resin include: polyimide resins, polyamide resins, polyetherimide resins, polyamideimide resins, polyester resins, polyesterimide resins, phenoxy resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins, polyetherketone resins, and the like, among which polyimide resins and phenoxy resins are preferably used, and as the latter thermoplastic resins, polymers containing functional groups are preferably used.

The polyimide resin can be obtained by condensation reaction of tetracarboxylic dianhydride and diamine by a known method. That is, an addition reaction is carried out in an organic solvent using an equimolar or substantially equimolar amount of tetracarboxylic dianhydride and diamine (the order of addition of the components is arbitrary) at a reaction temperature of 80 ℃ or less, preferably 0 to 60 ℃. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid as a precursor of polyimide is produced. The polyamic acid may be depolymerized by heating at 50 to 80 ℃ to adjust its molecular weight. The polyimide resin can be obtained by dehydration ring closure of the above reactant (polyamic acid). The dehydration ring closure can be carried out by a thermal ring closure method in which heat treatment is performed, or a chemical ring closure method using a dehydrating agent.

The tetracarboxylic dianhydride used as a raw material for the polyimide resin is not particularly limited, for example, 1,2- (ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) 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), 96xzft 9696- (hexadecylene) bis (trimellitic anhydride), 1,18- (octadecamethylene) bis (trimellitic anhydride), pyromellitic dianhydride 32323292, 34zzft 6292- (phenyl6258, 346258-dicarboxyphenyl-bis (dicarboxyphenyl) bis (phenylzzf-4258-bis (dicarboxyphenyl-4258-bis (trimellitic anhydride), bis-4258-bis (dicarboxyphenyl-42zf-4258-bis-5-bis (dicarboxyphenyl-4258) bis (trimellitic dianhydride), 34zf-bis (dianhydride), 3458-5-bis (dicarboxyphenyl-5) bis (dicarboxyphenyl-6258-bis (trimellitic dianhydride), or dianhydride, bis (-dicarboxyphenyl) sulfone dianhydride, -perylenetetracarboxylic acid dianhydride, bis (-dicarboxyphenyl) ether dianhydride, benzene-tetracarboxylic acid dianhydride, ',4' -benzophenonetetracarboxylic acid dianhydride, ',3' -benzophenonetetracarboxylic acid dianhydride, ',4' -benzophenonetetracarboxylic acid dianhydride, -naphthalenetetracarboxylic acid anhydride, -naphthalenetetracarboxylic acid dianhydride, -dichloronaphthalene-tetracarboxylic acid dianhydride, -tetrachloronaphthalene-tetracarboxylic acid dianhydride, phenanthrene-tetracarboxylic acid dianhydride, pyrazine-tetracarboxylic acid dianhydride, thiophene-tetracarboxylic acid dianhydride, ',4' -biphenyltetracarboxylic acid dianhydride, ',3' -biphenyltetracarboxylic acid dianhydride, bis (-dicarboxyphenyl) dimethylsilane dianhydride, bis (-dicarboxyphenyl) methylphenylsilane dianhydride, bis (-dicarboxyphenyl) diphenylsilane dianhydride, -bis (-dicarboxyphenyldimethylsilyl) benzene dianhydride, -bis (-dicarboxyphenyl) -tetramethylbicyclohexane dianhydride, p-phenylenebis (trimellitic acid dianhydride), ethylidenetetracarboxylic acid dianhydride, -heptanedioxybutanetetracarboxylic acid dianhydride, -dimethylnaphthalene-hexahydro-naphthalene-tetracarboxylic acid dianhydride, -dimethylnaphthalene-tetracarboxylic acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3584-bis [4- (3,4-dicarboxyphenyl) phenyl ] hexafluoropropane dianhydride, 4,4' -bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 1,3-bis (2-hydroxyisopropyl) benzene bis (345756-hydroxy-propyl) dianhydride, or more than these tetrahydronaphthalene-3838-tetracarboxylic dianhydride can be used as tetrahydrobenzofuran-3-diol dianhydride, or as tetrahydrobenzofuran-345749.

In addition, as the diamine used as a raw material of polyimide, without particular limitation, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 3,3' -diaminodiphenyl methane, 3,4 '-diaminodiphenyl methane, 4,4' -diaminodiphenyl methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3 '-diaminodiphenyl difluoromethane, 3,4' -diaminodiphenyl difluoromethane, 58 zxft 6258 '-diaminodiphenyl sulfone, etc. may be used 3,4' -diaminodiphenyl sulfide, 3,4 '-diaminobenzophenone, 3,4-bis (3-aminophenyl) propane, 3,4' - (58 zxft 6258 '-diaminodiphenyl) propane, 3,4-bis (4-aminophenyl) propane, 3,4-bis (3-aminophenyl) hexafluoropropane, 3,4- (58 zxft 6258' -diaminodiphenyl) hexafluoropropane, 3,4-bis (4-aminophenyl) hexafluoropropane, 3,4-bis (3-aminophenoxy) benzene, 58 zxft 6258-bis (3-aminophenoxy) benzene, families of 2 zxft 8652-bis (4-aminophenoxy) benzene, 3,3' - (1,4-phenylenebis (1-methylethylidene)) dianiline, 3,4' - (1,4-phenylenebis (1-methylethylidene)) dianiline, 4,4' - (1,4-phenylenebis (1-methylethylidene)) dianiline, 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) phenyl) sulfone, bis (3434-aminophenoxy) phenyl) sulfone, 3434-aromatic diamine, and the like; 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-aminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, a diaminopolysiloxane represented by the following general formula (1), 1,3-bis (aminomethyl) cyclohexane, JEFFAMINE D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-148, EDR-148 and the like, and 1 or more aliphatic and 2 or more thereof may be used. The glass transition temperature of the polyimide resin is preferably 0 to 200 ℃ and the weight average molecular weight thereof is preferably 1 to 20 ten thousand.

[ chemical formula 1]

(wherein R1 and R2 each represent a divalent hydrocarbon group having 1 to 30 carbon atoms and may be the same or different, R3 and R4 each represent a monovalent hydrocarbon group and may be the same or different, and m is an integer of 1 or more).

The phenoxy resin, which is one of the other preferable thermoplastic resins described 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 examples of bisphenol include bisphenol a, bisphenol AF, bisphenol AD, bisphenol F, and bisphenol S. The phenoxy resin has a structure similar to that of an epoxy resin, and therefore, has good compatibility with an epoxy resin and is suitable for imparting good adhesion to an adhesive film.

Examples of the phenoxy resin used in the present invention include: a resin having a repeating unit represented by the following general formula (2).

[ chemical formula 2]

In the general formula (2), X represents a single bond or a 2-valent linking group. Examples of the 2-valent linking group include: alkylene, phenylene, -O-) -S-, -SO-or-SO 2-. Here, the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably — C (R1) (R2). R1 and R2 each represent a hydrogen atom or an alkyl group, and the alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, isooctyl, 2-ethylhexyl, 1,3,3-trimethylbutyl, and the like. The alkyl group may be substituted with a halogen atom, and examples thereof include: a trifluoromethyl group. <xnotran> X , -O-, -S-, -SO2-, , -SO2-. </xnotran> <xnotran> , -C (CH 3) 2-, -CH (CH 3) -, -CH2-, -SO2-, -C (CH 3) 2-, -CH (CH 3) -, -CH2-, -C (CH 3) 2-. </xnotran>

The phenoxy resin represented by the above general formula (2), if having a repeating unit, may be a resin having a plurality of repeating units of the above general formula (2) in which X is different, or may be composed of only repeating units in which X is the same. In the present invention, a resin composed of only the same repeating unit as X is preferred.

When the phenoxy resin represented by the above general formula (2) contains a polar substituent such as a hydroxyl group or a carboxyl group, the compatibility with the thermally polymerizable component is improved, and uniform appearance and properties can be provided.

When the mass average molecular weight of the phenoxy resin is 5000 or more, it is excellent in film-forming properties. More preferably 10,000 or more, and still more preferably 30,000 or more. When the mass average molecular weight is 150,000 or less, it is preferable in view of fluidity at the time of thermocompression bonding and compatibility with other resins. More preferably 100,000 or less. When the glass transition temperature is-50 ℃ or higher, the film-forming property is excellent, and the glass transition temperature is more preferably 0 ℃ or higher, and still more preferably 50 ℃ or higher. When the glass transition temperature is 150 ℃, the adhesive force of adhesive layer 13 at the time of dicing is excellent, more preferably 120 ℃ or less, and further preferably 110 ℃ or less.

On the other hand, examples of the functional group in the functional group-containing polymer include: glycidyl groups, acryloyl groups, methacryloyl groups, hydroxyl groups, carboxyl groups, isocyanurate groups, amino groups, amide groups, and the like, and among them, glycidyl groups are preferable.

Examples of the high molecular weight component containing the functional group include (meth) acrylic copolymers containing a functional group such as a glycidyl group, a hydroxyl group, and a carboxyl group.

As the (meth) acrylic copolymer, for example, a (meth) acrylate copolymer, an acrylic rubber, and the like can be used, and an acrylic rubber is preferable. The acrylic rubber is a rubber mainly composed of an acrylic ester and mainly composed of a copolymer of butyl acrylate and acrylonitrile or a copolymer of ethyl acrylate and acrylonitrile.

When the functional group contains a glycidyl group, the amount of the glycidyl group-containing repeating unit is preferably 0.5 to 6.0% by weight, more preferably 0.5 to 5.0% by weight, and particularly preferably 0.8 to 5.0% by weight. The glycidyl group-containing repeating unit is a constituent monomer of a glycidyl group-containing (meth) acrylic copolymer, and specifically is glycidyl acrylate or glycidyl methacrylate. When the amount of the glycidyl group-containing repeating unit is within this range, adhesion can be secured and gelation can be prevented.

Examples of the constituent monomers of the (meth) acrylic copolymer other than glycidyl acrylate and glycidyl methacrylate include: ethyl (meth) acrylate, butyl (meth) acrylate, and the like, and these may be used alone or in combination of 2 or more. In the present invention, ethyl (meth) acrylate means ethyl acrylate and/or ethyl methacrylate. The mixing ratio in the case of using the functional monomers in combination may be determined in consideration of the glass transition temperature of the (meth) acrylic copolymer. When the glass transition temperature is-50 ℃ or higher, the film forming property is excellent, and it is preferable that the excessive viscosity at room temperature can be controlled. When the tack force at normal temperature is excessive, handling of the adhesive layer becomes difficult. More preferably-20 ℃ or higher, and still more preferably 0 ℃ or higher. When the glass transition temperature is 30 ℃ or lower, the adhesive strength of the adhesive layer at the time of dicing is excellent, and more preferably 20 ℃ or lower.

When the monomer is polymerized to produce a high molecular weight component containing a functional monomer, the polymerization method is not particularly limited, and for example, a method such as bead polymerization or solution polymerization can be used, and 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, the high molecular weight component is excellent in film forming property, more preferably 200,000 or more, and further preferably 500,000 or more. When the weight average molecular weight is adjusted to 2,000,000 or less, the adhesive layer is excellent in that the fluidity under heating is improved when the adhesive layer is applied. When the fluidity of the adhesive layer is improved by heating at the time of application, the adhesive layer adheres well to the adherend, the adhesive strength can be improved, and the unevenness of the adherend can be easily filled to suppress the voids. More preferably 1,000,000 or less, still more preferably 800,000 or less, and when 500,000 or less, a larger effect can be obtained.

The thermally polymerizable component is not particularly limited as long as it is a component that is polymerized by heat, and examples thereof include: the compound having a functional group such as a glycidyl group, an acryloyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an isocyanurate group, an amino group, an amide group and the like, and the excitable material may be used alone or in combination of 2 or more, and when considering the heat resistance as an adhesive layer, it is preferable to contain a thermosetting resin which is cured by heat to exhibit an adhesive action together with a curing agent and an accelerator. Examples of the thermosetting resin include: epoxy resins, acrylic resins, silicone resins, phenol resins, thermosetting polyimide resins, polyurethane resins, melamine resins, urea resins, and the like, and in particular, epoxy resins are most preferably used in order to obtain an adhesive layer having excellent heat resistance, workability, and reliability.

The epoxy resin is not particularly limited as long as it is an epoxy resin having an adhesive action by curing, and a bifunctional epoxy resin such as bisphenol a epoxy resin; and novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins. In addition, conventionally known epoxy resins such as a polyfunctional epoxy resin, a glycidylamine-type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin can be used.

Examples of the bisphenol a type epoxy resin include: EPIKOTE series (EPIKOTE 807, EPIKOTE815, EPIKOTE825, EPIKOTE827, EPIKOTE828, EPIKOTE834, EPIKOTE1001, EPIKOTE1004, EPIKOTE1007, EPIKOTE 1009) manufactured by Mitsubishi chemical corporation; DER-330, DER-301, and DER-361 manufactured by Dow Chemical company; and YD8125 and YDF8170, manufactured by Nissan Tekken chemical Co., ltd. Examples of the phenol novolac-type epoxy resin include: EPIKOTE 152, EPIKOTE 154 manufactured by Mitsubishi chemical corporation; EPPN-201 manufactured by Nippon Kagaku K.K.; DEN-438 manufactured by Dow Chemical company, and the above-mentioned o-cresol novolac epoxy resin include: EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025 and EOCN-1027, all of which are manufactured by Nippon chemical Co., ltd; YDCN701, YDCN702, YDCN703, YDCN704, and the like, available from Nissan Tekko chemical Co., ltd. Examples of the polyfunctional epoxy resin include: epon1031S, manufactured by Mitsubishi chemical corporation; araldite 0163 manufactured by Ciba Specialty Chemicals; denacol EX-611, EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, etc., manufactured by Nagase ChemteX corporation. Examples of the amine-type epoxy resin include: EPIKOTE604 manufactured by Mitsubishi chemical corporation; YH-434 manufactured by Doudou Kabushiki Kaisha; TETRAD-X and TETRAD-C available from Mitsubishi gas chemical; ELM-120 manufactured by Sumitomo chemical industries, ltd. Examples of the heterocyclic ring-containing epoxy resin include: araldite PT810 manufactured by Ciba Specialty Chemicals; ERL4234, ERL4299, ERL4221, ERL4206 and the like manufactured by UCC. These epoxy resins may be used alone or in combination of 2 or more.

In order to cure the above thermosetting resin, additives may be appropriately added. Examples of such additives include: curing agents, curing accelerators, catalysts and the like, and when a catalyst is added, a co-catalyst may be used as necessary.

In the case where an epoxy resin is used for the above thermosetting resin, an epoxy resin curing agent or a curing accelerator is preferably used, and more preferably used in combination. Examples of the curing agent include: phenol resin, dicyandiamide, boron trifluoride complex, organic hydrazide compound, amine, polyamide resin, imidazole compound, urea or thiourea compound, polythiol compound, polysulfide resin having a mercapto group at the terminal, acid anhydride, and light/ultraviolet curing agent. These may be used alone or in combination of 2 or more.

Among them, examples of the boron trifluoride complex compound include boron trifluoride-amine complexes with various amine compounds (preferably primary amine compounds), and examples of the organic hydrazide compound include isophthaloyl hydrazide.

Examples of the phenol resin include: phenol novolac type phenol resins such as phenol novolac resin, phenol aralkyl resin, cresol novolac resin, tert-butylphenol novolac resin, and nonylphenol novolac resin; a resol-type phenol resin; and polyoxyethylene such as poly-p-hydroxystyrene. Among them, a phenol compound having at least 2 phenolic hydroxyl groups in the molecule is preferable.

Examples of the phenolic compound having at least 2 phenolic hydroxyl groups in the molecule include: phenol novolac resin, cresol novolac resin, t-butylphenol novolac resin, cyclopentadiene cresol novolac resin, cyclopentadiene phenol novolac resin, xylylene-modified phenol novolac resin, naphthol novolac resin, triphenol novolac resin, tetraphenol novolac resin, bisphenol a novolac resin, poly (p-vinylphenol) resin, phenol aralkyl resin, and the like. Among these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferable, and connection reliability can be improved.

Examples of the amines include: linear aliphatic amines (diethylene triamine, triethylene tetramine, hexamethylene diamine, N-dimethylpropylamine, benzyldimethylamine, 2- (dimethylamino) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, m-xylylenediamine, etc.), cyclic aliphatic amines (N-aminoethylpiperazine, bis (3-methyl-4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, N-dimethylpropylamine, benzyldimethylamine, 2- (dimethylamino) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, m-xylylenediamine, etc.), cyclic aliphatic amines (N-aminoethylpiperazine, bis (3-methyl-4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, etc.),

Alkanediamine, isophoronediamine, 1,3-bis (aminomethyl) cyclohexane, etc.), heterocyclic amines (piperazine, N-dimethylpiperazine, triethylenediamine, melamine, guanamine, etc.), aromatic amines (m-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4' -diaminodiphenylsulfone, etc.), polyamide resins (preferably polyamide-amine, a condensate of dimer acid and polyamine), imidazole compounds (2-phenyl-4,5-dihydroxymethylimidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-N-heptadecylimidazole, 1-cyanoethyl-2-undecylimidazole-trimellitate, epoxy-imidazole adduct, etc.), urea or thiourea compounds (N, N-dialkylurea compounds, N-dialkylthiourea compounds, etc.), polythiol compounds, polysulfide resins having a mercapto group at the terminal, acid anhydrides (tetrahydrophthalic anhydride, etc.), light/ultraviolet curing agents (diphenyliodonium phosphate, triphenylsulfonium hexafluorophosphate, etc.).

The curing accelerator is not particularly limited as long as it is a curing accelerator for curing a thermosetting resin, and examples thereof include: imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate, and the like.

Examples of imidazoles include: imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 2-phenyl-4-methyl-5-hydroxydimethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.

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

The mixing ratio of the epoxy resin and the phenol resin is preferably such that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents to 1 equivalent of the epoxy group in the epoxy resin component. More preferably 0.8 to 1.2 equivalents. That is, if the mixing ratio of the two is outside the above range, a sufficient curing reaction cannot proceed, and the properties of the adhesive layer are likely to deteriorate. The other thermosetting resin and the curing agent are used in an amount of 0.5 to 20 parts by mass in one embodiment and 1 to 10 parts by mass in another embodiment, based on 100 parts by mass of the thermosetting resin. The content of the curing accelerator is preferably smaller than that of the curing agent, and the curing accelerator is preferably 0.001 to 1.5 parts by mass, more preferably 0.01 to 0.95 parts by mass, per 100 parts by mass of the thermosetting resin. By adjusting the amount to the above range, the progress of the sufficient curing 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 part by mass, based on 100 parts by mass of the thermosetting resin.

The adhesive layer 13 of the present invention may contain a filler as appropriate depending on the application. This can improve the cuttability, handleability, adjustment of melt viscosity, and imparting thixotropy of the adhesive layer in an uncured state, and further can improve the heat conductivity and adhesion of the adhesive layer in a cured state.

The filler used in the present invention is preferably an inorganic filler. The inorganic filler is not particularly limited, and for example, it may be used: aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, antimony oxide, and the like. Further, they may be used alone or in combination of 2 or more.

Among the above inorganic fillers, alumina, aluminum nitride, boron nitride, crystalline silica, amorphous silica, and the like are preferably used from the viewpoint of improving thermal conductivity. In addition, from the viewpoint of adjustment of melt viscosity and imparting thixotropy, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline silica, amorphous silica, and the like are preferably used. In addition, from the viewpoint of improving the cuttability, alumina and silica are preferably used.

The adhesive layer of the present invention may contain 2 or more fillers having different average particle diameters as the filler. In this case, in comparison with the case of using a single filler, in the raw material mixture before forming a film, it is easy to prevent an increase in viscosity when the content ratio of the filler is high or a decrease in viscosity when the content ratio of the filler is low, and it is easy to obtain good film formability, and it is possible to optimally control the fluidity of the uncured adhesive layer, and it is easy to obtain excellent adhesion after curing of the adhesive layer.

The adhesive layer of the present invention preferably has an average particle size of the filler of 2.0 μm or less, more preferably 1.0 μm or less. When the average particle diameter of the filler is 2.0 μm or less, the film can be easily made thin. Here, the thin film means a thickness of 20 μm or less. Further, when the particle diameter is 0.01 μm or more, the dispersibility is good.

Further, from the viewpoint of preventing an increase or decrease in viscosity of the raw material mixture before film formation, controlling the fluidity of the uncured adhesive layer to be optimum, and improving the adhesion after curing of the adhesive layer, it is preferable to contain the 1 st filler having an average particle diameter in the range of 0.1 to 1.0 μm, and the 2 nd filler having an average particle diameter of the primary particle diameter in the range of 0.005 to 0.03 μm. Preferably, the composition contains a1 st filler having an average particle diameter in the range of 0.1 to 1.0 μm and 99% or more of particles distributed in the range of 0.1 to 1.0 μm, and a2 nd filler having an average primary particle diameter in the range of 0.005 to 0.03 μm and 99% or more of particles distributed in the range of 0.005 to 0.1 μm.

The average particle diameter in the present invention means a D50 value of a cumulative volume distribution curve in which 50% by volume of particles have a diameter smaller than that. In the present invention, the average particle diameter or D50 value can be measured by a laser diffraction method using, for example, a Malvern Mastersizer 2000 manufactured by Malvern Instruments. In this technique, the size of the particles in the dispersion can be determined by diffraction using laser light, based on the application of either fraunhofer or mie theory. In the present invention, the average particle diameter or D50 value is related to the scattering measurement at 0.02 to 135 ° with respect to the incident laser light using the mie theory or the modified mie theory for non-spherical particles.

In one embodiment of the present invention, the adhesive layer 13 may contain 10 to 40 mass% of a thermoplastic resin having a weight average molecular weight of 5000 to 200,000, 10 to 40 mass% of a thermopolymerizable component, and 30 to 75 mass% of a filler, based on the entire adhesive composition. In this embodiment, the content of the filler may be 30 to 60% by mass, or 40 to 60% by mass. The mass average molecular weight of the thermoplastic resin may be 5000 to 150,000, or 10,000 to 100,000.

In another embodiment, the thermoplastic resin having a weight average molecular weight of 200,000 to 2,000,000 may be contained in an amount of 10 to 20 mass%, the thermopolymerizable component in an amount of 20 to 50 mass%, and the filler in an amount of 30 to 75 mass% with respect to the entire adhesive composition constituting adhesive layer 13. In this embodiment, the content of the filler may be 30 to 60% by mass, or 30 to 50% by mass. 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 blending ratio, the storage elastic modulus and the fluidity of the adhesive layer 13 after curing can be optimized, and heat resistance at high temperature tends to be sufficiently obtained.

The adhesive layer 13 preferably has a light transmittance of 90% or more with respect to light having a wavelength of 550 nm. In the case of a device having a structure in which glass is laminated on the image sensor via an adhesive layer, if the light transmittance is less than 90%, the sensor may not operate reliably. The light transmittance can be adjusted by the blending composition of the adhesive layer in general, and particularly, by selecting the matrix resin and the filler, both the mounting reliability and the high transmittance can be satisfied. The particle diameter of the filler can be reduced to suppress scattering of light and improve transmittance, for example. As the resin having high transmittance, for example, epoxy resin or silicone resin is preferably used, and particularly, bisphenol type epoxy resin is preferably used in order to achieve both of mounting reliability, but the invention is not limited thereto.

The light transmittance can be determined by measuring the amount of transmitted light with a spectrophotometer (spectrophotometer U-4100 solid sample measurement system, manufactured by Hitachi High-Technologies). Specifically, an adhesive layer having a thickness of 20 μm was bonded to glass, and light was allowed to enter the glass surface in the normal direction, and the light transmittance of 550nm at 25 ℃ to the glass was determined. Specifically, it is calculated by the following formula (2).

Light transmittance I (%) = I1/I0 (2) of adhesive layer

I1 (%): light transmittance of glass including adhesive layer

I0 (%): light transmittance of glass

In the glass processing tape 10 of the present invention, the adhesive layer 13 may be formed by directly or indirectly laminating an adhesive (hereinafter referred to as an adhesive film) formed in advance on the base film 11. The temperature at the time of lamination is preferably set in the range of 10 to 100 ℃, and a linear load of 0.01 to 10N/m is preferably applied. In this case, the release film may be peeled after lamination, or may be directly used as a cover film of the tape for glass processing 10 and peeled when bonding glass.

The adhesive film may be laminated on the entire surface of the adhesive layer 12, or an adhesive film cut (precut) in accordance with the shape of glass to be laminated in advance may be laminated on the adhesive layer 12. When an adhesive film corresponding to glass is laminated in this manner, as shown in fig. 3, the adhesive layer 13 is present in the portion where the glass W is bonded, and the adhesive layer 13 is not present in the portion where the ring frame 20 is bonded, and only the adhesive layer 12 is present. In general, since the adhesive layer 13 is not easily peeled from an adherend, the ring frame 20 can be bonded to the adhesive layer 12 by using a precut adhesive film, and an effect that a paste residue on the ring frame 20 is not easily generated when a tape after use is peeled can be obtained.

< use >

The glass processing tape 10 of the present invention is used in a glass processing method including at least a step of expanding to divide an adhesive layer 13. Therefore, the other steps, the order of the steps, and the like are not particularly limited. For example, the present invention can be suitably used in the following glass processing methods (a) to (C).

Glass processing method (A)

A method of processing glass comprising:

(a) A step of bonding the adhesive film bonded to the adhesive layer of the tape for processing a glass body to glass in a state where the glass is heated at 70 to 80 ℃,

(b) Irradiating the planned division portion of the glass with laser light to form a modified region by multiphoton absorption in the glass,

(c) A step of obtaining a plurality of adhesive film-attached chips by separating the glass and the adhesive film along separation lines by expanding the semi-glass processing tape,

(d) A step of holding the spacing between the chips by removing the slack generated in the expanding step by heating and shrinking a portion of the glass processing tape which is not overlapped with the chips, and

(e) And picking up the chip with the adhesive layer from the adhesive layer of the glass processing tape.

The processing method of the glass adopts a method of invisible cutting.

Glass processing method (B)

A method of processing glass comprising:

(a) A step of bonding the adhesive film bonded to the adhesive layer of the tape for glass processing to glass in a state where the glass is heated at 70 to 80 ℃,

(b) Irradiating the surface of the glass with laser light along the dividing line to divide the glass into individual chips,

(c) A step of obtaining a plurality of adhesive film-attached chips by expanding the adhesive tape for glass processing to divide the adhesive film into pieces corresponding to the chips,

(d) A step of holding the spacing between the chips by removing the slack generated in the expanding step by shrinking a portion of the glass processing tape which is not overlapped with the chips by heating, and

The processing method of the glass adopts a full-cutting laser cutting method.

Glass processing method (C)

A method of processing glass comprising:

(b) Cutting the glass along the cutting line by using a cutter blade to separate the glass into chips,

The processing method of the glass adopts a full-cutting blade cutting method.

< method of use >

A method of using the glass-processing tape 10 of the present invention in the case of applying the above-described glass-processing method (a) will be described with reference to fig. 2 to 5.

As shown in fig. 2, a glass W is placed on a heating stage 25 of a wafer laminator (wafer mounter) with its front surface facing downward, and then a glass processing tape 10 is bonded to the back surface of the glass W. The glass processing tape 10 used here is a laminate of an adhesive film cut (precut) in advance into a shape corresponding to the glass W to be bonded, and the adhesive layer 12 is exposed on the surface bonded to the glass W around the region where the adhesive layer 13 is exposed. The exposed part of the adhesive layer 13 of the tape 10 for glass processing is bonded to the back surface of the glass W, and the exposed part of the adhesive layer 12 around the adhesive layer 13 is bonded to the ring frame 20. At this time, the heating stage 25 is set to 70 to 80 ℃ to perform heating bonding. In the present embodiment, the glass-processing tape 10 having the adhesive tape 15 including the base film 11 and the adhesive layer 12 provided on the base film 11 and the adhesive layer 13 provided on the adhesive layer 12 is used, but the adhesive tape and the film-like adhesive may be used separately. In this case, first, a film-like adhesive is bonded to the back surface of the glass to form an adhesive layer, and the adhesive layer of the adhesive tape is bonded to the adhesive layer. At this time, as the adhesive tape, the adhesive tape 15 according to the present invention was used.

Next, the glass W to which the glass processing tape 10 is bonded is carried out from the heating stage 25, and as shown in fig. 3, the planned dividing portions of the glass W are irradiated with laser light, whereby the modified regions 32 by multiphoton absorption are formed in the glass W.

Next, as shown in fig. 4 (a), the glass processing tape 10 with the glass W and the ring frame 20 bonded thereto is placed on the stage 21 of the expanding device with the base film 11 side facing downward.

Next, as shown in fig. 4 (b), the hollow cylindrical push-up member 22 of the expanding device is raised in a state where the ring frame 20 is fixed, and the tape 10 for glass processing is expanded (expanded). The expansion rate is, for example, 5 to 500mm/sec, and the expansion amount (push-up amount) is, for example, 5 to 25mm. As described above, by stretching the glass processing tape 10 in the radial direction of the glass W, the glass W is divided into the chip 34 units with the modified region 32 as a starting point. At this time, the adhesive layer 13 is prevented from being broken by the elongation (deformation) due to the expansion at the portion bonded to the back surface of the glass W, but is broken by the concentration of the tension due to the expansion of the tape at the position between the chips 34. Therefore, as shown in fig. 4 (c), the adhesive layer 13 is also divided together with the glass W. This makes it possible to obtain a plurality of chips 34 with adhesive layer 13.

Next, as shown in fig. 5, the pushing-up member 22 is returned to the original position, and the slack of the glass processing tape 10 generated in the previous expanding step is removed, thereby stabilizing the interval between the chips 34. In this step, for example, in the glass processing tape 10, the base film 11 is heated and shrunk by blowing 40 to 120 ℃ hot air using the hot air nozzle 29 in the annular heat-shrinking region 28 between the region where the chip 34 is present and the ring frame 20, and the glass processing tape 10 is put in a stretched state. After that, the adhesive layer 12 is subjected to energy ray curing treatment, thermosetting treatment, or the like to weaken the adhesive force of the adhesive layer 12 to the adhesive layer 13, and then the chip 34 is picked up.

The glass-processing tape 10 according to the present embodiment has the adhesive layer 13 on the adhesive layer 12, but may not have the adhesive layer 13. In this case, glass may be bonded to the pressure-sensitive adhesive layer 12 only for dividing the glass, and when the glass-processing tape is used, an adhesive film produced in the same manner as the pressure-sensitive adhesive layer 13 may be bonded to the pressure-sensitive adhesive layer 12 together with the glass, and the glass and the adhesive film may be divided.

< example >

Next, examples and comparative examples will be described in detail to further clarify the effects of the present invention, but the present invention is not limited to these examples.

[ production of adhesive tape for glass processing ]

(1) Production of substrate film

< substrate film A >

Resin beads of a zinc ionomer (15% methacrylic acid, 5% ethyl methacrylate, 72% softening point, 90 ℃ melting point, 0.96g/cm3 density, 5% zinc ion content) of an ethylene-methacrylic acid-ethyl methacrylate copolymer synthesized by a radical polymerization method were melted at 230 ℃ and molded into a long film having a thickness of 150 μm using an extruder. Then, the long film was stretched in the TD direction to have a thickness of 90 μm, thereby producing a base film a.

< substrate film B >

A base film B was produced in the same manner as the base film a except that the thickness of the long film was set to 180 μm and the long film was stretched in the TD direction to have a thickness of 90 μm.

< substrate film C >

A base film C was produced in the same manner as the base film a except that the thickness of the long film was 215 μm and the long film was stretched in the TD direction to have a thickness of 90 μm.

< substrate film D >

A resin bead of a zinc ionomer (11% methacrylic acid content, 9% isobutyl methacrylate content, 64 ℃ softening point, 83 ℃ melting point, 0.95g/cm3 density, 4% by mass zinc ion content) of an ethylene-methacrylic acid-isobutyl methacrylate copolymer synthesized by a radical polymerization method was melted at 230 ℃ and molded into a long film having a thickness of 150 μm using an extruder. Then, the long film was stretched in the TD direction to have a thickness of 90 μm, thereby producing a base film D.

< substrate film E >

Will be calculated at 52:48 of the above-mentioned thermoplastic elastomer composition, and polypropylene (PP) were mixed and melted at 200 ℃ to form a resin bead into a long film having a thickness of 150 μm by using an extruder. Then, the long film was stretched in the TD direction to have a thickness of 90 μm, thereby producing a base film E.

< substrate film F >

The ratio of 64: resin beads obtained by mixing a hydrogenated styrene-based thermoplastic elastomer and polypropylene (PP) at a mixing ratio of 36 were melted at 200 ℃ and molded into a long film having a thickness of 150 μm using an extruder. Then, the long film was stretched in the TD direction to have a thickness of 90 μm, thereby producing a base film F.

< substrate film G >

A base film G was produced in the same manner as the base film a except that the thickness of the long film was 150 μm and the long film was stretched in the MD to a thickness of 90 μm.

< substrate film H >

A base film H was produced in the same manner as the base film D except that the thickness of the long film was 150 μm and the long film was stretched in the MD to a thickness of 90 μm.

< substrate film I >

A base film I was produced in the same manner as the base film a except that the thickness of the long film was 90 μm and the long film was not subjected to the stretching treatment.

< substrate film J >

A 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 long film was not subjected to stretching treatment.

< substrate film K >

A 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 long film was not subjected to the stretching treatment.

The base film L was produced in the same manner as the base film F except that the thickness of the long film was set to 90 μm and the long film was not subjected to the stretching treatment.

< substrate film M >

A base film M was produced in the same manner as the base film a except that the thickness of the long film was set to 110 μ M and the long film was stretched in the TD direction to have a thickness of 90 μ M.

< substrate film N >

A base film N was produced in the same manner as the base film a except that the thickness of the long film was set to 120 μm and the long film was stretched in the TD direction to have a thickness of 90 μm.

(2) Preparation of acrylic copolymer

As the acrylic copolymer (A1) having a functional group, a copolymer comprising 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and methacrylic acid, wherein the ratio of 2-ethylhexyl acrylate was 60 mol% and the mass average molecular weight was 70 ten thousand, was prepared. Then, 2-isocyanoethyl methacrylate was added so that the iodine value became 25 to prepare an acrylic copolymer having a glass transition temperature of-50 ℃, a hydroxyl value of 10mgKOH/g and an acid value of 5 mgKOH/g.

(3-1) preparation of adhesive composition A

100 parts by mass of an epoxy resin "1256" (product name of Mitsubishi chemical corporation, bisphenol A type phenoxy resin, epoxy equivalent 7500), 100 parts by mass of an epoxy resin "828" (product name of Mitsubishi chemical corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 220, specific gravity 1.17), 4 parts by mass of a curing agent "DICY7" (product name of Mitsubishi chemical corporation, dicyandiamide), and 0.4 part by mass of "curezol 2PZ" (product name of Shikoku chemical corporation, 2-phenyl-4,5-dihydroxymethylimidazole) as a curing accelerator were added to the mixture, and MEK was added thereto and the mixture was stirred and mixed to be uniform. Then, the mixture was filtered through a 100-mesh filter and vacuum defoamed to obtain a varnish of the adhesive composition.

(3-2) preparation of adhesive composition B

MEK was added to a composition containing 40 parts by mass of an epoxy resin "1002" (a solid bisphenol A-type epoxy resin, manufactured by Mitsubishi chemical corporation, epoxy equivalent 600), 100 parts by mass of an epoxy resin "806" (a trade name, manufactured by Mitsubishi chemical corporation, a bisphenol F-type epoxy resin, epoxy equivalent 160, specific gravity 1.20), 5 parts by mass of a curing agent "Dyhard100SF" (a trade name, manufactured by Degussa, dicyandiamide), 200 parts by mass of a silica filler "SO-C2" (a trade name, manufactured by ADMAFINE corporation, an average particle diameter of 0.5 μm), and 3 parts by mass of a silica filler "Aerosil R972" (a trade name, manufactured by Japanese Aerosil corporation, an average particle diameter of 0.016 μm) to stir and mix the mixture to prepare a uniform composition.

To this, 100 parts by mass of a phenoxy resin "PKHH" (trade name, mass average molecular weight 52,000, glass transition temperature 92 ℃ C. Manufactured by INCHEM), 0.6 part by mass of "KBM-802" (trade name, mercaptopropyltrimethoxysilane, manufactured by shin-Silicone corporation) as a coupling agent, and 0.5 part by mass of "CUREZOL 2PHZ-PW" (trade name, 2-phenyl-4,5-dihydroxymethylimidazole, decomposition temperature 230 ℃ C. Manufactured by Sikko chemical Co., ltd.) as a curing accelerator were added, and the mixture was stirred and mixed until uniform. Then, the mixture was filtered through a 100-mesh filter and vacuum defoamed to obtain a varnish of the adhesive composition.

< example 1>

To 100 parts by mass of the acrylic copolymer, 5 parts by mass of coronate L (manufactured by Polyurethane, japan) as a polyisocyanate and 3 parts by mass of Esacure KIP 150 (manufactured by Lamberti) as a photopolymerization initiator were added, and the obtained mixture was dissolved in ethyl acetate and stirred to prepare an adhesive composition.

Then, the pressure-sensitive adhesive composition was applied to a release liner made of polyethylene terephthalate film subjected to release treatment so that the thickness after drying became 10 μm, dried at 110 ℃ for 3 minutes, and then bonded to a base film to prepare a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed on the base film.

Next, the adhesive composition a was applied to a release liner made of polyethylene terephthalate film subjected to release treatment so that the thickness after drying became 20 μm, and dried at 110 ℃ for 5 minutes to prepare an adhesive film having an adhesive layer formed on the release liner.

The pressure-sensitive adhesive sheet is cut into a shape shown in fig. 3 and the like so as to be attached to the ring frame so as to cover the opening. The adhesive film is cut into a shape as shown in fig. 3 or the like so as to cover the back surface of the glass. Then, the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive film are bonded to each other so as to form a portion where the pressure-sensitive adhesive layer 12 is exposed around the pressure-sensitive adhesive film, as shown in fig. 3 and the like, thereby producing a tape for glass processing.

< examples 2 to 8, comparative examples 1 to 6>

Glass processing tapes of examples 2 to 8 and comparative examples 1 to 6 were produced in the same manner as in example 1 except that the base material film and the adhesive composition described in table 1 were used.

The adhesive tape of the glass processing tape of examples and comparative examples was cut so as to have a length of 24mm (direction in which the amount of deformation was measured) and a width of 5mm (direction orthogonal to the direction in which the amount of deformation was measured), and sample pieces were prepared. The resulting test piece was subjected to a tensile load method using a thermomechanical property tester (product name: TMA8310, rigaku corporation) to measure the deformation in 2 directions of MD and TD due to temperature under the following measurement conditions.

(measurement conditions)

Measuring temperature: 60 ℃ below zero to 100 DEG C

Temperature rise rate: 5 ℃/min

And (3) measuring the load: 19.6mN

Ambient gas: nitrogen environment (100 ml/min)

Sampling: 0.5s

The distance between the clamps: 20mm

Then, the thermal deformation rate is calculated by the following formula (1), and the integrated values calculated from the sum of the thermal deformation rates at 1 ℃ between 40 ℃ and 80 ℃ in the MD direction and the TD direction are obtained, and the sum of the integrated values is calculated. The results are shown in tables 1 and 2.

Thermal deformation rate TMA (%) = (change in sample length/sample length before measurement) × 100 (1)

[ evaluation of holding Property of slit Width ]

With respect to each of the tapes for glass processing of examples and comparative examples, the glass was divided into chips by the following method, and the holding property of the notch width was evaluated.

The following steps are carried out:

(a) Irradiating the planned division portion of the glass with laser light to form a modified region by multiphoton absorption in the glass,

(b) A step of bonding the adhesive layer of the tape for glass processing to the glass in a state where the glass is heated to 70 to 80 ℃,

(c) A step of obtaining a plurality of adhesive film-attached chips by spreading the glass processing tape to separate the glass and the adhesive layer along separation lines,

(d) A step of heating and shrinking a portion of the glass processing tape not overlapping the chip (a ring-shaped region between a region where the chip is present and a ring frame) to remove a slack generated in the expanding step of (c) and to maintain the spacing between the chips, and

In the step (b), the glass is bonded to the glass processing tape so that the glass separation line extends in the MD direction and the TD direction of the substrate film.

In the step (c), the cutting ring frame attached to the tape for glass processing was pushed down by an expanding ring of the DDS2300 manufactured by Disco, inc, and the portion of the outer periphery of the glass attachment portion of the tape for glass processing, which portion did not overlap with the glass, was pushed against the circular push-up member, thereby expanding the tape for glass processing, using the DDS2300 manufactured by Disco. As the conditions of the step (c), the expansion amount was adjusted so that the expansion speed became 300mm/sec and the expansion height became 10 mm. Here, the amount of expansion refers to the amount of change in the relative positions of the ring frame and the push-up member before and after the pressing. The chip size was set to 1X 1mm square.

(d) The process comprises the steps of expanding the film again at an expansion rate of 1mm/sec and an expansion height of 10mm at room temperature, and then performing heat shrinkage treatment under the following conditions.

[ Condition 1]

Setting temperature of a heater: 220 deg.C

Hot air quantity: 40L/min

Interval between heater and glass-processing tape: 20mm

Heater rotation speed: 7 DEG/sec

[ Condition 2]

Setting temperature of a heater: 220 deg.C

Hot air quantity: 40L/min

Interval between heater and glass-processing tape: 20mm

Heater rotation speed: 5 deg./sec

Immediately after the step (d), as shown in fig. 6, the tapes for glass processing of examples 1 to 8 and comparative examples 1 to 6 were measured for the notch width X (notch width in MD) between the chip 50a at the rightmost end of the adhesive tape in fig. 6, which was not defective in the MD direction, and the chip near the center in the MD direction, and for the notch width Y (notch width in TD) between the chip 50a and the chip near the center in the TD direction. Similarly, the MD slit width and the TD slit width were measured for the chip 50b on the leftmost side in fig. 6, which was not defective in the MD direction of the adhesive tape. The MD slit width and the TD slit width were also measured for the chip 51 at the outermost ends and the chip 52 at the center, which were not defective in the TD direction of the adhesive tape. The average value of the 5-point MD-direction slit width and the average value of the 5-point TD-direction slit width are calculated. Then, the smaller of the average value of 5 points of the MD-direction slit width and the average value of 5 points of the TD-direction slit width is set as the minimum slit width. An excellent product having a minimum notch width of 7 μm or more under both conditions 1 and 2 of the step (g) was evaluated as "excellent"; good products with a minimum notch width of 7 μm or more in condition 2 were evaluated as "o"; the minimum notch width of 5 μm or more under condition 2 was evaluated as "Δ" as a non-defective product; the defective product having a minimum notch width of less than 5 μm under both conditions 1 and 2 was evaluated as "x". The results are shown in tables 1 and 2.

[ measurement of the transmittance of adhesive layer ]

The adhesive layers of the examples and comparative examples were measured for transmittance by the following method.

After an adhesive layer having a thickness of 20 μm formed on a release liner was bonded to glass, the release liner was peeled off to prepare a glass sample containing the adhesive layer. The transmittance of 550nm light at 25 ℃ to glass was measured using a spectrophotometer (model U-4100 solid sample measurement system manufactured by Hitachi High-Technologies) by allowing light to enter the glass and the glass including the adhesive layer in the normal direction to the glass surface, and the transmittance of the adhesive layer was calculated by the following formula (2). The results are shown in tables 1 and 2.

Light transmittance I (%) = I1/I0 (2) of adhesive layer

I1 (%): light transmittance of glass including adhesive layer

I0 (%): light transmittance of glass

[ Table 1]

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7	Example 8
									Substrate film	A	B	C	D	E	F	G	H
Adhesive composition	A	A	A	A	A	A	A	B
									Thickness [ mu ] m before processing]	150	180	215	150	150	150	150	150
Thickness after processing [ μm]	90	90	90	90	90	90	90	90
									Integral value calculated from the sum of thermal deformation rates in the MD direction	-48	-25	5	41	47	29	-303	-104
Integral value calculated from the sum of thermal deformation rates in the TD direction	-310	-341	-356	-193	-138	-66	138	103
									Sum of integrated values calculated from the sum of thermal deformation rates in MD and TD directions	-358	-366	-351	-152	-91	-37	-165	-1
Evaluation results of notch width	◎	◎	◎	○	△	△	○	△
									Transmissivity of adhesive layer	90％	90％	90％	90％	90％	90％	90％	5％

[ Table 2]

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
							Substrate film	I	J	K	L	M	N
Adhesive composition	A	A	A	A	A	A
							Thickness [ mu ] m before processing]	90	90	90	90	110	120
Thickness after processing [ mu ] m]	90	90	90	90	90	90
							Integral value calculated from the sum of thermal deformation rates in the MD direction	-59	0	14	31	-56	-54
Integral value calculated from the sum of thermal deformation rates in the TD direction	142	107	39	32	103	55
							Sum of integrated values calculated from the sum of thermal deformation rates in the MD and TD directions	83	107	53	63	47	1
Evaluation results of notch width	×	×	×	×	×	×
							Transmissivity of adhesive layer	90％	90％	90％	90％	90％	90％

As shown in table 1, in the adhesive tapes for glass processing of examples 1 to 8, the sum of the integrated value calculated from the sum of the thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by the thermomechanical property tester at the time of temperature rise in the MD direction of the adhesive tape and the integrated value calculated from the sum of the thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by the thermomechanical property tester at the time of temperature rise in the TD direction is negative, and therefore, the notch width retentivity is excellent. This can prevent the adhesive layers from coming into contact with each other and re-bonding.

On the other hand, as shown in table 2, the tapes for glass processing of comparative examples 1 to 6 had poor retention of the notch width because the sum of the integrated value calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by the thermomechanical property tester at the time of temperature rise in the MD direction of the adhesive tape and the integrated value calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by the thermomechanical property tester at the time of temperature rise in the TD direction was not negative.

Description of the reference numerals

10: an adhesive tape for glass processing;

11: a substrate film;

12: an adhesive layer;

13: an adhesive layer;

22: a push-up member;

28: heating the shrinkage zone;

29: a warm air nozzle.

Claims

1. A glass processing tape is characterized by comprising an adhesive tape, wherein the adhesive tape comprises a substrate film and an adhesive layer formed on at least one surface side of the substrate film;

the base film has uniform and isotropic expansibility, is formed of an ionomer resin or a mixed resin composition of polypropylene and a styrene-butadiene copolymer, and has a thickness of 70 to 200 μm,

the adhesive composition constituting the adhesive layer is an energy ray-curable adhesive composition containing, as a base resin, a polymer containing an energy ray-curable carbon-carbon double bond having an iodine value of 5 to 30 and containing 60 mol% or more of a (meth) acrylate having an alkyl chain of 6 to 12 carbon atoms,

a negative value is the sum of an integral value calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by a thermomechanical property tester at a temperature rise in the MD direction and an integral value calculated from the sum of thermal deformation rates per 1 ℃ at 40 to 80 ℃ measured by a thermomechanical property tester at a temperature rise in the TD direction;

the glass processing tape is used for processing glass comprising an expansion step of expanding the adhesive tape,

the MD direction is a flow direction when a film is formed, and the TD direction is a direction perpendicular to the MD direction.

2. A glass processing tape is characterized by comprising an adhesive tape, wherein the adhesive tape comprises a substrate film and an adhesive layer formed on at least one surface side of the substrate film;

the base film is formed of an ionomer resin or a mixed resin composition of polypropylene and a styrene-butadiene copolymer;

the base film has uniform and isotropic extensibility and a thickness of 70 to 200 μm,

the adhesive tape has a negative sum of an integral value in the MD direction calculated from the sum of thermal deformation rates per 1 ℃ between 40 ℃ and 80 ℃ measured at a temperature rise by a thermomechanical property tester and an integral value in the TD direction calculated from the sum of thermal deformation rates per 1 ℃ between 40 ℃ and 80 ℃ measured at a temperature rise by a thermomechanical property tester,

3. The adhesive tape for glass processing according to claim 1 or claim 2, which is used for full-cut blade cutting, laser cutting, or stealth cutting using a laser.

4. The adhesive tape for glass processing according to claim 1 or 2, wherein an adhesive layer is laminated on the adhesive layer side;

the adhesive layer has a light transmittance of 90% or more with respect to light having a wavelength of 550 nm.