CN112351859B - Adhesive tape for glass processing - Google Patents

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 material film (11) and an adhesive layer (12) formed on at least one surface side of the base material film (11), the sum of the average value of the thermal deformation rates per 1 ℃ between 40 and 80 ℃ measured by a thermomechanical property tester in the MD direction and the average value of the thermal deformation rates per 1 ℃ between 40 and 80 ℃ measured by a thermomechanical property tester in the TD direction is the negative value, and the adhesive tape (10) for glass processing comprising the expansion step of expanding the adhesive tape (15) is used for processing glass.

Description

Tape for glass processing

technical field

The present invention relates to an expandable adhesive tape for glass processing, which can be used to fix the glass in the cutting process of dividing the glass into chip-shaped elements, and can be used between the cut chip and the chip, or between the chip and the substrate. It can also be used in the die bonding process or the mounting process of bonding between them, and it can also be used in the process of dividing the adhesive layer along the chip by expansion.

Background technique

Glasses with various characteristic optical properties are installed in cameras and sensors installed in smartphones and the like. These glasses are generally produced by subjecting various materials to vacuum deposition or the like on glass as a matrix. After that, after adhering adhesive and stretchable glass processing tape to these glasses, a dicing process of dividing the glass into chip units, an expanding process of expanding (expanding) the glass processing tape, and picking up the divided chips are carried out. The pick-up process of the chip, and then the bonding process of bonding the picked-up chip to a specific position.

In the above-mentioned glass cutting process, cutting with a blade has been the mainstream in the past, but due to the thinning of the glass itself and the influence of vapor deposition, breakage called chipping has become a problem, and thus there has been a problem that productivity will decrease.

In order to solve such a problem, in recent years, as a cutting method of glass, a so-called stealth cutting method that can cut glass in a non-contact manner using a laser processing device has been proposed. For example, Patent Document 1 discloses, as a stealth dicing method, a method for cutting a semiconductor substrate including the step of focusing a focal point inside a semiconductor substrate on which a chip is attached by inserting an adhesive layer (die bonding resin layer). light, irradiating laser light to form a modified region based on multiphoton absorption inside the semiconductor substrate, using the modified region as a part to be cut; and expanding the sheet to cut the semiconductor substrate and the part along the part to be cut. Adhesive layer process.

In addition, as another method of cutting a wafer using a laser processing apparatus, for example, Patent Document 2 proposes a method of dividing a wafer including a step of attaching an adhesive layer for die bonding (adhesive layer) on the back surface of the wafer. bonding film); a step of bonding an elongated protective adhesive tape to the adhesive layer side of the wafer to which the adhesive layer is bonded; from the surface of the wafer to which the protective adhesive tape is bonded The process of irradiating laser light along the dicing line to divide into individual chips; the process of expanding the protective adhesive tape to apply tensile force to the adhesive layer, and cutting the adhesive layer for each chip; There is a process in which the chip with the cut adhesive layer is detached from the protective adhesive tape.

According to the wafer cutting method described in these patent documents 1 and patent document 2, the wafer is cut in a non-contact manner by irradiation of laser light and expansion of the tape, so the physical load on the wafer is small, and it is possible to do so without generating Wafer cutting is carried out on the premise of cutting chips of the wafer in the case of the current mainstream blade dicing. In addition, since the adhesive layer is divided by expansion, cutting chips of the adhesive layer are not generated. Therefore, it is attracting attention as an excellent technology that can replace blade dicing.

The division techniques described in the aforementioned documents mainly target wafers, but can also be applied to glass by changing the laser engine of the device to glass.

However, as described in the above-mentioned Patent Documents 1 and 2, in the method of dividing the adhesive layer by expanding by expanding, when the conventional adhesive tape for semiconductor processing is used, there is a problem that the increased The portion pushed up by the expansion ring stretches, and when the expansion is released, this portion becomes loose, and the gap between the chips cannot be maintained (hereinafter referred to as "slit width").

Therefore, a method has been proposed in which, 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 shrunk to maintain the slit width (for example, Patent Documents 3 and 4). .

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2003-338467

Patent Document 2: Japanese Patent Laid-Open No. 2004-273895

Patent Document 3: International Publication No. 2016/152957

Patent Document 4: Japanese Patent Laid-Open No. 2015-211081

Contents of the invention

The problem to be solved by the invention

However, as a method of shrinking the slack of the tape for semiconductor processing due to expansion by heating, generally speaking, a method is used in which a pair of warm air nozzles are surrounded by an annular tape that is pushed up by the expansion ring to generate slack. part, so that warm air is blown to the part to heat it and make it shrink.

In the tape for semiconductor processing described in Patent Document 3 above, the heat shrinkage rate in both the longitudinal direction and the width direction of the tape when heated at 100° C. for 10 seconds is 0% or more and 20% or less. However, when heating is performed by surrounding the hot air nozzle, the temperature near the surface of the tape for glass processing rises gradually, and therefore there is a problem that it takes time to remove the slack in all the ring-shaped positions. In addition, the maintenance of the kerf width is not sufficient, and when it is transferred to the division of glass, there is a problem that the yield of the glass processing process deteriorates because adjacent chips contact each other at the time of picking up to cause chip defects.

In addition, the tape for semiconductor processing described in Patent Document 4 above has a shrinkage rate of 0.1% or more at 130° C. to 160° C. (see claim 1 of the specification of Patent Document 4), and the temperature at which shrinkage occurs is high. Therefore, in the case of heating and shrinking with warm air, high temperature and long heating time are required, and the hot air affects the adhesive layer near the outer periphery of the wafer, and there is a risk that the divided adhesive layer will melt and fuse again. . In addition, the maintenance of the kerf width is not sufficient, and when it is transferred to the division of glass, there is a problem that the yield of the glass processing process deteriorates because adjacent chips contact each other at the time of picking up to cause chip defects.

Therefore, an object of the present invention is to provide a tape for glass processing that can sufficiently heat shrink in a short time and can maintain a slit width sufficiently to prevent chip defects from being caused by contact between adjacent chips when picking up. .

means to solve the problem

In order to solve the above problems, the tape for glass processing of the present invention is characterized in that it has an adhesive tape, the adhesive tape has a base film and an adhesive layer formed on at least one side of the base film, and the adhesive tape The average value of the thermal deformation rate per 1°C between 40°C and 80°C measured with a thermomechanical property testing machine in the MD direction of the tape when the temperature is raised, and 40°C measured with a thermomechanical property tester in the TD direction when the temperature is raised The average sum of the thermal deformation rates per 1°C between -80°C is a negative value, and the above-mentioned tape for glass processing is used for processing of glass including an expanding step of expanding the above-mentioned pressure-sensitive adhesive tape.

In addition, in order to solve the above problems, the tape for glass processing of the present invention is characterized by comprising an adhesive tape having a base film and an adhesive layer formed on at least one side of the base film. The base film is formed of ionomer resin or a mixed resin composition of polypropylene film and styrene-butadiene copolymer. The MD direction of the above-mentioned adhesive tape is measured at 40°C when the temperature is raised by a thermomechanical characteristic testing machine. The average value of the thermal deformation rate per 1 °C between ～80 °C and the average value of the thermal deformation rate per 1 °C between 40 °C and 80 °C measured by a thermomechanical characteristic testing machine in the TD direction when the temperature is raised and is a negative value.

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

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

Invention effect

According to the tape for glass processing of the present invention, heat shrinkage can be sufficiently performed in a short time, and the width of the slit can be maintained sufficiently to prevent the generation of chip defects due to contact between adjacent chips during pickup.

Description of 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 cross-sectional view illustrating a step 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 in which modified regions are formed in glass by laser processing.

Fig. 4(a) is a cross-sectional view showing a state in which the tape for glass processing according to the embodiment of the present invention is mounted on an expansion device. (b) is a sectional view showing the process of dividing the glass into chips by expanding the glass processing tape. (c) is a cross-sectional view showing the expanded glass processing tape, adhesive layer, and chip.

Fig. 5 is a cross-sectional view for explaining a heat shrinking step.

FIG. 6 is an explanatory diagram showing measurement points of incision widths in evaluations of Examples and Comparative Examples.

Fig. 7 is an example of measurement results of thermal deformation rate.

Detailed ways

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

FIG. 1 is a cross-sectional view showing a glass processing tape 10 according to an embodiment of the present invention. When the glass processing tape 10 of the present invention divides glass into chips by expansion, the transparent adhesive layer 13 is divided along the chips. This tape 10 for glass processing has an adhesive tape 15 including a base film 11 and an adhesive layer 12 provided on the base film 11 , and a transparent adhesive layer 13 provided on the adhesive layer 12 , on the transparent adhesive layer 13, the back surface of the glass is bonded. It should be noted that each layer can be pre-cut (pre-cut) into a predetermined shape in accordance with the process and equipment used. Furthermore, the tape 10 for glass processing of the present invention may be a form cut for each glass, or may be a long sheet formed of a plurality of tapes for glass processing cut for each glass, and may be wound into a Rolled form. In the following, the configuration of each layer will be described.

<Base film>

When the base film 11 has uniform and isotropic expandability, it is preferable that the glass can be cut without deviation in all directions in the expanding process, and its material is not particularly limited. Generally, a cross-linked resin has a larger recovery force against stretching than a non-cross-linked resin, and a larger shrinkage stress when heated in a stretched state after the expansion step. Therefore, it is excellent in that the slack generated in the tape is removed by heating and shrinking after the expansion step, and the tape is tensioned to stably maintain the interval (kerf width) between the individual chips. Among crosslinked resins, thermoplastic crosslinked resins are more preferably used. On the other hand, a non-crosslinked resin has a smaller recovery force against stretching than a crosslinked resin. Therefore, the tape is not easy to shrink after the expansion process in the low temperature range of -15°C to 0°C after the expansion process, and returns to normal temperature to proceed to the pick-up process and the mounting process, so the adhesive layer attached to the chip is prevented from contacting each other. excellent. Among non-crosslinked resins, olefin-based non-crosslinked resins are more preferably used.

Examples of such thermoplastic cross-linked resins include terpolymers containing ethylene-(meth)acrylic acid binary copolymers or ethylene-(meth)acrylic acid-alkyl (meth)acrylates as main polymer components. An ionomer resin obtained by cross-linking a copolymer with metal ions. They are particularly suitable in that they are suitable for an expansion process in terms of uniform expandability and exhibit strong restoring force when heated due to 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 above-mentioned alkyl (meth)acrylates of the terpolymer, an alkyl group having 1 to 4 carbon atoms is preferable because it has a high modulus of elasticity 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 methacrylate, esters, butyl acrylate, etc.

In addition, as the above-mentioned thermoplastic cross-linked resin, in addition to the above-mentioned ionomer resin, low-density polyethylene with a specific gravity of 0.910 or more to less than 0.930, ultra-low-density polyethylene with a specific gravity of less than 0.910, and ethylene-vinyl acetate Resins obtained by irradiating energy rays such as electron beams to crosslink resins of ester copolymers are also suitable. Such a thermoplastic cross-linked resin has a certain degree of uniform expansion because cross-linked sites and non-cross-linked sites coexist in the resin. In addition, since it exerts a strong restoring force when heated, it is also suitable for removing the slack of the adhesive tape generated in the expansion process, and since the composition of the molecular chain contains almost no chlorine, it becomes unnecessary even after use. Even if the tape is incinerated, chlorinated aromatic hydrocarbons such as dioxin and its analogues will not be produced, so the environmental burden is also small. A resin having sufficient uniform expandability can be obtained by appropriately adjusting the amount of energy rays irradiated to the above-mentioned polyethylene or ethylene-vinyl acetate copolymer.

Moreover, as a non-crosslinking resin, the mixed resin composition of polypropylene and a styrene-butadiene copolymer can be illustrated, for example.

As the polypropylene, for example, a homopolymer of propylene, or a block type or random type propylene-ethylene copolymer can be used. The random type propylene-ethylene copolymer preferably has low rigidity. When the content rate of the ethylene structural unit in a propylene-ethylene copolymer is 0.1 weight% or more, it is excellent in the rigidity of an adhesive tape, and the compatibility of resins in a mixed resin composition is high. When the rigidity of the adhesive tape is appropriate, the cuttability of the glass is improved, and when the compatibility between the resins is high, the extrusion discharge amount is easily stabilized. More preferably, it is 1 weight% or more. In addition, when the content of the ethylene structural unit in the propylene-ethylene copolymer is 7% by weight or less, it is excellent in that polypropylene is easily and stably polymerized. More preferably, it is 5 weight% or less.

As the styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymers can also be used. When the styrene-butadiene copolymer is hydrogenated, it has good compatibility with propylene, and can prevent embrittlement and discoloration due to oxidative deterioration caused by double bonds in butadiene. In addition, when the content rate of the styrene structural unit in a styrene-butadiene copolymer is 5 weight% or more, it is preferable at the point that a styrene-butadiene copolymer is easy to polymerize stably. Moreover, when it is 40 weight% or less, it is soft and it is preferable in terms of expansibility. More preferably, it is 25 weight% or less, More preferably, it is 15 weight% or less. As the styrene-butadiene copolymer, either a block type copolymer or a random type copolymer can be used. The styrene phase of the random type copolymer is uniformly dispersed, and since the rigidity can be suppressed from becoming too large and the expansibility can be improved, it is preferable.

When the content of polypropylene in the mixed resin composition is 30% by weight or more, it is excellent in that thickness unevenness of the base film can be suppressed. When the thickness is uniform, the expandability is easy to be isotropic, and it is easy to prevent the stress relaxation property of the base film from becoming too large, the distance between chips becoming smaller with time, and the adhesive layers contacting each other to prevent re-fusion. More preferably, it is 50 weight% or more. Moreover, when the content rate of polypropylene is 90 weight% or less, it becomes easy to adjust the rigidity of a base film suitably. When the rigidity of the base film becomes too large, the force required to expand the base film becomes larger, so the burden on the device becomes larger, and it may not be possible to perform sufficient expansion for the division of the glass and the adhesive layer 13. Therefore, Moderation 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 it is easy to adjust to the rigidity of the base film of the device. When the upper limit is 70% by weight or less, it is excellent in that thickness unevenness can be suppressed, and it is more preferably 50% by weight or less.

It should be noted that, in the example shown in FIG. 1 , the base film 11 is a single layer, but it is not limited thereto, and may be a multilayer structure in which two or more resins are laminated, or one resin may be laminated. More than 2 floors. If two or more resins are uniformly cross-linked or non-cross-linked, it is preferable from the viewpoint of further strengthening and expressing each characteristic. Aspects of the respective disadvantages are preferred. The thickness of the base film 11 is not particularly limited, and it may be easily stretched in the expanding step of the glass processing tape 10 and has sufficient strength as long as it does not break. For example, it may be about 50 to 300 μm, more preferably 70 to 200 μm.

As a method for producing the multilayer base film 11 , conventionally known extrusion methods, lamination methods, and the like can be used. When using a lamination method, a transparent adhesive may be interposed between layers.

<Adhesive layer>

The adhesive layer 12 can be formed by coating the adhesive composition on the base film 11 . The adhesive layer 12 constituting the adhesive tape 10 for glass processing of the present invention has retention properties to the extent that no peeling from the adhesive layer 13 occurs during dicing, and no defects such as chip flying occur, and it is easy to bond with the adhesive when picking up. The peeling property of the layer 13 is sufficient.

In the adhesive tape 10 for glass processing of the present invention, the composition of the adhesive composition constituting the adhesive layer 12 is not particularly limited, but an energy ray-curable adhesive composition is preferable in order to improve the pick-up property after dicing. , it is preferably a material that is easily peeled off from the adhesive layer 13 after curing. As one embodiment, an adhesive composition containing, as a base resin, 60 mol % or more of a (meth)acrylate having an alkyl chain having 6 to 12 carbon atoms and having an iodine value of 5 ~30 energy ray curable carbon-carbon double bond polymer (A). It should be noted that, here, energy rays refer to rays such as ultraviolet rays, or ionizing radiation such as electron beams.

In such a polymer (A), when the amount of the energy ray-curable carbon-carbon double bond introduced is 5 or more in terms of iodine value, it is excellent in that the effect of reducing the adhesive force after energy ray irradiation becomes high. More preferably, it is 10 or more. In addition, when the iodine value is 30 or less, the holding force of the chip after energy ray irradiation to pick-up is high, and it is preferable that the gap between chips is easy to expand at the time of expansion immediately before the pick-up process. When the gap between the chips can be sufficiently widened before the pick-up process, image recognition of each chip at the time of pick-up is easy, and pick-up is easy, which is preferable. In addition, when the amount of carbon-carbon double bonds introduced is 5 to 30 in terms of iodine value, the polymer (A) itself is stable and easy to manufacture, which is preferable.

Furthermore, the polymer (A) has excellent heat resistance to heat accompanying energy ray irradiation when the glass transition temperature is -70°C or higher, and is more preferably -66°C or higher. In addition, if it is 15° C. or lower, various films are formed in the surface state, and it is excellent in the effect of preventing chip flying after dicing of glass having a surface level difference, more preferably 0° C. or lower, and even more preferably Below -28°C.

The above-mentioned polymer (A) can be produced by any method, for example, a product obtained by mixing an acrylic copolymer and a compound having an energy ray-curable carbon-carbon double bond can be used; an acrylic copolymer having a functional group or having a A product obtained by reacting a functional group methacrylic copolymer (A1) with a compound (A2) having a functional group capable of reacting with the functional group and having an energy ray-curable carbon-carbon double bond.

Among them, as the above-mentioned methacrylic acid-based copolymer (A1) having a functional group, a monomer (A1-1) having a carbon-carbon double bond, such as an alkyl acrylate or an alkyl methacrylate, and a monomer having a carbon-carbon double bond can be exemplified. A product obtained by copolymerizing a monomer (A1-2) having a carbon-carbon double bond and a functional group. Examples of the monomer (A1-1) include hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate having an alkyl chain having 6 to 12 carbon atoms. acrylate, decyl acrylate, lauryl acrylate; or pentyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate as a monomer with an alkyl chain having 5 or less carbon atoms; or These same methacrylates etc.

In addition, among monomer (A1-1), since the component whose alkyl chain number of carbon atoms is 6 or more can reduce the peeling force of an adhesive layer and an adhesive layer, it is excellent in pick-up property. In addition, a component of 12 or less has a low elastic modulus at room temperature and is excellent in terms of the adhesive force at the interface between the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer. When the adhesive strength of the interface between the adhesive layer and the adhesive layer is high, when the tape is expanded to cut the glass, deviation of the interface between the adhesive layer and the adhesive layer can be suppressed, and the cutting property is improved, which is preferable.

Furthermore, as the monomer (A1-1), the glass transition temperature is lower when the monomer with a larger alkyl chain carbon number is used, so by selecting appropriately, it is possible to prepare an adhesive with a desired glass transition temperature. agent composition. In addition, low molecular weight compounds having carbon-carbon double bonds such as vinyl acetate, styrene, and acrylonitrile may be blended for the purpose of improving various properties such as compatibility in addition to the glass transition temperature. In this case, these low molecular weight compounds are blended in the range of 5% by mass or less of the total mass of the monomer (A1-1).

On the other hand, the functional groups possessed by the monomer (A1-2) include: carboxyl group, hydroxyl group, amino group, cyclic acid anhydride group, epoxy group, isocyanate group, etc., as specific examples of the monomer (A1-2) Examples include: 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-Alkylaminoethylacrylates, N - Alkylaminoethyl methacrylates, acrylamides, methacrylamides, maleic anhydride, itaconic anhydride, fumaric anhydride, phthalic anhydride, glycidyl acrylate, glycidyl methacrylate , Allyl glycidyl ether, etc.

Furthermore, in the compound (A2), as the functional group used, when the functional group possessed by the compound (A1) is a carboxyl group or a cyclic acid anhydride group, examples include: a hydroxyl group, an epoxy group, an isocyanate group, and the like. In the case of: cyclic acid anhydride group, isocyanate group, etc., in the case of amino group: epoxy group, isocyanate group, etc., in the case of epoxy group: carboxyl group, cyclic Specific examples of the acid anhydride group, amino group, etc. include the same compounds as those listed in the specific examples of the monomer (A1-2). In addition, as the compound (A2), a polyisocyanate compound obtained by urethanizing a part of the isocyanate group with a monomer having a hydroxyl group or a carboxyl group and an energy ray-curable carbon-carbon double bond can also be used.

In addition, in the reaction of compound (A1) and compound (A2), by remaining an unreacted functional group, it becomes possible to produce desired thing about characteristics, such as an acid value and a hydroxyl value. When the OH group remains so that the hydroxyl value of a polymer (A) becomes 5-100, the risk of a pick-up error can be further reduced by reducing the adhesive force after energy-beam irradiation. In addition, when the COOH group remains so that the acid value of the polymer (A) becomes 0.5 to 30, it is preferable to obtain the effect of improving the recovery of the pressure-sensitive adhesive layer after expanding the adhesive tape for glass processing of the present invention. . When the hydroxyl value of the polymer (A) is 5 or more, it is excellent in reducing the adhesive force after energy ray irradiation, and when it is 100 or less, it is excellent in the fluidity of the adhesive after energy ray irradiation excellent. Moreover, when an acid value is 0.5 or more, it is excellent in tape recovery property, and when it is 30 or less, it is excellent in the fluidity|liquidity of an adhesive agent.

In the synthesis of the above-mentioned polymer (A), as the organic solvent in the case of carrying out the reaction by solution polymerization, ketone-based, ester-based, alcohol-based, and aromatic-based organic solvents can be used, among which toluene, ethyl acetate Esters, isopropanol, benzyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, etc. are generally good solvents for acrylic polymers and have a boiling point of 60-120°C. As a polymerization initiator, α is usually used, Free generators of azo-based products such as α'-azobisisobutyronitrile, and organic peroxide-based products such as benzoyl peroxide. At this time, if necessary, a catalyst and a polymerization inhibitor may be used in combination, and a polymer (A) having a desired molecular weight can be obtained by adjusting the polymerization temperature and polymerization time. In addition, for adjusting the molecular weight, it is preferable to use a mercaptan or carbon tetrachloride-based solvent. It should be noted that this reaction is not limited to solution polymerization, and may be another method such as bulk polymerization or suspension polymerization.

As above, the polymer (A) can be obtained, and in the present invention, when the molecular weight of the polymer (A) is 300,000 or more, it is excellent in that the cohesive force can be improved. When the cohesive force is high, there is an effect of suppressing deviation at the interface with the adhesive layer during expansion, and the adhesive layer easily transmits tensile force, which is preferable in terms of improving the separability of the adhesive layer. When the molecular weight of the polymer (A) is 2 million or less, it is excellent in suppressing gelation during synthesis and coating. In addition, the molecular weight in this invention means the mass average molecular weight of polystyrene conversion.

Moreover, in the tape 10 for glass processing of this invention, the resin composition which comprises the adhesive layer 12 may have the compound (B) functioning as a crosslinking agent other than a polymer (A). For example, polyisocyanate, a melamine-formaldehyde resin, and an epoxy resin are mentioned, These can be used individually or in combination of 2 or more types. The compound (B) reacts with the polymer (A) or the substrate film to form a cross-linked structure, and through the cross-linked structure, the polymer (A) and (B) can be enhanced after the adhesive composition is applied. ) as the cohesion of the adhesive of the main component.

The polyisocyanates are not particularly limited, and examples thereof include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, 4,4'-diphenylethyl ether diisocyanate, Aromatic isocyanates such as 4,4'-[2,2-bis(4-phenoxyphenyl)propane]diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene Diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, lysine diisocyanate, lysine triisocyanate, etc., specifically , Coronate L (manufactured by Japan Polyurethane Co., Ltd., trade name) and the like can be used. As the melamine-formaldehyde resin, specifically, Nikalac MX-45 (manufactured by Sanwa Chemical Co., Ltd., trade name), MELAN (manufactured by Hitachi Chemical Industries, Ltd., trade name) and the like can be used. As an epoxy resin, TETRAD-X (made by Mitsubishi Chemical Corporation, a brand name) etc. can be used. In the present invention, polyisocyanates are particularly preferably used.

The pressure-sensitive adhesive layer in which the added amount of the compound (B) is 0.1 parts by mass or more relative to 100 parts by mass of the polymer (A) is excellent in terms of cohesive force. More preferably, it is 0.5 mass part or more. In addition, an adhesive layer set at 10 parts by mass or less is excellent in suppressing rapid gelation at the time of coating, and the workability of blending of the adhesive, coating, and the like is good. More preferably, it is 5 parts by mass or less.

Moreover, in this invention, the photoinitiator (C) may be contained in the adhesive layer 12. The photopolymerization initiator (C) contained in the pressure-sensitive adhesive layer 12 is not particularly limited, and conventionally known photopolymerization initiators can be used. For example, benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone and other diphenyl ketones; acetophenones such as acetophenone and diethoxyacetophenone, anthraquinones such as 2-ethylanthraquinone and tert-butylanthraquinone; 2-chlorothioxanthone, benzoin ethyl ether, Benzoin isopropyl ether, dibenzoyl, 2,4,5-triaryl imidazole dimer (lophine dimer), acridine-based compounds, and the like can be used alone or in combination of two or more. The amount of the photopolymerization initiator (C) added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the polymer (A). In addition, the upper limit thereof is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

Furthermore, in the energy ray-curable adhesive used in the present invention, a thickener, an adhesion regulator, a surfactant, or the like, or other modifiers, etc., may be blended as necessary. In addition, an inorganic compound filler may be added appropriately.

The adhesive layer 12 can be formed by a conventional adhesive layer forming method. For example, it can be formed by applying the above-mentioned adhesive composition to a predetermined surface of the base film 11, or by applying the above-mentioned adhesive composition to a spacer (such as a plastic material coated with a release agent). The adhesive layer 12 is formed on the base film 11 by a method of transferring the adhesive layer 12 to a predetermined surface of the substrate after forming the adhesive layer 12 on a film or a sheet, etc. In addition, the pressure-sensitive adhesive layer 12 may have the form of a single layer, and may have the form of lamination|stacking.

The thickness of the adhesive layer 12 is not particularly limited, but when the thickness is 2 μm or more, it is excellent in terms of adhesive force, and more preferably 5 μm or more. The pick-up property is excellent when it is 15 micrometers or less, More preferably, it is 10 micrometers or less.

For the adhesive tape 15, the average value of the thermal deformation rate per 1°C between 40°C and 80°C measured in the MD (Machine Direction) direction when the temperature is raised by using a thermomechanical characteristic testing machine and TD ( Vertical direction, Transverse Direction) The sum of the average values of the thermal deformation rate per 1°C measured by the thermomechanical characteristics testing machine at the time of heating between 40°C and 80°C is a negative value, that is, less than 0. The MD direction is the flow direction when the film is formed, and the TD direction is the direction perpendicular to the MD direction.

The average value of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermomechanical property testing machine in the MD direction of the adhesive tape 15 when the temperature was raised and the temperature rise in the TD direction by the thermomechanical property testing machine The average sum of the average values of the thermal deformation rates per 1° C. measured between 40° C. and 80° C. is a negative value, and the tape 10 for glass processing can be shrunk by heating at a low temperature for a short time. Therefore, even in the case where a pair of hot air nozzles are used to surround the slack portion of the glass processing tape 10 to perform thermal shrinkage, it is not necessary to heat and shrink the tape 10 multiple times while reducing the amount of expansion. The slack caused by expansion is removed in a short time, and an appropriate incision width is maintained.

The thermal deformation rate can be calculated from the following formula (1) by measuring the amount of deformation due to temperature in accordance with JIS K7197:2012.

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

In addition, the deformation|transformation amount is shown with the expansion direction of a sample being positive, and the contraction direction being negative.

The thermal deformation rate between 40°C and 80°C is like the curve in the MD direction or the curve in the TD direction in Fig. °C, the adhesive tape generally shows a shrinking behaviour.

In order to make the sum of the average value of the thermal deformation rate in the MD direction and the average value of the thermal deformation rate in the TD direction a negative value, it is possible to add a step of stretching the resin film after forming a film. The thickness of the adhesive tape 15, and the stretching amount in the MD direction or the TD direction are adjusted according to the type. As a method of stretching the adhesive tape in the TD direction, a method using a tenter, a method based on blow molding (inflation), a method using an expansion roll, etc., can be mentioned as a method of stretching the adhesive tape in the MD direction. Examples include: a method of stretching at the time of ejection from a die, a method of stretching with conveying rollers, and the like. Any method can be employed as a method of obtaining the adhesive tape 15 of the present invention.

<Adhesive layer>

In the glass processing tape 10 of the present invention, the adhesive layer 13 is peeled from the adhesive layer 12 and attached to the chip when the chip is picked up after the glass is bonded and diced. Also, it is used as an adhesive when fixing chips to substrates and lead frames.

The adhesive layer 13 is not particularly limited, and may be a film-like adhesive generally used for glass, for example, an adhesive layer containing a thermoplastic resin and a thermopolymerizable component. The above-mentioned thermoplastic resin used in the adhesive layer 13 of the present invention is preferably a thermoplastic resin, or a resin that has thermoplasticity in an uncured state and forms a crosslinked structure after heating, and is not particularly limited. As one embodiment, A thermoplastic resin with a weight average molecular weight of 5,000 to 200,000 and a glass transition temperature of 0 to 150°C is produced. Moreover, as another form, the thermoplastic resin whose weight average molecular weight is 100,000-1,000,000 and whose glass transition temperature is -50-20 degreeC is mentioned.

Examples of the former thermoplastic resin include polyimide resins, polyamide resins, polyetherimide resins, polyamideimide resins, polyester resins, polyesterimide resins, and phenoxy resins. , polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyether ketone resin, etc. Among them, polyimide resin and phenoxy resin are preferably used, and as the latter thermoplastic resin, polymeric resins containing functional groups are preferably used. things.

The polyimide resin can be obtained by subjecting tetracarboxylic dianhydride and diamine to condensation reaction by a well-known method. That is, the addition reaction is performed at a reaction temperature of 80° C. or lower, preferably 0 to 60° C., using equimolar or substantially equimolar tetracarboxylic dianhydride and diamine (addition order of each component is arbitrary) in an organic solvent. As the reaction proceeds, the viscosity of the reaction liquid gradually increases, and polyamic acid, which is a precursor of polyimide, is produced. The molecular weight can also be adjusted by depolymerizing this polyamic acid by heating at the temperature of 50-80 degreeC. The polyimide resin can be obtained by dehydrating and ring-closing the above reactant (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method of heat treatment, or a chemical ring closure method using a dehydrating agent.

Tetracarboxylic dianhydride used as a raw material of 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 base) bis(trimellitic anhydride), 1,12-(dodecamethylene)bis(trimellitic anhydride), 1,16-(hexadecylmethylene)bis(trimellitic anhydride), 1,18-(octadecylethylene) Bis(trimellitic anhydride), pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2- Bis(3,4-dicarboxyphenyl)malonic anhydride, 2,2-bis(2,3-dicarboxyphenyl)malonic anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane Dianhydride, 1,1-bis(3,4-dicarboxyphenyl)oxalic anhydride, bis(2,3-dicarboxyphenyl)methanedianhydride, bis(3,4-dicarboxyphenyl)methanedi anhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, benzene-1, 2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,2',3'-benzophenone tetracarboxylic dianhydride, 3 , 3,3',4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6, 7-naphthalene tetracarboxylic anhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid Dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride , 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilane Dianhydride, bis(3,4-dicarboxyphenyl)methylphenylsilane dianhydride, bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride, 1,4-bis(3,4- Dicarboxyphenyldimethylsilyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexanedianhydride, p- Phenyl bis(trimellitic anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4, 8-Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dicarboxylic acid Anhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic 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-dicarboxybenzene base) hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy base) diphenyl sulfide dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride) , 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, etc., One or more of these may be used in combination.

In addition, the diamine used as a raw material of polyimide is not particularly limited, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, 3,3'-diamino Diphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4' -Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfone, 4,4'-diaminobis Phenylsulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis(3-aminobenzene base) propane, 2,2'-(3,4'-diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexa Fluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy Base) benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-phenylene bis(1 -Methylethylene)) bisaniline, 3,4'-(1,4-phenylenebis(1-methylethylene))bisaniline, 4,4'-(1,4-phenylene Bis(1-methylethylene))bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy) base) phenyl) propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane Fluoropropane, bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(4-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy) ) phenyl) sulfone, bis (4-(4-aminophenoxy) phenyl) sulfone, 3,5-diaminobenzoic acid and other aromatic diamines; 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, the following general formula Diaminopolysiloxane shown in (1), 1,3-bis(aminomethyl)cyclohexane, JEFFAMINE D-230, D-400, D-2000, D-4000, ED manufactured by Japan Santekunokemikaru Co., Ltd. Aliphatic diamines such as polyoxyalkylene diamines such as -600, ED-900, ED-2001, and EDR-148 may be used in combination of one or two or more of them. It is preferable that it is 0-200 degreeC as a glass transition temperature of the said polyimide resin, and it is preferable that it is 10,000-200,000 as a weight average molecular weight.

[chemical formula 1]

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

The phenoxy resin, which is one of the above-mentioned other preferable thermoplastic resins, is preferably a resin obtained by reacting various bisphenols with epichlorohydrin, or by reacting a liquid epoxy resin with bisphenols, as Bisphenols include bisphenol A, bisphenol AF, bisphenol AD, bisphenol F, and bisphenol S. Since the phenoxy resin is similar in structure to an epoxy resin, it has good compatibility with an epoxy resin, and is suitable for imparting favorable adhesiveness to an adhesive film.

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

[chemical formula 2]

In the above general formula (2), X represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene, phenylene, -O-, -S-, -SO-, or -SO2-. Here, the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably -C(R1)(R2). R1 and R2 represent a hydrogen atom or an alkyl group, and the alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, and isopropyl , Isooctyl, 2-ethylhexyl, 1,3,3-trimethylbutyl, etc. In addition, this alkyl group may be substituted by a halogen atom, for example, a trifluoromethyl group is mentioned. X is preferably an alkylene group, -O-, -S-, fluorenyl group or -SO2-, more preferably an alkylene group, -SO2-. Among them, -C(CH3)2-, -CH(CH3)-, -CH2-, -SO2- are preferred, -C(CH3)2-, -CH(CH3)-, -CH2- are more preferred, especially Preferred is -C(CH3)2-.

With respect to the phenoxy resin represented by the above-mentioned general formula (2), if it has a repeating unit, it may be a resin having a plurality of repeating units of the above-mentioned general formula (2) different from X, or it may only be made of the same X. repeating unit. In the present invention, a resin composed only of repeating units identical to X is preferable.

In addition, 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 thermally polymerizable components is improved, and uniform appearance and properties can be imparted.

When the mass average molecular weight of a phenoxy resin is 5000 or more, it is excellent in film formability. More preferably, it is 10,000 or more, and it is still more preferable that it is 30,000 or more. In addition, when the mass average molecular weight is 150,000 or less, it is preferable in terms of fluidity during thermocompression bonding and compatibility with other resins. More preferably, it is 100,000 or less. In addition, when the glass transition temperature is -50°C or higher, it is excellent in film formability, more preferably 0°C or higher, and still more preferably 50°C or higher. When the glass transition temperature is 150° C., the adhesive force of the adhesive layer 13 at the time of dicing is excellent, and it is more preferably 120° C. or lower, and still more preferably 110° C. or lower.

On the other hand, examples of functional groups in the polymer containing functional groups include glycidyl groups, acryloyl groups, methacryloyl groups, hydroxyl groups, carboxyl groups, isocyanurate groups, amino groups, and amido groups. , preferably glycidyl.

As a high molecular weight component containing the said functional group, the (meth)acrylic-type copolymer etc. which contain functional groups, such as a glycidyl group, a hydroxyl group, and a carboxyl group, are mentioned, for example.

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

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 refers to a monomer constituting a glycidyl group-containing (meth)acrylic copolymer, specifically glycidyl acrylate or glycidyl methacrylate. When the amount of the glycidyl group-containing repeating unit is within this range, adhesive force can be ensured and gelation can be prevented.

Examples of constituent monomers of the aforementioned (meth)acrylic copolymers other than glycidyl acrylate and glycidyl methacrylate include ethyl (meth)acrylate, butyl (meth)acrylic acid Esters and the like can be used alone or in combination of two or more. In addition, in this invention, ethyl (meth)acrylate means ethyl acrylate and/or ethyl methacrylate. The mixing ratio in the case of using a functional monomer in combination may be determined in consideration of the glass transition temperature of the (meth)acrylic copolymer. When the glass transition temperature is -50° C. or higher, film formability is excellent and excessive viscosity at normal temperature can be controlled, which is preferable. When the adhesive force at normal temperature is excessive, handling of the adhesive layer becomes difficult. More preferably, it is -20°C or higher, and still more preferably, it is 0°C or higher. In addition, when the glass transition temperature is 30° C. or lower, it is excellent in terms of the adhesive force of the adhesive layer at the time of dicing, and it is more preferably 20° C. or lower.

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

In the present invention, when the weight average molecular weight of the high molecular weight component containing a functional monomer is 100,000 or more, it is excellent in film formability, more preferably 200,000 or more, and still more preferably 500,000 or more. Moreover, when a weight average molecular weight is adjusted to 2,000,000 or less, it is excellent in the point which improves the heating fluidity of the adhesive bond layer at the time of bonding. When the heating fluidity of the adhesive layer during bonding is improved, the adhesive layer and the adherend can adhere well, the adhesive force can be improved, and the unevenness of the adherend can be easily filled to suppress voids. It is more preferably 1,000,000 or less, still more preferably 800,000 or less, and when it is 500,000 or less, a greater effect can be obtained.

In addition, the thermally polymerizable component is not particularly limited as long as it is a component that polymerizes by heat, and examples include: A compound with a functional group such as an amide group and an excitation material can be used alone or in combination of two or more. When considering the heat resistance of the adhesive layer, it is preferably contained together with a curing agent and an accelerator to be cured by heat to exert adhesion. Functional thermosetting resin. Examples of thermosetting resins include epoxy resins, acrylic resins, silicone resins, phenol resins, thermosetting polyimide resins, polyurethane resins, melamine resins, and urea resins. In terms of an adhesive layer excellent in workability and reliability, it is most preferable to use an epoxy resin.

The above-mentioned epoxy resins are not particularly limited as long as they are solidified and have a bonding epoxy resin, and bifunctional epoxy resins such as bisphenol A type epoxy can be used; Novolac epoxy resins such as epoxy resins, etc. In addition, commonly known epoxy resins such as polyfunctional epoxy resins, glycidylamine epoxy resins, heterocyclic ring-containing epoxy resins, or alicyclic epoxy resins can be used.

Examples of the above-mentioned bisphenol A type epoxy resin include EPIKOTE series (EPIKOTE807, EPIKOTE815, EPIKOTE825, EPIKOTE827, EPIKOTE828, EPIKOTE834, EPIKOTE1001, EPIKOTE1004, EPIKOTE1007, EPIKOTE100) manufactured by Mitsubishi Chemical Corporation. 9); DER manufactured by Dow Chemical Company -330, DER-301, DER-361; and YD8125, YDF8170 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. As above-mentioned phenolic novolac type epoxy resin, can enumerate: Mitsubishi Chemical Co., Ltd. make EPIKOTE 152, EPIKOTE 154; Nippon Kayaku Co., Ltd. make EPPN-201; Dow Chemical company make DEN-438 etc., in addition as The above-mentioned o-cresol novolac type epoxy resins include: EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027 manufactured by Nippon Kayaku Co., Ltd.; YDCN701, YDCN702, YDCN703, YDCN704 etc. manufactured by Sumikin Chemical Co., Ltd. Examples of the above-mentioned polyfunctional epoxy resin include: Epon 1031S manufactured by Mitsubishi Chemical Corporation; Araldite 0163 manufactured by Ciba Specialty Chemicals; Denacol EX-611, EX-614, EX-614B, EX-622 manufactured by Nagase ChemteX Co., Ltd. , EX-512, EX-521, EX-421, EX-411, EX-321, etc. Examples of the aforementioned amine-type epoxy resins include: EPIKOTE 604 manufactured by Mitsubishi Chemical Corporation; YH-434 manufactured by Tohto Chemical Co., Ltd.; TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd.; Sumitomo Chemical Industries, Ltd. Co., Ltd. make ELM-120 etc. As the above-mentioned heterocycle-containing epoxy resin, Araldite PT810 manufactured by Ciba Specialty Chemicals; ERL4234, ERL4299, ERL4221, ERL4206 manufactured by UCC, etc. are mentioned. These epoxy resins can be used individually or in combination of 2 or more types.

In order to cure the above-mentioned thermosetting resin, additives may be added as appropriate. Examples of such additives include curing agents, curing accelerators, catalysts, and the like, and when adding a catalyst, a co-catalyst can be used as needed.

When an epoxy resin is used for the above-mentioned thermosetting resin, it is preferable to use an epoxy resin curing agent or a curing accelerator, and it is more preferable to use them in combination. Examples of curing agents include phenol resins, dicyandiamide, boron trifluoride complexes, organic hydrazide compounds, amines, polyamide resins, imidazole compounds, urea or thiourea compounds, polythiol compounds, Polysulfide resins, acid anhydrides, light/ultraviolet curing agents with mercapto groups at the end. These can be used individually or in combination of 2 or more types.

Among them, examples of boron trifluoride complexes include boron trifluoride-amine complexes with various amine compounds (preferably primary amine compounds), and examples of organic hydrazide compounds include m-phthalidine hydrazide.

Examples of the phenolic resin include: phenol novolak resins, phenol aralkyl resins, cresol novolac resins, tert-butylphenol novolak resins, nonylphenol novolak resins, and other novolak-type phenol resins; Type phenolic resin; polyoxystyrene such as poly-p-hydroxystyrene, etc. Among these, phenolic compounds having at least two phenolic hydroxyl groups in the molecule are preferred.

Examples of the phenolic compound having at least two phenolic hydroxyl groups in the molecule include: phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, cyclopentadiene cresol novolak resin, Cyclopentadiene phenol novolac resin, xylylene modified phenol novolac resin, naphthol novolac resin, triphenol novolac resin, tetraphenol novolac resin, bisphenol A novolac resin, polyvinyl Phenol resin, phenol aralkyl resin, etc. Furthermore, among these phenol resins, phenol novolac resins and phenol aralkyl resins are particularly preferable, since connection reliability can be improved.

烷二胺、异佛尔酮二胺、1，3-双(氨基甲基)环己烷等)、杂环胺(哌嗪、N，N-二甲基哌嗪、三亚乙基二胺、三聚氰胺、胍胺等)、芳香族胺(间苯二胺、4，4’-二氨基二苯基甲烷、4，4’-二氨基二苯砜等)、聚酰胺树脂(优选聚酰胺-胺，二聚酸与多胺的缩合物)、咪唑化合物(2-苯基-4，5-二羟基甲基咪唑、2-甲基咪唑、2，4-二甲基咪唑、2-正十七烷基咪唑、1-氰乙基-2-十一烷基咪唑-偏苯三酸酯、环氧-咪唑加成物等)、脲或硫脲化合物(N，N-二烷基脲化合物、N，N-二烷基硫脲化合物等)、多硫醇化合物、在末端具有巯基的多硫化物树脂、酸酐(四氢邻苯二甲酸酐等)、光/紫外线固化剂(二苯基碘鎓六氟磷酸盐、三苯基锍六氟磷酸盐等)。Examples of amines include chain aliphatic amines (diethylenetriamine, triethylenetetramine, hexamethylenediamine, N,N-dimethylpropylamine, benzyldimethylamine, 2- (Dimethylamino)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, m-xylylenediamine, etc.), cyclic aliphatic amines (N-aminoethylpiperazine, bis(3-methyl Base-4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)methane,

Alkanediamine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, etc.), heterocyclic amines (piperazine, N,N-dimethylpiperazine, triethylenediamine, Melamine, guanamine, etc.), aromatic amines (m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, etc.), polyamide resins (preferably polyamide-amine , the condensation product of dimer acid and polyamine), imidazole compound (2-phenyl-4,5-dihydroxymethylimidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-heptadecane Alkylimidazole, 1-cyanoethyl-2-undecylimidazole-trimellitate, epoxy-imidazole adduct, etc.), urea or thiourea compound (N,N-dialkylurea compound, N, N-dialkylthiourea compounds, etc.), polythiol compounds, polysulfide resins with mercapto groups at the end, acid anhydrides (tetrahydrophthalic anhydride, etc.), light/ultraviolet curing agents (diphenyl iodide Onium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, etc.).

The above-mentioned curing accelerator is not particularly limited as long as it is a curing accelerator that cures a thermosetting resin, for example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenyl Phosphine tetraphenyl borate, 2-ethyl-4-methylimidazolium-tetraphenyl borate, 1,8-diazabicyclo[5.4.0]undecene-7-tetraphenyl Borate etc.

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

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

The compounding ratio of the said epoxy resin and a phenol resin is preferably compounded so that the hydroxyl group in a phenol resin becomes 0.5-2.0 equivalent with respect to 1 equivalent of epoxy groups in the said epoxy resin component, for example. More preferably, it is 0.8-1.2 equivalent. That is, it is because when the compounding ratio of both is out of the said range, sufficient hardening reaction cannot progress, and the characteristic of an adhesive bond layer will deteriorate easily. Regarding other thermosetting resins and curing agents, in one embodiment, the curing agent is 0.5-20 parts by mass relative to 100 parts by mass of the thermosetting resin, and in another embodiment, the curing agent is 1-10 parts by mass. The content of the curing accelerator is preferably less than that of the curing agent, and is preferably 0.001 to 1.5 parts by mass, more preferably 0.01 to 0.95 parts by mass, based on 100 parts by mass of the thermosetting resin. By adjusting to be within the above-mentioned range, it is possible to assist the advancement of sufficient curing reaction. The content of the catalyst is preferably 0.001 to 1.5 parts by mass, more preferably 0.01 to 1.0 parts by mass relative to 100 parts by mass of the thermosetting resin.

In addition, the adhesive layer 13 of the present invention may appropriately contain a filler according to its use. Thereby, it is possible to improve the cuttability of the adhesive layer in the uncured state, improve the handleability, adjust the melt viscosity, and impart thixotropy, and further improve the thermal conductivity of the adhesive layer in the cured state. Improving of imparting and adhesive force.

As a filler used in this invention, an inorganic filler is preferable. The inorganic filler is not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate crystal whiskers, boron nitride, crystalline silica, amorphous silica, antimony oxide, etc. In addition, these can be used individually or in mixture of 2 or more types.

In addition, among the above-mentioned inorganic fillers, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica, and the like are preferably used from the viewpoint of improving thermal conductivity. In addition, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystalline Silica, amorphous silica, etc. In addition, alumina and silica are preferably used from the viewpoint of cutting property improvement.

The adhesive layer of the present invention may contain two or more types of fillers having different average particle diameters as the fillers. In this case, compared with the case of using a single filler, in the raw material mixture before film formation, it is easy to prevent the viscosity increase when the filler content is high or the viscosity decrease when the filler content is low, and it is easy to obtain Good film formability, the fluidity of the uncured adhesive layer can be optimally controlled, and excellent adhesive force can be easily obtained after the adhesive layer is cured.

In addition, the adhesive layer of the present invention preferably has an average particle diameter 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, thinning of the film becomes easy. Here, a thin film means a thickness of 20 μm or less. Moreover, when it is 0.01 micrometer or more, dispersibility becomes favorable.

Furthermore, from the viewpoint of preventing the viscosity of the raw material mixture before film formation from increasing or decreasing, controlling the fluidity of the uncured adhesive layer optimally, and improving the adhesive force of the adhesive layer after curing, it is preferable It contains the 1st filler whose average particle diameter exists in the range of 0.1-1.0 micrometers, and the 2nd filler whose primary particle diameter exists in the range of 0.005-0.03 micrometers. It is preferable to contain the first filler whose average particle diameter is in the range of 0.1 to 1.0 μm, and 99% or more of the particles are distributed in the range of particle diameters of 0.1 to 1.0 μm, and the average particle diameter of the primary particle diameter is in the range of 0.005 to 0.03 μm. The second filler in which 99% or more of the particles are distributed within the range of particle diameters from 0.005 to 0.1 μm.

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

In the present invention, in one embodiment, 10 to 40% by mass of a thermoplastic resin having a weight average molecular weight of 5,000 to 200,000, 10 to 40% by mass of thermally polymerizable components, and 30 to 75% by mass of fillers. In this embodiment, the content of the filler may be 30 to 60% by mass, or may be 40 to 60% by mass. Moreover, the mass average molecular weight of a thermoplastic resin may be 5000-150,000, and may be 10,000-100,000.

In another embodiment, 10 to 20% by mass of a thermoplastic resin having a weight-average molecular weight of 200,000 to 2,000,000 and 20 to 50% by mass of a thermopolymerizable ingredients, and 30 to 75% by mass of fillers. In this embodiment, the content of the filler may be 30 to 60% by mass, or may be 30 to 50% by mass. Moreover, the mass average molecular weight of a thermoplastic resin may be 200,000-1,000,000, and may be 200,000-800,000.

By adjusting the compounding ratio, the storage elastic modulus and fluidity after curing of the adhesive layer 13 can be optimized, and there is a tendency that sufficient heat resistance at high temperatures can also be obtained.

The light transmittance of the adhesive layer 13 to light having a wavelength of 550 nm is preferably 90% or more. In the case of a device having a structure in which glass is laminated on top of an image sensor via an adhesive layer, if the light transmittance is less than 90%, the sensor may not operate reliably. The light transmittance can generally be adjusted by the composition of the adhesive layer, especially by selecting the matrix resin and the filler, so that mounting reliability and high transmittance can be achieved at the same time. It can be adjusted by reducing the particle size of the filler to suppress light scattering and increase the transmittance. As a high-transmittance resin, for example, an epoxy resin or a silicone resin is preferably used, and a bisphenol-type epoxy resin is particularly preferably used in consideration of mounting reliability, but is not limited thereto.

The light transmittance can be obtained by measuring the amount of transmitted light with a spectrophotometer (manufactured by Hitachi High-Technologies, Spectrophotometer U-4100 Solid Sample Measurement System). Specifically, an adhesive layer with a thickness of 20 μm was bonded to glass, light was made to penetrate in the normal direction to the glass surface, and the light transmittance of light of 550 nm to the glass at 25° C. was obtained. Specifically, it is calculated by the following formula (2).

The light transmittance of the adhesive layer I(%)=I1/I0 (2)

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

I0(%): light transmittance of glass

In the tape 10 for glass processing of the present invention, the adhesive layer 13 can be formed by directly or indirectly laminating a film-formed adhesive (hereinafter referred to as an adhesive film) on the base film 11. . The temperature during lamination is preferably in the range of 10 to 100° C., and it is preferable to apply a linear load of 0.01 to 10 N/m. It should be noted that such an adhesive film may be an adhesive film in which the adhesive layer 13 is formed on a release film. In this case, the release film may be peeled off after lamination, or may be used as a glass as it is. The cover film of the processing tape 10 is peeled off when bonding the glass.

The above-mentioned adhesive film may be laminated on the entire surface of the adhesive layer 12 , or an adhesive film cut (pre-cut) according to the shape of glass to be bonded in advance may be laminated on the adhesive layer 12 . In this way, when the adhesive film corresponding to the glass is laminated, as shown in FIG. Instead, only the adhesive layer 12 is present. Generally speaking, the adhesive layer 13 is not easy to peel off from the adherend, so by using a pre-cut adhesive film, the ring frame 20 can be bonded to the adhesive layer 12, and the tape after use can be peeled off. The effect of paste residue on the ring frame 20 is not easily produced.

<purpose>

The glass processing tape 10 of this invention is used for the processing method of glass including the expansion process of dividing|segmenting the adhesive bond layer 13 at least by expansion. Therefore, other steps, the order of the steps, and the like are not particularly limited. For example, it can be suitably used for the following glass processing methods (A)-(C).

Glass processing method (A)

A method for processing glass, comprising:

(a) A step of attaching the adhesive film attached to the adhesive layer of the aforementioned adhesive tape for glass body processing to glass while heating the glass at 70 to 80°C,

(b) a step of irradiating a portion of the glass to be divided with laser light to form a modified region by multiphoton absorption inside the glass,

(c) dividing the above-mentioned glass and the above-mentioned adhesive film along the dividing line by expanding the above-mentioned semi-glass processing tape to obtain a plurality of chips with the adhesive film attached,

(d) a step of maintaining the gap between the chips by removing the slack generated in the expanding step by heating and shrinking the portion of the glass processing tape that does not overlap the chips, and

(e) The process of picking up the said chip|tip with the said adhesive bond layer attached from the adhesive layer of the tape for glass processing.

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

Glass processing method (B)

A method for processing glass, comprising:

(a) A process of bonding the adhesive film bonded to the adhesive layer of the adhesive tape for glass processing to glass while heating the glass at 70 to 80°C,

(b) a process of irradiating laser light along the dividing line from the surface of the above-mentioned glass to divide into individual chips,

(c) dividing the above-mentioned adhesive film corresponding to the above-mentioned chip by expanding the above-mentioned tape for glass processing to obtain a plurality of chips with the adhesive film attached,

(d) a step of maintaining the gap between the chips by removing the slack generated in the expanding step by heating and shrinking the portion of the glass processing tape that does not overlap the chips, and

(e) The process of picking up the said chip|tip with the said adhesive bond layer attached from the adhesive layer of the tape for glass processing.

The processing method of this glass adopts the laser cutting method of full cutting.

Glass processing method (C)

A method for processing glass, comprising:

(a) A process of bonding the adhesive film bonded to the adhesive layer of the adhesive tape for glass processing to glass while heating the glass at 70 to 80°C,

(b) the process of cutting the above-mentioned glass along the dividing line with a dicing knife and dividing it into individual chips,

(c) dividing the above-mentioned adhesive film corresponding to the above-mentioned chip by expanding the above-mentioned tape for glass processing to obtain a plurality of chips with the adhesive film attached,

(d) a step of maintaining the gap between the chips by removing the slack generated in the expanding step by heating and shrinking the portion of the glass processing tape that does not overlap the chips, and

(e) The process of picking up the said chip|tip with the said adhesive bond layer attached from the adhesive layer of the tape for glass processing.

The processing method of this glass is a method of cutting with a full-cut blade.

<How to use>

The usage method of the tape when applying the glass processing tape 10 of this invention to the said glass processing method (A) is demonstrated, referring FIGS. 2-5.

As shown in FIG. 2 , the glass W is placed on a heated table 25 of a wafer mounter with the front side facing down, and then the glass W is bonded with a glass processing tape 10 on the back surface thereof. Here, the glass processing tape 10 used is laminated with an adhesive film that has been previously cut (precut) into a shape corresponding to the glass W to be bonded. Around the area, the adhesive layer 12 is exposed. The portion of the glass processing tape 10 where the adhesive layer 13 is exposed is bonded to the back surface of the glass W, and the portion around the adhesive layer 13 where the adhesive layer 12 is exposed is bonded to the ring frame 20 . At this time, the heating stage 25 is set to 70-80 degreeC, and heat bonding is implemented by this. In this embodiment, an adhesive tape 15 including a base film 11 and an adhesive layer 12 provided on the base film 11 and an adhesive agent provided on the adhesive layer 12 are used. The tape 10 for glass processing of the layer 13, however, an adhesive tape and a film 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, the adhesive tape 15 based on this invention was used as an adhesive tape.

Next, the glass W bonded with the glass processing tape 10 is carried out from the heating table 25, and as shown in FIG. Modified area 32.

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

Next, as shown in FIG. 4( b ), in a state in which the ring frame 20 is fixed, the hollow cylindrical push-up member 22 of the expansion device is raised to expand the tape 10 for glass processing. As the expansion conditions, the expansion speed is, for example, 5 to 500 mm/sec, and the expansion amount (pushing amount) is, for example, 5 to 25 mm. In this way, by stretching the glass processing tape 10 in the radial direction of the glass W, the glass W is divided into chips 34 starting from the reformed region 32 . At this time, in the adhesive layer 13, the elongation (deformation) due to the expansion is suppressed at the portion bonded to the back surface of the glass W without cracking, but at the position between the chips 34, the The tension caused by the expansion of the tape concentrates and ruptures. Therefore, the adhesive layer 13 is also divided together with the glass W as shown in FIG. 4( c ). Thereby, a plurality of chips 34 with adhesive layer 13 can be obtained.

Next, as shown in FIG. 5 , the push-up member 22 is returned to the original position, and the slack of the glass processing tape 10 generated in the previous expansion step is removed to stably maintain the interval between the chips 34 . In this process, for example, in the annular heat-shrinkable region 28 between the region where the chip 34 exists in the tape 10 for glass processing and the ring frame 20, hot air at 40 to 120° C. is blown using the hot air nozzle 29 to make the base material The film 11 heat-shrinks, and the tape 10 for glass processing becomes a tense state. Thereafter, the adhesive layer 12 is subjected to energy ray curing treatment, thermal curing treatment, etc. to weaken the adhesive force of the adhesive layer 12 to the adhesive layer 13 , and then the chip 34 is picked up.

In addition, the adhesive tape 10 for glass processing based on this embodiment has the structure provided with the adhesive bond layer 13 on the adhesive bond layer 12, However, You may comprise so that the adhesive bond layer 13 may not be provided. In this case, the glass can be bonded to the adhesive layer 12 and only used for dividing the glass. When using a tape for glass processing, an adhesive film produced in the same manner as the adhesive layer 13 can be used. It is bonded to the adhesive layer 12 together with the glass, and the glass and the adhesive film are divided.

<Example>

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

[Production of tape for glass processing]

(1) Production of substrate film

<Base film A>

Zinc ionomer of ethylene-methacrylic acid-ethyl methacrylate copolymer (15% methacrylic acid content, 5% ethyl methacrylate content, softening point 72°C, melting point Resin beads of 90° C., density 0.96 g/cm 3 , and zinc ion content 5% by mass) were melted at 230° C. and molded into a long film with a thickness of 150 μm using an extruder. Then, the substrate film A was produced by stretching this elongated film in the TD direction so as to have a thickness of 90 μm.

<Base film B>

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

<Base film C>

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

<Base film D>

Zinc ionomer (methacrylic acid content 11%, isobutyl methacrylate content 9%, softening point 64° C. , a melting point of 83° C., a density of 0.95 g/cm 3 , and a zinc ion content of 4% by mass) were melted at 230° C. and molded into a long film with a thickness of 150 μm using an extruder. Then, the substrate film D was produced by stretching this elongated film in the TD direction so as to have a thickness of 90 μm.

<Base film E>

Resin beads obtained by mixing a hydrogenated styrene-based thermoplastic elastomer and polypropylene (PP) at a compounding ratio of 52:48 were melted at 200° C. and molded into a long film with a thickness of 150 μm using an extruder. Then, the substrate film E was produced by stretching this elongated film in the TD direction so as to have a thickness of 90 μm.

<Base film F>

Resin beads obtained by mixing a hydrogenated styrene-based thermoplastic elastomer and polypropylene (PP) at a compounding ratio of 64:36 were melted at 200° C. and molded into a long film with a thickness of 150 μm using an extruder. Then, the base film F was produced by stretching this elongated film in the TD direction so as to have a thickness of 90 μm.

<Base film G>

The thickness of the elongated film was 150 μm, and the base film G was produced in the same manner as the base film A except that the elongated film was stretched in the MD direction so as to have a thickness of 90 μm.

<Base film H>

The thickness of the elongated film was 150 μm, and the base film H was produced in the same manner as the base film D except that the elongated film was stretched in the MD direction so as to have a thickness of 90 μm.

<Base Film I>

The thickness of the long film was made into 90 micrometers, and it carried out similarly to the base film A except having not performed the stretching process of this long film, and produced the base film I.

<Base Film J>

The thickness of the elongated film was 90 μm, and the stretching process of the elongated film was not performed, and the base film J was produced in the same manner as the base film D.

<Base film K>

The thickness of the elongated film was 90 μm, and the stretching process of the elongated film was not performed, and the base film K was produced in the same manner as the base film E.

<Base film L> The thickness of the elongated film was 90 micrometers, and it carried out similarly to the base film F except having not performed the stretching process of this elongated film, and produced the base film L.

<Base film M>

The thickness of the elongated film was 110 μm, and the base film M was produced in the same manner as the base film A except that the elongated film was stretched in the TD direction so as to have a thickness of 90 μm.

<Base film N>

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

(2) Preparation of acrylic copolymer

As an acrylic copolymer (A1) having a functional group, it is prepared from 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and methacrylic acid. The ratio of 2-ethylhexyl acrylate is 60 mol%, and the mass average A copolymer with a molecular weight of 700,000. Next, 2-isocyanatoethyl methacrylate was added so that the iodine value might become 25, and an acrylic copolymer having a glass transition temperature of −50° C., a hydroxyl value of 10 mgKOH/g, and an acid value of 5 mgKOH/g was prepared.

(3-1) Preparation of Adhesive Composition A

Add 100 parts by mass of epoxy resin "1256" (manufactured by Mitsubishi Chemical Corporation, bisphenol A type phenoxy resin, epoxy equivalent 7500), epoxy resin "828" (trade name manufactured by Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 220, specific gravity 1.17) 100 parts by mass, curing agent "DICY7" (manufactured by Mitsubishi Chemical Corporation, dicyandiamide) 4 parts by mass, and "curezol 2PZ" (Shikoku Kasei Co., Ltd. product name, 2-phenyl-4,5-dihydroxymethylimidazole) 0.4 parts by mass, MEK was added, and stirred until uniform. Furthermore, the varnish of the adhesive composition was obtained by filtering this with a 100-mesh filter, and performing vacuum defoaming.

(3-2) Preparation of Adhesive Composition B

40 parts by mass of epoxy resin "1002" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin, epoxy equivalent 600), epoxy resin "806" (trade name, bisphenol F-type epoxy resin, epoxy equivalent 160, specific gravity 1.20) 100 parts by mass, curing agent "Dyhard100SF" (trade name, dicyandiamide manufactured by Degussa) 5 parts by mass, silica filler "SO-C2" (Admafine Co., Ltd. Composition of 200 parts by mass of the manufacturer's trade name, average particle diameter of 0.5 μm) and 3 parts by mass of "Aerosil R972" (trade name of Japan Aerosil Co., Ltd., average particle diameter of primary particle diameter of 0.016 μm) as a silica filler , add MEK, stir and mix to make a homogeneous composition.

100 parts by mass of phenoxy resin "PKHH" (trade name manufactured by INCHEM Corporation, mass average molecular weight 52,000, glass transition temperature 92°C) and "KBM-802" (product manufactured by Shin-Etsu Silicon Corporation) as a coupling agent were added thereto. name, mercaptopropyltrimethoxysilane) 0.6 parts by mass, and "CUREZOL 2PHZ-PW" (trade name of Shikoku Chemicals Co., Ltd., 2-phenyl-4,5-dihydroxymethylimidazole decomposed Temperature 230°C) 0.5 parts by mass, stirred and mixed until uniform. Furthermore, the varnish of the adhesive composition was obtained by filtering this with a 100-mesh filter, and performing vacuum defoaming.

<Example 1>

5 parts by mass of coronate L (manufactured by Japan Polyurethane) as a polyisocyanate was added to 100 parts by mass of the above-mentioned acrylic copolymer, and 3 parts by mass of Esacure KIP 150 (manufactured by Lamberti Co.) was added as a photopolymerization initiator, and the resulting mixture was dissolved. An adhesive composition was prepared by stirring in ethyl acetate.

Next, the pressure-sensitive adhesive composition was applied to a release liner formed of a polyethylene terephthalate film subjected to mold release treatment so that the thickness after drying was 10 μm, and dried at 110° C. for 3 minutes. It is bonded to the base film, and the pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is formed on the base film is produced.

Next, the above-mentioned adhesive composition A was applied to a release liner formed of a polyethylene terephthalate film subjected to mold release treatment so that the thickness after drying became 20 μm, and dried at 110° C. for 5 minutes. , and an adhesive film in which an adhesive layer was formed on a release liner was produced.

The pressure-sensitive adhesive sheet is cut into a shape shown in FIG. 3 and the like that can be attached to the ring frame so as to cover the opening. In addition, the adhesive film is cut into a shape as shown in FIG. 3 etc. that can cover the back surface of the glass. Then, as shown in FIG. Combined to make tapes for glass processing.

<Examples 2-8, Comparative Examples 1-6>

Except having used the base film and adhesive composition described in Table 1, the tape for glass processing of Examples 2-8 and Comparative Examples 1-6 was produced by the method similar to Example 1.

The adhesive tapes of the glass processing tapes of Examples/Comparative Examples were cut to have a length of 24 mm (the direction in which the amount of deformation was measured) and a width of 5 mm (the direction perpendicular to the direction in which the amount of deformation was measured) to prepare samples. piece. For the obtained sample piece, using a thermomechanical properties testing machine (manufactured by Rigaku Co., Ltd., trade name: TMA8310), the tensile load method was used to measure MD and TD due to temperature in two directions under the following measurement conditions. out of shape.

(measurement conditions)

Measuring temperature: -60～100℃

Heating rate: 5°C/min

Measured load: 19.6mN

Ambient gas: nitrogen environment (100ml/min)

Sampling: 0.5s

Fixture spacing: 20mm

Then, the thermal deformation rate was calculated by the following formula (1), and the average value of the thermal deformation rate per 1° C. between 40° C. and 80° C. in the MD direction and the TD direction was obtained, and the sum was 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 Chip Defects]

With the method shown below, glass was divided|segmented into chips about each tape for glass processing of the said Example and the said comparative example, and chip defect was evaluated.

Carry out the following procedures:

(a) a step of irradiating a portion of the glass to be divided with laser light to form a modified region by multiphoton absorption inside the glass,

(b) A step of bonding the adhesive layer of the glass processing tape to the glass while heating the glass to 70 to 80° C.,

(c) dividing the above-mentioned glass and the above-mentioned adhesive layer along the dividing line by expanding the above-mentioned tape for glass processing to obtain a plurality of chips with an adhesive film,

(d) The portion of the above-mentioned glass processing tape that does not overlap the above-mentioned chip (annular region between the region where the chip exists and the ring frame) is heated and shrunk, thereby removing the adhesive tape in the expanding step (c). resulting slack, the process of maintaining the chip spacing, and

(e) The process of picking up the said chip|tip with the said adhesive bond layer attached from the adhesive layer of the tape for glass processing.

In addition, in (b) process, glass is bonded to the tape for glass processing so that the dividing line of glass may follow the MD direction of a base film, and a TD direction.

In step (c), use DDS2300 manufactured by Disco Co., Ltd. to press down the ring frame for dicing attached to the tape for glass processing by using the expansion ring of DDS2300 manufactured by Disco Co., Ltd. The portion of the glass that does not overlap the glass is pressed to the circular push-up member, thereby implementing expansion. As conditions of the step (c), the amount of expansion was adjusted so that the expansion speed became 300 mm/sec and the expansion height became 10 mm. Here, the amount of expansion refers to the amount of change in the relative position of the ring frame and the push-up member before and after the push-down. The chip size is set to 1×1 mm square.

(d) Step After re-expanding at room temperature under conditions of an expansion speed of 1 mm/sec and an expansion height of 10 mm, heat shrinkage treatment was performed under the following conditions.

[Condition 1]

Heater set temperature: 220°C

Hot air volume: 40L/min

Distance between heater and tape for glass processing: 20mm

Heater rotation speed: 7°/sec

[Condition 2]

Heater set temperature: 220°C

Hot air volume: 40L/min

Distance between heater and tape for glass processing: 20mm

Heater rotation speed: 5°/sec

The tape for glass processing of Examples 1-8 and Comparative Examples 1-6 was picked up after the said (g) process, and the presence or absence of a chip defect was evaluated. Under both conditions of condition 1 and condition 2 of the above (g) process, the chip defect that does not interfere with the adjacent chip when the pick-up target chip is lifted is regarded as an excellent product, and is evaluated as "◎"; Chip defects caused by interference with adjacent chips, but under condition 2, chip defects occurred and the occurrence rate was less than 1% as good products, evaluated as "○"; under condition 2 due to interference with adjacent chips Chip defects caused by the occurrence rate of 1% or more and less than 3% are evaluated as "△" as good products; chips caused by interference with adjacent chips under both conditions 1 and 2 A configuration in which the occurrence rate of defects was 3% or more was regarded as a defective product and evaluated as "x". The results are shown in Tables 1 and 2.

It should be noted that, in the evaluation, as shown in FIG. 6, for the periphery of the chip 50a at the rightmost end in FIG. 6, around the leftmost chip 50b in FIG. 6 , around the chip 51 at both ends without a defect in the TD direction of the adhesive tape, and around the chip 52 in the center, each 100 chips were picked up and evaluated.

[Measurement of transmittance of adhesive layer]

The transmittance was measured about the adhesive bond layer of the said Example and the said comparative example by the method shown below.

After bonding the 20-micrometer-thick adhesive bond layer formed on the release liner to glass, the release liner was peeled off, and the sample of the glass containing an adhesive bond layer was produced. For glass and glass containing an adhesive layer, let light intrude in the direction normal to the glass surface, and use a spectrophotometer (manufactured by Hitachi High-Technologies, spectrophotometer U-4100 solid sample measurement system) to measure The light transmittance of light of 550 nm to glass at 25° C. was calculated from the following formula (2) to calculate the transmittance of the adhesive bond layer. The results are shown in Tables 1 and 2.

The light transmittance of the adhesive layer I(%)=I1/I0 (2)

I1(%): Light transmittance of glass 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 before processing [μm] 150 180 215 150 150 150 150 150 Thickness after processing [μm] 90 90 90 90 90 90 90 90 Average value of thermal deformation rate in MD direction -1.0 -0.6 0.1 1.0 1.2 0.7 -6.7 -2.4 Average value of thermal deformation rate in TD direction -7.1 -7.9 -8.5 -4.6 -3.3 -1.6 3.0 2.3 The sum of the average values of thermal deformation rates in MD and TD directions -8.1 -8.5 -8.4 -3.6 -2.1 -0.9 -3.7 -0.1 Chip defect evaluation results ◎ ◎ ◎ ○ △ △ ○ △ Transmittance 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 l J K L m N adhesive composition A A A A A A Thickness before processing [μm] 90 90 90 90 110 120 Thickness after processing [μm] 90 90 90 90 90 90 Average value of thermal deformation rate in MD direction -1.4 0 0.3 0.8 -1.3 -1.2 Average value of thermal deformation rate in TD direction 3.6 2.6 0.9 0.8 2.0 1.3 The sum of the average values of thermal deformation rates in MD and TD directions 2.1 2.6 1.3 1.6 0.7 0.1 Chip defect evaluation results x x x x x x Transmittance of adhesive layer 90% 90% 90% 90% 90% 90%

As shown in Table 1, for the tapes for glass processing of Examples 1 to 8, the MD direction of the adhesive tape is measured at the temperature rise of 40°C to 80°C by a thermomechanical characteristic testing machine. The sum of the average value of the thermal deformation rate and the average value of the thermal deformation rate per 1 °C between 40 °C and 80 °C measured by a thermomechanical characteristic testing machine in the TD direction at the time of temperature rise is a negative value, so it can be suppressed well. Chip defects during pick-up due to contact between adjacent chips.

On the other hand, as for the glass processing tapes of Comparative Examples 1 to 6, as shown in Table 2, the MD direction of the adhesive tape is measured at the time of temperature rise by a thermomechanical characteristic tester between 40°C and 80°C. The sum of the average value of the thermal deformation rate per 1°C and the average value of the thermal deformation rate per 1°C between 40°C and 80°C measured by the thermomechanical characteristic testing machine in the TD direction when the temperature rises is not a negative value, Therefore, it is a result of poor suppression of the chip defect at the time of pick-up accompanying contact with an adjacent chip.

Explanation of reference signs

10: Tape for glass processing;

11: Substrate film;

12: adhesive layer;

13: adhesive layer;

22: push up components;

28: heating shrinkage area;

29: warm air nozzle.

Claims (3)

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 a uniform and isotropic extensibility, is formed from an ionomer resin or a mixed resin composition of polypropylene and a styrene-butadiene copolymer, and has a thickness of 70 to 200 [ mu ] m,

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,

the sum of the average value of the thermal deformation rates per 1 ℃ at 40-80 ℃ measured by a thermomechanical property tester in the MD direction and the average value of the thermal deformation rates per 1 ℃ at 40-80 ℃ measured by a thermomechanical property tester in the TD direction is a negative value;

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

an adhesive layer 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 550nm,

the MD direction is a flow direction during film formation, 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 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,

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

an adhesive layer 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 550nm,

the MD direction is a flow direction during film formation, and the TD direction is a direction perpendicular to the MD direction.

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.

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