TWI387536B - Self-rolling laminated sheet and self-rolling pressure-sensitive adhesive sheet - Google Patents

Abstract

79 SELF-ROLLING LAMINATED SHEET AND SELF-ROLLING PRESSURE- SENSITIVE ADHESIVE SHEET ABSTRACT OF THE DISCLOSURE THE PRESENT INVENTION RELATES TO A SELF-ROLLING PRESSURE-SENSITIVE ADHESIVE SHEET, 5 COMPRISING A SHRINKABLE FILM LAYER WHICH IS CONTRACTIBLE IN AT LEAST ONE AXIAL DIRECTION, A RESTRICTION LAYER RESTRICTING A CONTRACTION OF THE SHRINKABLE FILM LAYER, THE RESTRICTION LAYER BEING DISPOSED ON A SIDE OF THE SHRINKABLE FILM LAYER; AND A PRESSURE-SENSITIVE ADHESIVE LAYER DISPOSED ON THE SIDE OF THE RESTRICTION LAYER WHICH IS OPPOSITE TO THE SIDE ON WHICH THE SHRINKABLE FILM LAYER IS DISPOSED, THE SELF-ROLLING PRESSURE-SENSITIVE 10 ADHESIVE SHEET BEING A RELEASABLE PRESSURE-SENSITIVE ADHESIVE SHEET, IN WHICH THE PRESSURE-SENSITIVE ADHESIVE LAYER OR THE PRESSURE-SENSITIVE ADHESIVE LAYER AFTER AN ADHESIVENESS DECREASING TREATMENT HAS A PRESSURE-SENSITIVE ADHESIVE POWER (I 80' PEELING, AGAINST A SILICON MIRROR WAFER, TENSILE SPEE& 300 MM/MIN) OF 6.5 NII 0 MM OR LESS, AND IN WHICH THE SELF-ROLLING PRESSURE-SENSITIVE ADHESIVE SHEET ROLLS UP IN ONE ,15 DIRECTION FROM AN END TO FORM ONE TUBULAR ROLL OR ROLLS UP FROM TWO OPPOSING ENDS TOWARD A CENTER OF THE TWO OPPOSING ENDS TO FORM TWO TUBULAR ROLLS, WHEN THE SELF-ROLLING PRESSUIC-SENSITIVE SHEET IS STIMULATED TO INDUCE THE CONTRACTION OF THE SHRINKABLE FILM LAYER. THE SELF-ROLLING PRESSURE-SENSITIVE ADHESIVE SHEET CAN BE VERY EASILY PEELED OFF FROM AN ADHEREND WITHOUT CAUSING A DAMAGE OR A CONTAMINATION ON THE ADHEREND, EVEN 20 WHEN IT IS ADHERED TO AN ADHEREND OF A RELATIVELY LOW STRENGTH.

Description

Self-rolling laminated sheet and self-rolling pressure sensitive adhesive sheet

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a self-rolling laminated sheet and a self-rolling pressure-sensitive adhesive sheet which can form a tubular reel spontaneously in a main shrinking axis direction, for example, by heat from one end. The self-rolling pressure-sensitive adhesive sheet is suitable for use as, for example, a pressure-sensitive adhesive sheet that can be released, such as a pressure-sensitive adhesive sheet for temporary wafer fixing or a pressure-sensitive adhesive sheet for wafer protection, for use in a semiconductor In the processing of wafers or the like. Further, the self-rolling laminated sheet is suitable as, for example, a supporting base material for a pressure-sensitive adhesive layer in a self-rolling pressure-sensitive adhesive sheet.

Recently, in semiconductor materials, the demand for lighter and thinner materials is increasing. In wafers for semiconductors, the thickness needs to be reduced to 100 microns or even less, but this thin wafer is quite brittle and prone to cracking. Therefore, in wafer processing, a method of supporting a wafer on a temporarily fixed pressure-sensitive adhesive sheet and releasing and recovering the wafer after necessary processing has been employed.

Such temporary fixed pressure sensitive adhesive sheets typically comprise an energy ray curable pressure sensitive adhesive layer and are used in a method comprising the steps of: adhering it to a wafer, followed by performing on a temporarily fixed wafer, such as After the polishing or the dicing process, the pressure-sensitive adhesive layer is cured by irradiation of energy rays, and the pressure-sensitive adhesive layer having the reduced pressure-sensitive adhesive force is peeled off from the wafer. However, the pressure-sensitive adhesive sheet whose pressure-sensitive adhesive force is lowered by the irradiation of the energy ray is still adhered to the wafer surface by atmospheric pressure. Therefore, in order to peel off the pressure-sensitive adhesive sheet from the wafer, for example, an operation of pulling the pressure-sensitive adhesive sheet apart is required, but this operation is easy, for example, problems such as edge breakage or wafer cracking due to stress during operation. In addition, when the thickness of the wafer is reduced after grinding (for example, when reduced to about 25 microns), the end edge of the pressure-sensitive adhesive sheet attached to the wafer protrudes more outward than the edge of the wafer. Therefore, there is a risk that the protruding portions adhere to the surface of the table or the portion of the square cutting tape provided on the polishing surface of the wafer, and the like, which causes difficulty in peeling.

Japanese Patent No. 3073239 discloses a pressure-sensitive adhesive sheet comprising an energy ray-curable pressure-sensitive adhesive layer and a heat-shrinkable film in a layered structure. According to the pressure-sensitive adhesive sheet, when the heat-shrinkable sheet shrinks upon irradiation with an energy ray, it is possible to prevent, for example, elongation or wrinkles in the sheet when the ultraviolet light is irradiated. However, the peelability of the pressure-sensitive adhesive sheet from the wafer is still insufficient.

JP-A-2000-129227 discloses a pressure-sensitive adhesive sheet for protecting a semiconductor wafer formed of a shrinkable film, a rigid film, and an energy ray-curable pressure-sensitive adhesive layer. According to the pressure-sensitive adhesive sheet, the adhesive force of the pressure-sensitive adhesive layer is lowered by the irradiation energy ray, and the shrinkable film can be shrunk in a desired manner, thereby causing deformation in the pressure-sensitive adhesive sheet and reducing the adhesion between the wafer and the pressure-sensitive adhesive layer. The contact area is such that the pressure sensitive adhesive sheet can be easily peeled off from the wafer. However, since the shrinkage of the shrinkable film occurs in a plurality of directions, the heated pressure-sensitive adhesive sheet is usually folded on the surface of the wafer, thereby making the peeling operation difficult. In general, even a commercially available uniaxial shrinkable film may be in an axis different from the main contraction axis due to residual stress at the time of manufacture or due to stress or thermal strain applied to the pressure-sensitive adhesive sheet during the manufacturing process. A secondary contraction (one or more contractions with relatively weak contractile forces) is caused, and the contraction occurs with a combination of such contractions.

When the area of the adherend is small, the deformation of the pressure-sensitive adhesive sheet caused by the shrinkage this time is small, so that the damage at the time of peeling tends to occur less frequently. However, as the size of the adherend increases, the secondary shrinkage also increases, and eventually the shrinkage in the direction of the main shrink axis is hindered. In particular, in a pressure-sensitive adhesive sheet having a size generally used for wafers, such suppression of shrinkage in the main shrinkage axis direction is liable to occur, and thus, such as incomplete peeling (some of which are pressure-sensitive adhesive sheets) After sticking to the wafer after peeling, the adhesive body is broken due to uneven stress during shrinkage, and the wafer is cured and the self-inductive pressure-sensitive adhesive sheet is contaminated by the pressure-sensitive adhesive. Further, it has been found that in the two-layer structure of the substrate and the pressure-sensitive adhesive, the warpage generated after the wafer is polished is too large, so that the handling property thereof is extremely poor.

Patent Reference 1: Japanese Patent No. 3073239, Patent Reference 2: JP-A-2000-129227

An object of the present invention is to provide a pressure-sensitive adhesive sheet which can be peeled off from an adherend relatively easily without causing damage or contamination of the adherend even when it is adhered to a relatively low-strength adhesive.

Another object of the present invention is to provide a laminated sheet which is suitable as a supporting base material for a pressure-sensitive adhesive sheet having the above-mentioned satisfactory characteristics.

Another object of the present invention is to provide a pressure sensitive adhesive sheet capable of suppressing wafer warpage caused by wafer polishing, which is most suitable for use as a pressure sensitive adhesive sheet when temporarily wafer fixing, and to provide a laminated sheet. It is used as a support substrate for pressure-sensitive adhesive sheets.

The inventors believe that in order to achieve the above object, there is a need for a pressure-sensitive adhesive sheet having an easily peelable function. When manually performing the operation of peeling the pressure-sensitive adhesive sheet from the adhesive body, first, in order to provide a peeling starting point, the tape of the edge portion of the adhesive body is picked up, and then the tape is pulled out to be peeled off. However, when the fragile adhesive is used, the tape is not picked up, and the tape is worn, that is, the peeling angle is maximized to minimize the peeling stress. Therefore, in many cases, a peeling starting point is provided to minimize the peeling stress, and the peeling angle is maximized without damaging the adhering body, even when the stripping angle is maintained to the maximum after the strip is peeled off, the pressure is applied. Adhesive sheets can be peeled off from fragile adherends.

Therefore, the inventors believe that when it is subjected to heat or other stimuli and has an easy peeling property, if the tape is deformed as a blanket to deform the shape when the tape is peeled off (the latter body is so deformed as a "tubular roll"), A pressure-sensitive adhesive tape is obtained for this purpose. The reason for this is that the peeling which induces this deformation is based on maintaining the peeling angle at the maximum at the time of peeling, and keeping the peeling stress on the adhering body to a minimum, that is, the possibility of impairing the weakly adhering body can be minimized. Further, the possibility of the pressure-sensitive adhesive which is transferred to the adherend by peeling is also lowered, and the small peeling stress can also reduce the possibility of contamination of the adherent by peeling. Also, since the peeling stress can be minimized, even when the pressure sensitive adhesive is adhered to the portion on the wafer grinding surface side, the risk of damaging the wafer can be lowered.

Therefore, a material test is performed to understand the tubular reel formed by thermal stimulation, and as a result, it has been found that when the shrinkable film layer provides a thermal stimulus, it can be shrunk in at least one direction, preferably 30% or more, and a restriction shrinkage. The confinement layer of the film layer is laminated thereon, and more preferably, the confinement layer is composed of an elastic layer and a laminate of a rigid film layer, and each layer has its predetermined properties, when subjected to heat or other stimuli. The contraction force of the shrink film and the repulsive force against the contraction force of the shrink film in the restraining layer are the driving force for lifting the outer edge portion (end portion), whereby the laminated sheet is oriented from one end or from the opposite ends in one direction The center (the center of the end portions) is spontaneously rolled up (where the shrinkable film layer is located inside) to form one or two tubular rolls.

Furthermore, it has also been found that when the releasable pressure-sensitive adhesive sheet (having a pressure-sensitive adhesive layer disposed on the side of the limiting layer of the laminated sheet) adheres to the adhesive body, and through the pressure-sensitive adhesive layer, the fixing such as the adhesive body is completed. After protection, and other predetermined effects, such as heat or other stimuli are applied during release to promote shrinkage of the shrinkable film layer to lose adhesion, the outer edge portion (end portion) is likewise lifted, thereby laminating the sheet In the horizontal direction, spontaneously rolling up from one end or from two opposite ends toward the center (the center of both ends) (in which the shrinkable film layer is located inside), forming one or two tubular reels, and feeling The pressure-sensitive adhesive sheet can be easily and cleanly peeled off from the adhesive body, so that the adhesive body is not damaged by the peeling stress thereon. It has also been found that such a configuration significantly reduces the contamination of the adherend due to peeling. The present invention has been completed on the basis of such findings.

In other words, the present invention relates to the following items.

(1) A self-rolling laminated sheet comprising: a shrinkable film layer which is contractible in at least one axial direction; and a restriction layer which restricts shrinkage of the shrinkable film layer, the restriction layer being disposed on the shrinkable film layer On one side, wherein when the self-rolling laminated sheet is stimulated to induce shrinkage of the shrinkable film layer, the self-rolling laminated sheet is rolled up from one end in one direction to form a tubular reel, or from opposite ends Two tubular reels are formed by rolling up toward the center of the opposite ends.

(2) The self-rolling laminated sheet according to (1), wherein the shrinkable film layer comprises heat shrinkable having a heat shrinkage ratio of 30 to 90% in a main shrinkage direction at a temperature in the range of 70 to 180 °C membrane.

(3) The self-rolling laminated sheet according to (1), wherein the constraining layer comprises an elastic layer on the side of the shrinkable film layer and a rigid film layer on the side opposite to the side of the shrinkable film layer.

(4) The self-rolling laminated sheet according to item (3), wherein the elastic layer has a product of a shear modulus at 80 ° C and a thickness in the range of 1 to 1000 N/m.

(5) The self-rolling laminated sheet according to (3), wherein the rigid film layer has a product of a Young's modulus at 80 ° C and a thickness of 3.0 × 10 ⁵ Newtons/meter or less.

(6) The self-rolling laminated sheet according to (3), wherein the elastic layer is formed of a crosslinked acrylic pressure sensitive adhesive.

(7) The self-rolling laminated sheet according to (1), wherein when the self-rolling laminated sheet is rolled up to stimulate the shrinkage of the shrinkable film layer of the self-rolling laminated sheet to form a tubular roll, The tubular reel formed has a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-shaped tubular reel and the length of the L-series self-rolling laminated sheet in the rolling direction.

(8) The self-rolling laminated sheet according to (1), wherein the self-rolling laminated sheet is rolled up to form two tubular reels after stimulating the shrinkage of the shrinkable film layer caused by the self-rolling laminated sheet The tubular reels formed each have a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-shaped tubular reel and the length of the L-series self-rolling laminated sheet in the rolling direction.

(9) A self-rolling pressure-sensitive adhesive sheet comprising: a shrinkable film layer which is contractible in at least one axial direction; and a restriction layer which restricts shrinkage of the shrinkable film layer, the restriction layer being provided on the shrinkable film a pressure sensitive adhesive layer disposed on one side of the layer and disposed on a side of the restricting layer opposite to the side on which the shrinkable film layer is disposed, the self-rolling pressure sensitive adhesive film being a release pressure sensitive adhesive sheet Wherein the pressure-sensitive adhesive layer or the pressure-sensitive adhesive layer after the reduced adhesion treatment has a pressure-sensitive adhesive force (tensile speed of 300 mm/min for a mirror wafer 180° peeling: 300 mm/min) is 6.5 Newtons /10 mm or less, and when the self-rolling pressure-sensitive adhesive sheet is stimulated to induce shrinkage of the shrinkable film layer, the self-rolling pressure-sensitive adhesive sheet is rolled up from one end in one direction to form a tubular reel, Or two tubular reels are formed by rolling up from the opposite ends toward the center of the opposite ends.

(10) The self-rolling pressure-sensitive adhesive sheet according to (9), wherein the shrinkable film layer comprises a heat shrinkage ratio of 30 to 90% in a main shrinkage direction at a temperature in the range of 70 to 180 °C Heat shrinkable film.

(11) The self-rolling pressure-sensitive adhesive sheet according to (9), wherein the constraining layer comprises an elastic layer on the side of the shrinkable film layer and a rigid film layer on the side opposite to the side of the shrinkable film layer.

(12) The self-rolling pressure-sensitive adhesive sheet according to (11), wherein the elastic layer has a product of a shear modulus at 80 ° C and a thickness in the range of 1 to 1000 N/m.

(13) The self-rolling pressure-sensitive adhesive sheet according to (11), wherein the rigid film layer has a product of a Young's modulus at 80 ° C and a thickness of 3.0 × 10 ⁵ N/m or less.

(14) The self-rolling pressure-sensitive adhesive sheet according to (11), wherein the elastic layer is formed of a crosslinked acrylic pressure sensitive adhesive.

(15) The self-rolling pressure-sensitive adhesive sheet according to (9), wherein the pressure-sensitive adhesive layer is formed of an energy ray-curable pressure-sensitive adhesive.

(16) The self-rolling pressure-sensitive adhesive sheet according to item (9), wherein the self-rolling pressure-sensitive adhesive sheet is rolled up after being stimulated by the shrinkage of the shrinkable film layer caused by the self-rolling pressure-sensitive adhesive sheet to form In the case of a tubular reel, the tubular reel formed has a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-shaped tubular reel and the L-series self-rolling pressure-sensitive adhesive sheet are in the rolling direction. The length.

(17) The self-rolling pressure-sensitive adhesive sheet according to (9), wherein the self-rolling pressure-sensitive adhesive sheet is rolled up to form a stimulus for inducing shrinkage of the shrinkable film layer of the self-rolling pressure-sensitive adhesive sheet to form In the case of two tubular reels, the tubular reels each have a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-shaped tubular reel and the L-series self-rolling pressure-sensitive adhesive sheet are in the rolling direction. The length in the middle.

(18) A method of processing an article, comprising: adhering a self-rolling pressure-sensitive adhesive sheet according to (9) to an object to temporarily fix the object, and then processing the article; and reducing the pressure-sensitive adhesive sheet The pressure-sensitive adhesive force and the pressure-sensitive adhesive sheet provide a stimulus for inducing shrinkage of the shrinkable film layer, thereby causing the pressure-sensitive adhesive sheet to spontaneously roll up from one end in one direction to form a tubular reel, or two The opposite ends are rolled up toward the center of the opposite ends to form two tubular reels, and thus are peeled from the article; and a finished article is obtained.

The self-rolling pressure-sensitive adhesive sheet and the laminated sheet according to the present invention can be similarly rolled up even when the length L of the sheets is increased in the rolling direction.

In the present specification, the shrinkage ratio (%) means a value calculated by the following equation.

[(size before shrinkage - size after shrinkage) / (size before shrinkage)] × 100

In this regard, unless otherwise specified, it refers to the rate of shrinkage in the primary shrinkage axis.

The self-rolling pressure-sensitive adhesive sheet of the present invention is subjected to a predetermined processing by an adhesive body temporarily fixed by an adhesive force, and is driven by a stimulus such as heat which induces shrinkage, and spontaneously rolls up under the peeling of the self-adhesive body ( Typically, the tubular reel is formed from the end portion (one end portion or opposite end portions) in the direction of the main contraction axis so that it can be extremely easily removed from the surface of the adherent without damaging the adherend or It is contaminated by incomplete peeling. Therefore, it is useful as a releasable pressure-sensitive adhesive sheet which is to be adhered particularly to a fragile adherend. In addition, the self-rolling laminated sheet of the present invention is spontaneously rolled up from the end portion (one end portion or two opposite end portions) to form a tubular reel in the direction of the main shrinking axis when stimulated by the induced shrinkage, so that It can be advantageously utilized as a supporting base material for the pressure-sensitive adhesive layer in the aforementioned self-rolling pressure-sensitive adhesive sheet.

In the present specification, "self-rolling property" means a property in which an object having such a property is spontaneously rolled up by applying a stimulus that induces contraction such as heat, light, and electrical stimulation.

"Self-rolling laminated sheets" are laminated sheets with self-rolling properties. When a self-rolling slab is subjected to a stimulus that induces contraction, it spontaneously rolls up in one direction from one end or from the opposite ends toward the center of the opposite ends to form one or two tubular reels.

The "self-rolling pressure-sensitive adhesive sheet" is a pressure-sensitive adhesive sheet having a self-rolling property, and includes a self-rolling laminated sheet and a pressure-sensitive adhesive layer provided on a surface of one of the limiting layers constituting the self-rolling laminated sheet. . When the pressure-sensitive adhesive force of the self-rolling pressure-sensitive adhesive sheet is reduced or lost and the stimuli are induced to the self-rolling pressure-sensitive adhesive sheet, it is in one direction from one end or from the opposite ends to the opposite ends. The center is spontaneously rolled up to form one or two tubular reels.

Specific examples of the present invention will be described below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a self-rolling laminated sheet of the present invention. Fig. 2 is a schematic cross-sectional view showing an example of a self-rolling pressure-sensitive adhesive sheet. The self-rolling laminated sheet illustrated in Fig. 1 includes a shrinkable film layer 1 having a uniaxial shrinkage property and a laminated member for restricting the shrinkage of the shrinkable film layer 1. The confinement layer 2 is composed of an elastic layer 21 on the side of the shrinkable film layer 1 and a rigid film layer 22 on the side opposite to the side of the shrinkable film layer 1. Further, the pressure-sensitive adhesive sheet described in Fig. 2 is formed by laminating the pressure-sensitive adhesive layer 3 on the side of the rigid film layer 22 of the self-rolling laminated sheet described in Fig. 1. In this case, the self-rolling laminated sheet is used as a supporting base material for the self-rolling pressure-sensitive adhesive sheet.

The shrinkable film layer 1 may be a film layer that can be shrunk in at least one axial direction, and may be any one of a heat shrinkable film, a film exhibiting properties by light contraction, and a film which is contracted by electrical stimulation. . Among them, the shrinkable film layer 1 is preferably a heat shrinkable film from the viewpoint of operability. The shrinkable film layer 1 may have shrinkage properties only in one axial direction, or may have a main shrinkage property in a specific direction (one axial direction) and a direction in another direction (for example, a direction perpendicular to the aforementioned direction) Secondary contraction properties. The shrinkable film layer 1 may be configured as a single layer, or a composite layer formed of two or more layers.

The shrinkable film constituting the shrinkable film layer 1 has a shrinkage ratio in the main shrinkage direction of preferably 30 to 90%. In the case where the shrinkable film layer 1 is formed of a heat shrinkable film, the heat shrinkable film has a general temperature of 30 to a predetermined temperature (for example, 95 ° C, 140 ° C, etc.) in the range of 70 to 180 ° C. 90% shrinkage in the main shrinkage direction. In the shrinkable film constituting the shrinkable film layer 1, the shrinkage ratio in the direction other than the main shrinkage direction is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. The heat shrinkage property of the heat shrinkable film can be provided, for example, by subjecting a film extruded by an extruder to a stretching process.

Examples of the heat shrinkable film include a uniaxially stretched film prepared from a resin selected from, for example, one or more of the following: polyester such as polyethylene terephthalate, polyolefin such as polyethylene or polypropylene, poly drop Alkene, polyimine, polyamine, polyurethane, polystyrene, polydivinylidene chloride and polyvinyl chloride. Among them, based on satisfactory coating operability for pressure sensitive adhesives, polyester resins, polyolefin resins (including cyclic polyolefin resins) such as polyethylene, polypropylene or polycondensation A uniaxially stretched film formed of an olefin or a polyurethane resin is preferred. For such a heat shrinkable film, commercial products such as Space Clean manufactured by Toyobo Co., Fancy Wrap manufactured by Gunze Ltd., Torayfan manufactured by Toray Industries Ltd., Lumirror manufactured by Toray Industries Ltd., and Arton manufactured by JSR Corp. can be used. And Zeonore manufactured by Nippon Zeon Co.

In the case of using the self-rolling laminated sheet as the supporting base material of the energy ray-curable pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive layer which is irradiated with the energy ray through the heat-shrinkable film layer 1 to make the energy ray curable When cured, the heat-shrinkable film layer 1 should be composed of a material (for example, a resin having transparency) which can transmit a predetermined amount or more of energy rays.

The heat shrinkable film layer 1 has a thickness of usually 5 to 300 μm, preferably 10 to 100 μm. The excessive thickness of the heat-shrinkable film layer 1 increases the rigidity, whereby spontaneous rolling does not occur, but separation occurs between the heat-shrinkable film layer 1 and the confinement layer 2, which may cause destruction of the laminated member. . Further, it is known that a film of high hardness has a high elastic stress caused by residual stress generated by bonding, and thus it is easy to increase warpage when the wafer is made thin. The surface of the heat shrinkable film layer 1 can be subjected to general surface treatment, for example, chemical or physical treatment such as treatment with chromic acid, exposure to ozone, exposure to flame, exposure to high voltage spark, treatment with free radiation, or coating Primer materials (such as pressure sensitive adhesives) to improve adhesion and adhesion to adjacent layers.

The confinement layer 2 restricts the contraction of the shrinkable film layer 1 to induce a reaction force which becomes a driving force by generating a force which is coupled to the entire laminate to cause scrolling. Further, the confinement layer 2 is considered to suppress the secondary shrinkage of the shrinkable film layer 1 in a direction different from its main contraction direction, whereby even when it is called a uniaxial shrinkable film, it is not necessarily the only shrinkable The shrinkage direction of the film layer 1 can be concentrated in one direction. Therefore, when the laminated film is given a stimulus for inducing shrinkage of the shrinkable film layer 1, it is considered that the repulsive force against the contraction force of the shrinkable film layer 1 in the confinement layer 2 becomes the outer edge portion of the lifted laminated sheet (one end or two Driving force at the opposite end, whereby the laminated sheet is spontaneously rolled up in one direction or in a direction toward the center (generally in the direction of the main shrinkable axis of the heat shrinkable film) (where the shrinkable film layer 1 is located inside) ), forming a tubular reel. Further, the confinement layer 2 can prevent the shearing force generated by the shrinkage deformation of the shrinkable film layer 1 from being transmitted to the pressure-sensitive adhesive layer 3 or the adherend, thereby avoiding the pressure-sensitive adhesive having a reduced pressure-sensitive adhesive force upon release. The adhesive layer (for example, the cured pressure-sensitive adhesive layer) is cracked, the adhesive body is broken, or the adhesive body is ruptured by the pressure-sensitive adhesive layer.

The confinement layer 2 has elasticity and adhesion properties to the shrinkable film layer 1 (including pressure-sensitive adhesive properties) to exhibit a function of restricting shrinkage of the shrinkable film layer 1. Further, in order to smoothly form the tubular reel, the confinement layer 2 preferably has a specific toughness or rigidity. The confinement layer 2 may be configured to have a single layer or be composed of a plurality of layers in which functions are shared by a plurality of layers.

In the example illustrated in FIGS. 1 and 2, the confinement layer 2 is composed of an elastic layer 21 and a rigid film layer 22. The elastic layer 21 is preferably at the shrinkage temperature of the shrinkable film layer 1 (at the peeling temperature of the pressure-sensitive adhesive sheet when the self-rolling laminated sheet is used as a supporting base material for the self-rolling pressure-sensitive adhesive sheet) It is easily deformed, that is, in a rubbery state. However, the material exhibiting fluidity does not generate sufficient reaction force, and finally the shrinkable film shrinks by itself, so that deformation (spontaneous scrolling) cannot be caused. Therefore, the elastic layer 21 preferably has, for example, fluidity that is suppressed via three-dimensional crosslinking. In addition, the elastic layer 21 also exhibits a function of resisting the weaker force component in the uneven contraction force of the shrinkable film layer 1 due to its thickness to prevent shrinkage deformation caused by the weaker force component, thereby achieving a unique transformation. Contraction direction. The warpage generated after wafer polishing is considered to be caused when stress is applied to bond the pressure-sensitive adhesive sheet to the remaining wafer, and the remaining stress causes elastic deformation of the shrinkable film. However, the elastic layer also has the function of releasing this residual stress to reduce warpage.

Therefore, it is desirable that the elastic layer 21 be formed of a resin having a pressure-sensitive adhesive property and having a glass transition temperature of, for example, 50 ° C or less, preferably room temperature (25 ° C) or less, and more preferably 0 ° C or less. . The pressure-sensitive adhesive force of the elastic layer 21 on the side of the shrinkable film layer 1 is a value obtained by a 180 peel test (based on JIS Z 0237, drawing speed: 300 mm/min, 50 ° C), preferably 0.5. Newton/10 mm or more. An excessively low pressure-sensitive adhesive force causes peeling between the heat-shrinkable film layer 1 and the elastic layer 21.

Further, the shear modulus G of the elastic layer 21 is preferably from 1 × 10 ⁴ Pa to 5 × 10 ⁶ Pa (especially 0.05 × 10) in the range of temperature from room temperature to peeling temperature (for example, 80 ° C). ⁶ Pa to 3 × 10 ⁶ Pa). When the shear modulus is too small, the effect of converting the shrinkage stress of the shrinkable film layer into the stress required for scrolling becomes insufficient, and on the other hand, when the shear modulus is too large, the rolling ability becomes insufficient. In addition to the increase in hardness, the adhesiveness with high elasticity is generally insufficient, and thus the preparation of the laminate may be difficult. The thickness of the elastic layer 21 is preferably about 15 to 150 μm. When the thickness is too small, it is difficult to obtain the limiting property of the shrinkage of the shrinkable film layer 1, and the effect of releasing the stress is also reduced. Conversely, when the thickness is too large, the self-rolling property is deteriorated and the processing ability and economic efficiency are also improved. Reduced, this system is not expected. Therefore, the product of the shear modulus G (e.g., the value at 80 ° C) and the thickness of the elastic layer 21 (shear modulus G × thickness) is preferably from 1 to 1000 Newtons/meter, more preferably from 1 to 150. Newton/meter, and more preferably 1.2 to 100 Newtons/meter.

Further, in the case where the pressure-sensitive adhesive layer 3 is formed by the energy ray-curable pressure-sensitive adhesive layer, the elastic layer 21 is preferably formed of a material which can easily transmit energy rays in consideration of manufacturing properties and operational efficiency, and has It is used to obtain satisfactory formability of a film having a suitably selected thickness.

As the elastic layer 21, for example, a foamed material (foamed film) such as a urethane foam which is subjected to pressure-sensitive adhesion treatment on a surface (at least on the surface on the side of the shrinkable film layer 1) can be used. Or a resin film (including a sheet) of an acrylic foam or a non-foamed resin film of a rubber or a thermoplastic elastomer. The pressure-sensitive adhesive to be used in the pressure-sensitive adhesive treatment is not particularly limited, and it can be known as a pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a rubber type pressure-sensitive adhesive, or a vinyl alkyl group. Ether pressure sensitive adhesive, polyoxygen pressure adhesive, polyester pressure sensitive adhesive, polyimide pressure sensitive adhesive, urethane pressure sensitive adhesive, and styrene-diene block copolymer type One of the pressure sensitive adhesives or a combination of two or more of them. Specifically, for example, an acrylic pressure-sensitive adhesive can be advantageously used in consideration of adjustment of pressure-sensitive adhesive force. In this regard, the resin of the pressure-sensitive adhesive to be used for the pressure-sensitive adhesive treatment and the resin of the foamed film or the non-foamed resin film are preferably of the same type to obtain high affinity. For example, in the case of performing a pressure-sensitive adhesive treatment using an acrylic pressure-sensitive adhesive, an acrylic foam can be advantageously used as the resin film.

Further, the elastic layer 21 may be formed of a resin composition having an adhesive property itself such as a crosslinked acrylic pressure sensitive adhesive. The layer (pressure-sensitive adhesive layer) formed by such a cross-linking type acrylic pressure-sensitive adhesive or the like can be produced by a relatively simple method without requiring an individual pressure-sensitive adhesive treatment, and it is excellent in The productive and economic properties are advantageously used.

The crosslinked acrylic pressure-sensitive adhesive has a composition in which a crosslinking agent is added to an acrylic pressure-sensitive adhesive containing an acrylic polymer as a base polymer. Examples of the acrylic polymer include alkyl (meth)acrylates such as a C ₁ -C ₂₀ alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) a homopolymer or copolymer of butyl acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; and the aforementioned alkyl (meth)acrylate and another copolymerizable single a copolymer of the body, the other copolymerizable monomer comprising a carboxyl group-containing or anhydride group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid or maleic anhydride; a hydroxyl group-containing monomer Such as 2-hydroxyethyl (meth)acrylate; amine-containing monomers such as (meth)acrylic acid a porphyrin ester; a guanamine-containing monomer such as (meth) acrylamide; a cyano group-containing monomer such as (meth) acrylonitrile; or a (meth) acrylate having an alicyclic hydrocarbon group such as (meth)acrylic acid different ester.

With respect to the acrylic polymer, one or more C ₁ -C ₁₂ alkyl (meth)acrylates such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate and at least one selected from the group consisting of hydroxyl groups are preferred. a copolymer such as 2-hydroxyethyl acrylate and a copolymerizable monomer containing a carboxyl group or an acid anhydride group-containing monomer such as acrylic acid, or one or more C ₁ -C ₁₂ alkyl (meth)acrylates, having an alicyclic ring a (meth) acrylate of a hydrocarbon group, and a copolymer of at least one copolymerizable monomer selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing or acid anhydride group-containing monomer.

The acrylic polymer is prepared, for example, by photopolymerizing (for example, using ultraviolet light) a monomer component (and a polymerization initiator) in the absence of a solvent to a high-viscosity liquid prepolymer. The crosslinked pressure-sensitive adhesive composition can be obtained by adding a crosslinking agent to the prepolymer. The crosslinking agent can be added at the time of preparing the prepolymer. The crosslinked acrylic pressure-sensitive adhesive composition can also be obtained by adding a crosslinking agent and a solvent (not required in the case of using a solution of an acrylic polymer) to the monomer component or a solution thereof by polymerization. It is obtained by using an acrylic polymer.

The crosslinking agent is not particularly limited and can be used, for example, an isocyanate type crosslinking agent, a melamine type crosslinking agent, an epoxy type crosslinking agent, an acrylate type crosslinking agent (polyfunctional acrylate), or an isocyanate. The base (meth) acrylate is used for this purpose. Examples of the acrylic crosslinking agent include hexanediol diacrylate, 1,4-butanediol diacrylate, trimethylolpropane triacrylate, neopentyltetraol tetraacrylate, and dipentaerythritol Acrylate. Examples of the (meth) acrylate having an isocyanate group include ethyl 2-isocyanate acrylate and 2-isocyanatoethyl methacrylate. Among them, an ultraviolet (UV) reactive crosslinking agent such as an acrylate type crosslinking agent (polyfunctional acrylate) or a (meth) acrylate having an isocyanate group is preferred. The crosslinking agent is generally used in an amount of from 0.01 to 15 parts by weight, preferably from 0.05 to 12 parts by weight, per 100 parts by weight of the base polymer.

The crosslinked acrylic pressure sensitive adhesive may contain, in addition to the base polymer and the crosslinking agent, appropriate additives such as a crosslinking accelerator, an adhesive resin (such as a rosin derivative resin, a polyterpene resin, a petroleum resin, Or oil-soluble phenolic resin), tackifiers, plasticizers, fillers, anti-aging agents, and antioxidants.

Providing the crosslinked acrylic pressure-sensitive adhesive layer as the elastic layer 21 can be carried out simply by using a well-known method such as a casting method to form a crosslinked acrylic pressure-sensitive adhesive composition by adding a crosslinking agent The film is prepared to a prepolymer and is formed into a film of a desired thickness and area, and is again irradiated with light to cause a crosslinking reaction (and polymerization of unreacted monomers), thereby achieving desired properties. The elastic layer (crosslinked acrylic pressure-sensitive adhesive layer) having the self-inductive pressure-bonding property thus obtained can be used by directly adhering between the shrinkable film layer 1 and the rigid film layer 22. As the crosslinked acrylic pressure-sensitive adhesive layer, a commercial double-sided tape such as HJ-9150W (trade name) manufactured by Nitto Denko Corporation can also be used. Further, the crosslinking reaction can be carried out by performing light irradiation again after the film-like pressure-sensitive adhesive is adhered between the shrinkable film layer 1 and the rigid film layer 22.

The crosslinked acrylic pressure-sensitive adhesive layer which is provided as the elastic layer 21 may be obtained by dissolving the above-mentioned acrylic polymer and a crosslinking agent in a solvent by a crosslinking type acrylic pressure-sensitive adhesive composition. It is prepared by coating on the surface of the rigid film layer 22, and then adhering the shrinkable film layer 1 thereto and performing light irradiation. When the pressure-sensitive adhesive layer 3 is an energy ray-curable pressure-sensitive adhesive layer, the cross-linked acrylic pressure-sensitive adhesive is irradiated with energy rays for curing the release pressure-sensitive adhesive layer 3 (Light irradiation) can be cured (crosslinked).

The elastic layer 21 in the present invention may further include beads such as glass beads or resin beads. The addition of glass beads or resin beads to the elastic layer 21 facilitates the control of the pressure-sensitive adhesive properties and the shear modulus. The beads have, for example, an average particle size of from about 1 to 100 microns, preferably from 1 to 20 microns. The beads are used in an amount of 0.1 to 10 parts by weight, preferably 1 to 4 parts by weight, per 100 parts by weight of the entire elastic layer 21. An excessively large amount of addition deteriorates the pressure-sensitive adhesive property, and an excessively small amount tends to provide only an insufficient effect.

The rigid film layer 22 has a function of inducing a reaction force to the shrinkage force of the shrinkable film layer by imparting rigidity or toughness of the restriction layer 2, and further generates force coupling required for scrolling. When the shrinkable film layer 1 is subjected to a stimulus such as heat for inducing contraction, the presence of the rigid film layer 22 allows the laminated sheet or the pressure-sensitive adhesive sheet to smoothly roll spontaneously without intermediate stop or direction. Moving, thus forming a tubular reel having a regular shape.

Examples of the resin film constituting the rigid film layer 22 include films formed of one or more resins selected from the group consisting of polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene dicarboxylic acid. Ethylene glycol; polyolefin such as polyethylene or polypropylene; polyimine; polyamine; polyurethane; styrene resin such as polystyrene; polydivinylidene; and polyvinyl chloride. Among them, a polyester resin film, a polypropylene film, and a polyamide film are preferable because of satisfactory coating workability for a pressure-sensitive adhesive. The rigid film layer 22 may have a single layer or a composite layer formed of two or more layers. The rigid film constituting the rigid film layer 22 is not shrinkable and has, for example, a shrinkage ratio of 5% or less, preferably 3% or less, and more preferably 1% or less.

The product of the Young's modulus and the thickness (Young's modulus x thickness) of the rigid film layer 22 at the peeling temperature (for example, at 80 ° C) is preferably 3.0 × 10 ⁵ Newtons / m or less (for example, 1.0 × 10 ² to 3.0 × 10 ⁵ Newtons / meter), and more preferably 2.8 × 10 ⁵ Newtons / meter or less (for example, 1.0 × 10 ³ to 2.8 × 10 ⁵ Newtons / meter). When the product of the Young's modulus and the thickness in the rigid film layer 22 is too small, the effect of converting the shrinkage stress of the shrinkable film layer into the rolling stress is insufficient, and it can also deteriorate the directional shrinkage. On the other hand, when the product is too large, the scrolling may be suppressed due to rigidity. The Young's modulus of the rigid film layer 22 at the peeling temperature (for example, at 80 ° C) is preferably 3 × 10 ⁶ to 2 × 10 ¹⁰ Newtons / square meter, and more preferably 1 × 10 ⁸ to 1 × 10 ¹⁰ Newtons. / square meter. When the Young's modulus is too small, it is difficult to obtain a tubular reel that is rolled in an appropriate shape. Conversely, when the Young's modulus is too large, it is difficult to generate spontaneous scrolling. The rigid film layer 22 has a thickness of, for example, about 20 to 150 μm, preferably 25 to 95 μm, more preferably 30 to 90 μm. When the thickness is too small, it is difficult to obtain a tubular reel which is rolled in an appropriate shape. When the thickness is too large, the self-rolling property is deteriorated and the handling ability and economic efficiency are lowered, which is undesirable.

In the case where the pressure-sensitive adhesive layer 3 is formed of an energy ray-curable pressure-sensitive adhesive, the rigid film layer 22 is preferably formed of a material which can easily transmit energy rays in consideration of manufacturing properties and operational efficiency, and has a use. A satisfactory formability is obtained for a film having a suitably selected thickness.

In the above specific example, the confinement layer 2 is composed of the elastic layer 21 and the rigid film layer 22, but such a configuration is not essential. For example, the rigid film layer 22 can be omitted by providing an elastic layer 21 of suitable rigidity.

As the pressure-sensitive adhesive layer 3, a pressure-sensitive adhesive layer having a small pressure-sensitive adhesive force can be used, but it is preferable to use a release pressure-sensitive adhesive layer which has adhesiveness to adhere to the adhesive body, and has After the predetermined action is completed, the adhesion may be deteriorated or the adhesion may be lost by any means (reducing the adhesive treatment). The releasable pressure-sensitive adhesive layer can be formed in the same manner as it is known to release the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet. From the viewpoint of the self-rolling property, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive layer having a reduced adhesive treatment (stretching speed of a 180° peeling of a mirror wafer: 300 mm/min) It is, for example, 6.5 Newtons/10 mm or less (especially 6.0 Newtons/10 mm or less) at room temperature (25 ° C).

The pressure-sensitive adhesive layer 3 is preferably an energy ray-curable pressure-sensitive adhesive layer. The energy ray-curable pressure-sensitive adhesive layer may be formed of a material having a pressure-sensitive adhesive property and forming a three-dimensional network structure by irradiating an energy ray such as infrared light, visible light, ultraviolet light, X-ray or electron beam, thereby exhibiting high elasticity. As the material, an energy ray-curable pressure-sensitive adhesive can be used. The energy ray curable pressure sensitive adhesive comprises a compound that is chemically modified with an energy ray reactive functional group to provide energy ray curable properties, or an energy ray curable compound (or energy ray curable resin). Therefore, the energy ray-curable pressure-sensitive adhesive is preferably a basic component chemically modified by an energy ray-reactive functional group, or a compound capable of curing an energy ray (or an energy ray-curable resin) and a basic component. A composition formed by blending is formed.

As the base component, a pressure-sensitive adhesive such as a known pressure-sensitive adhesive (viscose) can be used. Examples of the pressure-sensitive adhesive include the use of a rubber type polymer such as natural rubber, polyisobutylene rubber, styrene-butadiene rubber, styrene-isoprene-styrene block copolymer rubber, reclaimed rubber, butyl rubber Polyisobutylene rubber or NBR as a base polymer rubber type pressure sensitive adhesive; polyoxygen type pressure sensitive adhesive; and acrylic pressure sensitive adhesive. Among them, an acrylic pressure sensitive adhesive is preferred. The base component may be formed of a single component or two or more components.

Examples of the acrylic pressure-sensitive adhesive include an adhesive using the following components as a base polymer: an alkyl (meth)acrylate such as a C ₁ -C ₂₀ alkyl (meth)acrylate such as (meth)acrylic acid a homopolymer or copolymer of an ester, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; and a methyl methacrylate and another copolymerizable monomer (for example, a carboxyl group-containing or anhydride group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid or maleic anhydride; a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth)acrylate; an amine group-containing monomer such as (meth)acrylic acid a porphyrin; or a copolymer containing a guanamine monomer such as (meth) acrylamide. These materials may be used singly or in combination of two or more kinds.

The chemically modified energy ray-reactive functional group for energy ray curing of the pressure ray-curable or energy ray-curable compound to be used for energy ray curation is not particularly limited as long as it can utilize, for example, infrared light, visible light The energy ray of the ultraviolet light, the X-ray or the electron beam may be cured, but it is preferably three-dimensional network structure (networking) in the energy ray-curable pressure-sensitive adhesive after the irradiation of the energy ray. They may be used singly or in combination of two or more kinds. Examples of the energy ray-reactive functional group to be used for chemical modification include a functional group having a carbon-carbon multiple bond such as an acrylonitrile group, a methacryl group, a vinyl group, an allyl group, and an ethynyl group. In these functional groups, the carbon-carbon multiple bond is cleaved by energy ray irradiation to generate a radical, which constitutes a cross-linking site to form a three-dimensional network structure. Among them, in view of reactivity and operability, a (meth)acrylonitrile group is preferable, and since it exhibits a relatively high reactivity to energy rays, it can be selected from various acrylic pressure-sensitive adhesives and used in combination.

Representative examples of the base component of the energy ray-reactive functional group chemical modification include via an acrylic polymer containing a reactive functional group (through a monomer that contains a reactive functional group such as a hydroxyl group or a carboxyl group (such as a group obtained by copolymerizing 2-hydroxyethyl (meth)acrylate or (meth)acrylic acid with an alkyl (meth)acrylate) and a group capable of reacting with a reactive functional group in the molecule (such as an isocyanate) A polymer obtained by reacting a compound of a base or epoxy group and an energy ray-reactive functional group such as a propylene fluorenyl group or a methacryl oxime group such as ethylene (meth) propylene sulfonate.

In the acrylic polymer containing a reactive functional group, the ratio of the monomer having a reactive functional group to all of the monomers is, for example, from 5 to 40% by weight, preferably from 10 to 30% by weight. In the reaction with an acrylic polymer containing a reactive functional group, a compound having a group reactive with a reactive functional group in its molecule and having an energy ray-reactive functional group is relative to a compound having a reactive functional group The amount of reactive functional groups (such as hydroxyl groups and carboxyl groups) in the acrylic polymer is, for example, from 50 to 100 mol%, preferably from 60 to 95 mol%.

Examples of the energy ray-curable compound include compounds having two or more carbon-carbon double bonds, such as trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, and pentaerythritol triacrylate. Ester, neopentyl alcohol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate Esters, and compounds containing poly(meth)acrylonitrile groups such as polyethylene glycol diacrylate. These compounds may be used singly or in combination of two or more kinds. Among them, a compound containing a poly(meth)acrylinyl group as disclosed in, for example, JP-A-2003-292916 is mentioned. Hereinafter, a compound containing a poly(meth)acrylonitrile group can be referred to as an "acrylate type crosslinking agent".

The energy ray-curable compound may also be a mixture of an organic salt such as a phosphonium salt and a compound having a plurality of heterocyclic rings in its molecule. In such a mixture, the organic salt is cleaved by energy ray irradiation to generate ions which provide an initiating species as a ring opening reaction for inducing a hetero ring, thereby forming a three-dimensional network structure. Examples of the organic salt include a phosphonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, and a borate, and examples of the heterocyclic ring in the compound having a plurality of heterocyclic rings in the molecule include ethylene oxide, propylene oxide, and ketone. (oxorane), ethylene sulfide and anthracycline. More specifically, a compound described in Photocuring Technology (2000), Technical Information Institute Co., can be utilized.

Examples of the energy ray-curable resin include a photosensitive group-containing polymer or oligomer, for example, an ester (meth) acrylate, a urethane (meth) acrylate, an epoxy group (methyl group) Acrylate, melamine (meth) acrylate, and acrylic resin (meth) acrylate having a (meth) acrylonitrile group at the terminal of the molecule, a thiol-ene addition resin, and having a terminal at the molecule The allyl photocationic polymer resin, the cinnamyl group-containing polymer such as polyvinyl cinnamate, the diazotyl phenolic novolac resin and the acrylamide polymer. Further, examples of the polymer which can be reacted by high energy rays include epoxidized polybutadiene, unsaturated polyester, polyglycidyl methacrylate, polypropylene decylamine, and polyvinyl siloxane. In the case of using an energy ray curable resin, the aforementioned basic components are not necessary.

The energy ray-curable pressure-sensitive adhesive is particularly preferably an acrylic polymer chemically modified by an energy ray-reactive functional group or an acrylic acid in which an energy ray-reactive functional group is introduced into a side chain. A polymer) and a combination of the aforementioned energy ray-curable compounds (for example, a compound having two or more carbon-carbon double bonds). This combination is preferred in terms of reactivity and handling efficiency because it contains an acrylate group which exhibits a relatively high reactivity to energy rays, and it can be selected from various acrylic pressure-sensitive adhesives. Clear examples of such a combination include an acrylic polymer in which an acrylate group is introduced into a side chain and a compound including two or more functional groups (especially acrylate groups) having a carbon-carbon double bond. combination. Such a combination can be, for example, a combination disclosed in JP-A-2003-292916.

The acrylic polymer in which the acrylate group is introduced into the side chain can be, for example, by passing an isocyanate compound such as propylene oxide ethyl isocyanate or methacrylic acid methacrylate to the urethane. A method in which a bond is bonded to an acrylic polymer having a hydroxyl group in a side chain is prepared.

The amount of the energy ray-curable compound relative to 100 parts by weight of the base component (for example, the aforementioned acrylic polymer or the energy ray-reactive functional chemically modified acrylic polymer) is from about 0.5 to about 200 parts. The weight is preferably from 5 to 180 parts by weight and more preferably from 20 to 130 parts by weight.

In the energy ray-curable pressure-sensitive adhesive, an energy ray polymerization initiator for curing a compound which provides energy ray-curing properties can be blended to improve the reaction speed for forming a three-dimensional network structure.

The energy ray polymerization initiator may be selected from known or commonly used polymerization initiators depending on the type of energy ray used (for example, infrared light, visible light, ultraviolet light, X-ray or electron beam). In view of the operational efficiency, a compound which can initiate photopolymerization by ultraviolet light is preferred. Examples of representative energy ray polymerization initiators include ketone type initiators such as diphenyl ketone, acetophenone, benzoquinone, naphthoquinone, anthracene and anthrone; azo type initiators such as azobisisobutyronitrile; And peroxide-type initiators such as benzammonium peroxide and perbenzoic acid, but these examples are not superficial. Commercial products thereof include, for example, Irgacure 184 and Irgacure 651 (trade name) manufactured by Ciba-Geigy Ltd.

The energy ray polymerization initiators may be used singly or in combination of two or more kinds. The energy ray polymerization initiator is used in an amount of from about 0.01 to 10 parts by weight, preferably from about 1 to 8 parts by weight, per 100 parts by weight of the base component. The energy ray polymerization accelerator can be used in combination with the energy ray polymerization initiator as needed.

In the energy ray-curable pressure-sensitive adhesive, in addition to the foregoing components, it is also necessary to add appropriate additives such as a crosslinking agent, a curing (crosslinking) accelerator, an adhesive, before and after curing via energy rays. A vulcanizing agent, a tackifier for obtaining appropriate pressure-sensitive adhesive properties, and an anti-aging agent and an antioxidant for improving durability.

A preferred energy ray-curable pressure-sensitive adhesive is a composition containing an energy ray-curable compound in a base component (pressure-sensitive adhesive), preferably containing UV in an acrylic pressure-sensitive adhesive. A UV curable pressure sensitive adhesive that cures the compound. As a particularly preferable example of the energy ray-curable pressure-sensitive adhesive, an acrylic pressure sensitive adhesive comprising a side chain acrylate, an acrylate type crosslinking agent (a compound containing a poly(meth)acryl fluorenyl group; Or a polyfunctional acrylate), and a UV curable pressure sensitive adhesive for UV photoinitiators. The acrylic pressure-sensitive adhesive containing a side chain acrylate means an acrylic polymer in which an acrylate group is introduced into a side chain, and a material similar to the foregoing can be produced and used in a similar manner. The acrylate type crosslinking agent is the aforementioned low molecular weight compound as an example of a compound containing a poly(meth)acryl fluorenyl group. The ultraviolet photoinitiator can be an example of the foregoing as a representative energy ray polymerization initiator.

Further, as a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 3, a non-energy ray-curable pressure-sensitive adhesive based on the acrylic pressure-sensitive adhesive may be used, and in this case, it is suitable to have A pressure-sensitive adhesive having a pressure-sensitive adhesive having a lower peeling stress to form a tubular roll, for example, a 180° peel test (room temperature (25° C.)) using a mirror-finished wafer as an adherent, and a sense of use can be used. The adhesive force is 6.5 Newtons/10 mm or less (for example, 0.05 to 6.5 Newtons/10 mm), and particularly 6.0 Newtons/10 mm or less (for example, 0.05 to 6.0 Newtons/10 mm, preferably 0.2 to 6.0 Newtons) /10 mm) pressure sensitive adhesive.

As the non-energy ray-curable pressure-sensitive adhesive based on the acrylic pressure-sensitive adhesive having a small pressure-sensitive adhesive force, it is preferred to use a crosslinking agent capable of reacting with the aforementioned reactive functional group by adding [for example] Isocyanate crosslinker, melamine crosslinker, epoxy crosslinker, or the like] to alkyl (meth)acrylate [eg C ₁ -C ₁₀ alkyl (meth)acrylate, such as (methyl) a copolymer of methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate or the like, and one having a monomer having a reactive functional group [for example, a carboxyl group-containing or acid anhydride group-containing monomer such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic anhydride or the like; a hydroxyl group-containing monomer , such as 2-hydroxyethyl (meth)acrylate or the like; an amine-containing monomer such as (meth)acrylic acid a porphyrin ester and the like; a guanamine-containing monomer such as (meth) acrylamide or the like; or an analog thereof, and optionally a copolymerizable monomer (for example, having an alicyclic hydrocarbon group) Methyl) acrylate, such as (meth) acrylate An ester or the like, acrylonitrile, or the like, and the copolymer are crosslinked to prepare an acrylic pressure sensitive adhesive.

The pressure-sensitive adhesive layer 3 can be formed by a general method such as coating a coating liquid (which is prepared by a pressure-sensitive adhesive, an energy ray-curable compound, and an optional solvent) on the confinement layer 2 (at a method of attaching the coating liquid to a suitable release liner (spacer) to form a pressure-sensitive adhesive layer, and transferring the same to the restriction layer 2 . In the case of the transfer method, voids (gap) remain in the interface with the confinement layer 2. In this case, the voids can be diffused and removed by, for example, a heating/pressurizing process in the autoclave process. The pressure-sensitive adhesive layer 3 may have a single layer structure or a composite layer structure.

The pressure-sensitive adhesive layer 3 in the present invention may further include beads such as glass beads or resin beads. The addition of glass beads or resin beads to the pressure-sensitive adhesive layer 3 can increase the shear modulus and thus contribute to the reduction of the pressure-sensitive adhesive force. The beads have, for example, an average particle size of from about 1 to 100 microns, preferably from 1 to 20 microns. The beads are used in an amount of 25 to 200 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the entire pressure-sensitive adhesive layer 3. An excessively large amount of addition causes a dispersion of ruthenium, which makes coating of the pressure-sensitive adhesive difficult, and an excessively small amount tends to provide only an insufficient effect.

The pressure-sensitive adhesive layer 3 has a thickness generally from 10 to 200 μm, preferably from 20 to 100 μm, and more preferably from 30 to 60 μm. When the thickness is too small, the pressure-sensitive adhesive force becomes insufficient, and thus the support or temporary fixation of the adhesive body tends to be difficult. On the other hand, when it is too large, it is uneconomical and the processing property is deteriorated.

The self-rolling laminated sheet of the present invention can selectively overlap the shrinkable film layer 1 and the constraining layer 2 (the elastic layer 21 and the rigid film layer 22 in the foregoing specific examples) according to the use, and utilizes, for example, manual roll or lamination. A laminating device of the machine or an atmospheric pressure compressing device such as an autoclave is laminated to obtain such layers. Further, the self-rolling pressure-sensitive adhesive sheet of the present invention can be provided by applying the pressure-sensitive adhesive layer 3 to the surface of the confinement layer 2 of the self-rolling laminated sheet, or by providing pressure-sensitive adhesive on one side thereof in advance. The constraining layer 2 (or the rigid film layer 22) of the layer 3 is formed by laminating and laminating the shrinkable film layer 1 (or the shrinkable film layer 1 and the elastic layer 21).

The self-rolling pressure-sensitive adhesive sheet of the present invention can be utilized as a protective pressure-sensitive adhesive sheet for a semiconductor or the like, or a fixed pressure-sensitive adhesive sheet for a semiconductor wafer or the like, and can be used more clearly. A pressure-sensitive adhesive sheet for back surface polishing of a semiconductor semiconductor, a pressure-sensitive adhesive sheet for back surface polishing of a compound semiconductor, and a pressure-sensitive adhesive sheet for square-grain cutting of a semiconductor, for pellet cutting of a compound semiconductor Pressure-sensitive adhesive sheet for use, pressure-sensitive adhesive sheet for square-grain cutting of semiconductor package, pressure-sensitive adhesive sheet for glass square cutting, and pressure-sensitive adhesive sheet for ceramic square cutting . It is particularly useful as a pressure-sensitive adhesive sheet for semiconductors, such as a pressure-sensitive adhesive sheet for protecting a semiconductor and a pressure-sensitive adhesive sheet for fixing a semiconductor wafer.

The processing of the adherend using the self-rolling pressure-sensitive adhesive sheet of the present invention will be described below. The self-rolling pressure-sensitive adhesive sheet of the present invention is adhered to the adhesive body to be temporarily fixed. Subsequently, after performing necessary processing on the adherend (processed article), the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer of the self-rolling pressure-sensitive adhesive sheet is lowered, and a stimulus such as heat is provided to induce the shrinkable film layer 1 Shrinkage, thereby causing the self-rolling pressure-sensitive adhesive sheet to spontaneously roll up from one end or from the opposite ends toward the center (usually along the main shrink axis) in one direction (usually along the main shrink axis), thus forming one or two The tubular reels are thus peeled off from the adhesive, whereby the finished article can be obtained. In the case of spontaneous rolling of one end of the self-rolling pressure-sensitive adhesive sheet in one direction, a tubular reel (unidirectional rolling peeling) is formed, and at the opposite ends of the self-rolling pressure-sensitive adhesive sheet In the case of a center-spontaneous scrolling, two tubular reels arranged in parallel (two-way rolling peeling) are formed.

Representative examples of processed articles include semiconductor wafers. Examples of processing include cutting, square cutting, grinding, etching, car making, and heating (but in the case where the shrinkable film layer is a heat shrinkable film layer, it is limited to being equal to or lower than the heat shrinking starting temperature) The temperature is not particularly limited as long as it can be processed by the pressure-sensitive adhesive sheet.

After processing the processed object, for example, in the case where the pressure sensitive adhesive layer is an energy ray curable pressure sensitive adhesive layer and the shrinkable film layer is a heat shrinkable film layer, the pressure sensitive adhesive layer is irradiated with the energy ray. And heating the heat shrinkable film layer by a heating device. In this way, the pressure-sensitive adhesive layer is cured and loses the pressure-sensitive adhesive force, and the shrinkable film layer is gradually deformed by shrinkage, whereby the pressure-sensitive adhesive sheet is lifted in the outer edge portion thereof, and is rolled up in the pressure-sensitive adhesive sheet. The outer edge portion (or from the two opposite outer edge portions) spontaneously travels in one direction (or in two directions (toward the center) opposite each other), thereby forming a tubular reel (or two tubular volumes) cylinder). In this operation, the contraction direction of the pressure-sensitive adhesive sheet is regulated by the restriction layer, and the rolling occurs in an axial direction to rapidly form the tubular reel. Therefore, the pressure-sensitive adhesive sheet can be peeled off from the adherend (processed article) extremely easily and cleanly. The heating temperature can be appropriately selected depending on the shrinkage property of the heat shrinkable film layer, and is, for example, from 70 to 180 ° C, preferably from 70 to 140 ° C. The irradiation of energy rays and heating can be carried out simultaneously or stepwise. Furthermore, heating can be carried out not only by heating uniformly over the entire surface, but also by gradually heating the entire surface, and further by only partially heating to provide a starting point for peeling. The heating must be appropriately selected for the purpose of easily utilizing the peelability.

3A to 3D are diagrams (perspective views) illustrating a self-rolling mode of a self-rolling laminated sheet or a pressure-sensitive adhesive sheet of the present invention, wherein FIG. 3A illustrates the provision of a self-rolling laminated sheet or a pressure-sensitive adhesive sheet. The pattern before the stimulation of the contraction of the shrinkable film; FIG. 3B illustrates the self-rolling laminated sheet or the pressure-sensitive adhesive sheet provided by the stimulation of the shrinkage of the shrinkable film layer (the pressure-sensitive adhesive force on the pressure-sensitive adhesive layer) A pressure-sensitive adhesive sheet which has been lowered or lost) starts from a state in which a direction (generally along the main shrinkage axis of the shrinkable film) is rolled up from the outer edge portion (one end portion); FIG. 3C illustrates the sheet A drawing in which the scrolling is completed and a state in which a tubular reel (unidirectional rolling) is formed; and FIG. 3D illustrates that the sheet spontaneously rolls from the opposite ends toward the center (generally along the main shrinking axis of the shrinkable film) The pattern of the state of the two tubular reels (two-way scrolling) is thus formed. The difference in the spontaneous roll-up properties of the self-rolling laminated sheets and the self-rolling pressure-sensitive adhesive sheets is extremely small. Whether the laminated sheet or the pressure-sensitive adhesive sheet undergoes unidirectional rolling or bi-directional rolling, for example, depending on the pressure-sensitive adhesive force of the confinement layer on the shrinkable film layer and the shear modulus of the confinement layer (especially the elastic layer) .

In FIGS. 3A to 3D, L indicates the length of the self-rolling laminated sheet or the pressure-sensitive adhesive sheet 4 in the rolling direction (generally along the main shrinking axis of the shrinkable film layer) (or in the case of a circular sheet) Is the diameter) (see Figure 3A), and r indicates the diameter of the formed tubular reel (or when the diameter of the tubular reel is not uniform along the longitudinal direction of the scroll element, such as the maximum diameter in the case where the sheet is circular) (See Figures 3C and 3D). As the self-rolling laminated sheet or pressure-sensitive adhesive sheet of the present invention, r/L is preferably in the range of 0.001 to 0.333, and more preferably 0.01 to 0.2. L is, for example, 10 to 2000 mm, preferably 300 to 1000 mm. The laminated sheet or pressure-sensitive adhesive sheet is perpendicular to the length of L, for example, about 10 to 2000 mm, preferably 300 to 1000 mm. The value of r/L can be adjusted by adjusting the type, composition, thickness, etc. of the material of each of the shrinkable film layer 1, the constraining layer 2 (the elastic layer 21 and the rigid film layer 22), and the pressure-sensitive adhesive layer 3. The Young's modulus and thickness of the elastic layer 21 and the rigid film layer 22 constituting the confinement layer 2 are adjusted to the above range. In this embodiment, the self-rolling laminated sheet or the pressure-sensitive adhesive sheet has a quadrangular shape, but it is not limited to such a shape, but may be appropriately selected depending on the use, and may be circular, elliptical or polygonal. Any one. In the case of forming two tubular reels, the two tubular reels formed each have a ratio (r/L) within the aforementioned range.

When the self-rolling pressure-sensitive adhesive sheet of the present invention is used for processing of an adherend (processed article), it can prevent the processed article from being broken by stress at the time of peeling, and even if it is processed in a fragile adherend such as a thin semiconductor crystal. In the case of a circle, the pressure-sensitive adhesive sheet can be easily peeled off from the adhesive without causing cracking or contamination thereof.

[Examples]

The invention will be further illustrated by the following examples, but the invention is not limited thereto. The shear modulus of the elastic layer and the rigid film layer, and the pressure-sensitive adhesive force of the elastic layer to the shrinkable film were measured in the following manner.

Further, an index r/L for determining whether or not the sheet can be used as a tubular reel is as defined in the following description.

[Measurement of Young's Modulus (80 ° C) of rigid film layer]

The Young's modulus of the rigid film layer was measured in the following manner in accordance with JIS K7127. Using a tensile tester Autograph AG-1kNG (assembly heating cover) manufactured by Shimadzu Corporation, a rigid film of 200 mm × 10 mm wide was cut and adhered at a chuck distance of 100 mm, and a heating atmosphere of 80 ° C was provided. Thereafter, the sample was pulled at a tensile rate of 5 mm/min to obtain a measurement of the stress-strain relationship, and the Young's modulus was obtained by measuring the load at a stress of 0.2% and 0.45%. This measurement was repeated 5 times on the same sample and averaged.

[Measurement of Shear Modulus (80 ° C) of Elastic Layer]

The shear modulus of the elastic layer was measured in the following manner. The elastic layer described in each of the examples and the comparative examples was prepared to have a thickness of 1.5 to 2 mm, and was punched with a punch having a diameter of 7.9 mm to obtain a sample for measurement. Manufactured by a viscoelastic spectrometer (ARES) Rheometric Scientific Inc., measured at a chuck pressure of 100 g and a shear frequency of 1 Hz [8 mm parallel plate made of stainless steel (manufactured by TA Instruments, Inc., model 708.0157)] And the shear modulus at 80 ° C was used.

[Measurement of the pressure-sensitive adhesive force of the elastic layer on the shrinkable film]

The pressure-sensitive adhesive force of the elastic layer to the shrinkable film was measured by a 180 peel test (50 ° C). The laminated sheet is prepared in the same manner as the pressure-sensitive adhesive sheet except that no pressure-sensitive adhesive layer (energy ray-curable pressure-sensitive adhesive layer, non-energy ray-curable pressure-sensitive adhesive layer) is provided, provided that the laminated sheet is provided The ultraviolet ray-reactive cross-linking agent is contained in the elastic layer, but when the ultraviolet ray is not irradiated, the laminated sheet is irradiated with ultraviolet light having a strength of 500 mJ/cm ² and then cut into a width of 10 mm, and a rigid film layer thereof is used. The surface on the side (22 in Fig. 1) is adhered to the rigid support substrate (矽 wafer) via the pressure-sensitive adhesive tape, and the stretch type frame of the peel tester is adhered to the shrinkable film side by the pressure-sensitive adhesive tape. The surfaces were combined to place a rigid support substrate in contact with the heating stage on a heating stage (heater) of 50 °C. The tensile frame was pulled down at a stretching speed of 300 mm/min in the 180° direction, and the force (Newton/10 mm) when peeling occurred between the shrinkable film and the elastic layer was measured. In order to eliminate the measurement error of the thickness variation of the rigid supporting substrate, the thickness of the rigid supporting substrate was unified to 38 μm.

[Measurement of pressure-sensitive adhesive force of non-energy ray-curable pressure-sensitive adhesive layer on enamel mirror wafer]

The three forms of the non-energy ray-curable pressure-sensitive adhesive obtained by the following Production Examples 4 to 6 were bonded to a polyethylene terephthalate substrate (thickness: 38 μm) using a hand roller. It was cut to a width of 10 mm, removed to the release sheet, and then bonded to a 4-inch mirror-finished wafer using a hand roller (manufactured by Shin-Etsu Semiconductor Co., Ltd., trade name "CZ-N". "). A tensile type of a peel tester is bonded to the combination by using a pressure-sensitive adhesive tape which is pulled at a stretching speed of 300 mm/min in a 180° direction and measured as a shrinkable film. The force at which the peeling between the layer and the elastic layer occurs (Newton/10 mm).

Similarly, each of the energy ray-curable pressure-sensitive adhesive layers obtained in the following Production Examples 1 to 3 was measured in the same manner as above for a 4-inch mirror-finished wafer (manufactured by Shin-Etsu Semiconductor Co., Ltd., commercial product). The pressure-sensitive adhesive of the name "CZ-N" was only exposed to ultraviolet light having a intensity of 500 mJ/cm ² before measurement. As a result, when all the pressure-sensitive adhesives were peeled off at 0.01 Newton/10 mm or less, the pressure-sensitive adhesive force was sufficiently lowered. For this reason, the description of the pressure-sensitive adhesive force of the energy ray-curable pressure-sensitive adhesive layer for the tantalum wafer in the following embodiments will be omitted.

[Measurement of r/L value]

Each of the pressure-sensitive adhesive sheets obtained by the following examples was cut into a size of 100 mm × 100 mm, and then prepared by irradiating an energy ray-curable pressure-sensitive adhesive with ultraviolet light of 500 mJ/cm ² . The end portion of the pressure-sensitive adhesive sheet is immersed in hot water of 80 ° C in the direction of the contraction axis of the shrinkable film to promote deformation thereof. In order to make the pressure-sensitive adhesive sheet into a tubular roll, the diameter was measured by one foot, and this value was divided by 100 mm to obtain r/L.

In the self-winding property, the laminated sheet having no pressure-sensitive adhesive layer exhibits the same performance as the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer.

[Manufacturing Example of Pressure Sensitive Adhesive Layer] [Manufacturing Example 1]

[Production of energy ray-curable pressure-sensitive adhesive layer (1)] In an acrylic polymer, 80% of the hydroxyl group of 2-hydroxyethyl acrylate derived from an acrylic polymer is passed through butyl acrylate: ethyl acrylate : a composition of 2-hydroxyethyl acrylate = 50:50:20 (by weight) copolymerized to give methacrylic acid ethyl methacrylate (2-isocyanatoethyl methacrylate) bonded. An acrylic polymer having a methacrylate group in the side chain is produced. 50 parts by weight of pentaerythritol tetraacrylate as a compound containing two or more compounds having a carbon-carbon double bond, 6 parts by weight of a photoinitiator (manufactured by Ciba-Geigy Ltd., commercial product) "Irgacure 184"), 1.5 parts by weight of a crosslinking agent (trade name "Coronate L"), and 40 parts by weight of a tackifier (manufactured by Soken Chemical Co., Ltd., polymethyl methacrylate beads, commercial products) The name "MX500" is mixed with 100 parts by weight of an acrylic polymer having a methacrylate group in a side chain to produce an energy ray-curable pressure-sensitive adhesive.

The prepared energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38") by a coater, and dried to remove volatile substances such as a solvent. A laminate element having a 30 micron thick energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example 2]

[Production of energy ray-curable pressure-sensitive adhesive layer (2)] In an acrylic polymer, 80% of the hydroxyl group of 2-hydroxyethyl acrylate derived from an acrylic polymer [via butyl acrylate: ethyl acrylate) : 2-hydroxyethyl acrylate = 50:50:20 (by weight) composition obtained by copolymerization] with methacrylic acid methacrylate (2-isocyanatoethyl methacrylate) bonded And an acrylic polymer having a methacrylate group in the side chain is produced. 100 parts by weight of a compound having two or more functional groups having a carbon-carbon double bond, "Ultraviolet UV 1700" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., 3 parts by weight of light An initiator (manufactured by Ciba-Geigy Ltd., trade name "Irgacure 184"), and 1.5 parts by weight of a crosslinking agent (trade name "Coronate L") and 100 parts by weight of a methacrylate group in a side chain The acrylic polymer is mixed to produce an energy ray curable pressure sensitive adhesive.

The prepared energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38") by a coater, and dried to remove volatile substances such as a solvent. A laminate element having a 30 micron thick energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example 3]

[Production of energy ray-curable pressure-sensitive adhesive layer (3)] In an acrylic polymer, 80% of the hydroxyl group of 2-hydroxyethyl acrylate derived from an acrylic polymer [via butyl acrylate: ethyl acrylate) : 2-hydroxyethyl acrylate = 50:50:20 (by weight) composition obtained by copolymerization] with methacrylic acid methacrylate (2-isocyanatoethyl methacrylate) bonded And an acrylic polymer having a methacrylate group in the side chain is produced. 50 parts by weight of a compound having two or more functional groups having a carbon-carbon double bond, "Ultraviolet UV 1700" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., 3 parts by weight of light An initiator (manufactured by Ciba-Geigy Ltd., trade name "Irgacure 184"), and 1.5 parts by weight of a crosslinking agent (trade name "Coronate L") and 100 parts by weight of a methacrylate group in a side chain The acrylic polymer is mixed to produce an energy ray curable pressure sensitive adhesive.

The prepared energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38") by a coater, and dried to remove volatile substances such as a solvent. A laminate element having a 30 micron thick energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example 4]

[Production of Non-energy Ray Curable Pressure-Sensitive Adhesive Layer (1)] 0.7 parts by weight of "Tetrad C" (trade name) manufactured by Mitsubishi Gas Chemical Company, Inc. and 2 parts by weight of a crosslinking agent (product) The name "Coronate L" is mixed with 100 parts by weight of an acrylic copolymer [by copolymerizing butyl acrylate: acrylic acid = 100:3 (by weight)] to produce a non-energy ray curable pressure-sensitive adhesive. Agent.

The obtained non-energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38") by a coater, and dried to remove a volatile substance such as a solvent. A laminate element having a 30 micron thick non-energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example 5]

[Manufacture of non-energy ray-curable pressure-sensitive adhesive layer (2)] 1 part by weight of "Tetrad C" (trade name) manufactured by Mitsubishi Gas Chemical Company, Inc., 2 parts by weight of a crosslinking agent (product) "Coronate L"), and 0.05 parts by weight of "Epan 710" (trade name) manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd., and 100 parts by weight of acrylic copolymer [via making 2-2-acrylic acid Hexyl hexyl ester: acrylic acid The porphyrin ester: acrylic acid: 2-hydroxyethyl acrylate = 75:25:3:0.1 (by weight) copolymerized to obtain a non-energy ray-curable pressure-sensitive adhesive.

The obtained non-energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38") by a coater, and dried to remove a volatile substance such as a solvent. A laminate element having a 30 micron thick non-energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example 6]

[Production of Non-energy Ray Curable Pressure-Sensitive Adhesive Layer (3)] 0.5 parts by weight of "Tetrad C" (trade name) manufactured by Mitsubishi Gas Chemical Company, Inc. and 8 parts by weight of a crosslinking agent (product) "Coronate L", mixed with 100 parts by weight of acrylic copolymer (by Dai-ichi Lace Mfg. Co., Ltd., trade name "Rheocote R1020S") to produce non-energy ray curable pressure-sensitive adhesive Agent.

The obtained non-energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Po1yester Fi1m Co., trade name "MRF38") by a coater, and dried to remove volatile substances such as a solvent. A laminate element having a 30 micron thick non-energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example 7]

[Manufacture of non-energy ray-curable pressure-sensitive adhesive layer (4)] 0.5 parts by weight of "Tetrad C" (trade name) manufactured by Mitsubishi Gas Chemical Company, Inc., and 2 parts by weight of a crosslinking agent (product) "Coronate L"), and 0.05 parts by weight of cross-linking agent (trade name "Coronate L"), and 100 parts by weight of acrylic copolymer [via 2-ethylhexyl acrylate: acrylic acid The porphyrin ester: acrylic acid: 2-hydroxyethyl acrylate = 75:25:3:0.1 (by weight) copolymerized to obtain a non-energy ray-curable pressure-sensitive adhesive.

The obtained non-energy ray-curable pressure-sensitive adhesive is applied to a release sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38") by a coater, and dried to remove a volatile substance such as a solvent. A laminate element having a 30 micron thick non-energy ray curable pressure sensitive adhesive layer on the release sheet is obtained.

[Manufacturing Example of Pressure Sensitive Adhesive Sheet] [Example 1]

Make 45 parts by weight of acrylic acid Ester, 45 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of acrylic acid, 0.1 part by weight of hexanediol diacrylate, 0.05 part by weight of "Irgacure 651" (photoinitiator, manufactured by Ciba-Geigy Ltd.) And 0.1 part by weight of "Irgacure 184" (photoinitiator, manufactured by Ciba-Geigy Ltd.) was mixed and irradiated with ultraviolet light for 1 hour to obtain a prepolymer. The prepolymer was applied onto one surface of a polyethylene terephthalate film (PET film, thickness: 38 μm, trade name "Lumirror S10", manufactured by Toray Industries, Inc.) as a rigid film layer, and A heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, trade name "Space Clean S7053", manufactured by Toyobo Co.) was superposed thereon and laminated by hand roll. The final curing was carried out from both sides by ultraviolet irradiation, thereby obtaining a laminated sheet (thickness of the acrylic pressure-sensitive adhesive layer: 105 μm).

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (1) produced in Example 1 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The resulting laminate is closely adhered by a laminating machine, thereby obtaining an adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / PET film layer ( Rigid film layer)], energy ray curable pressure-sensitive adhesive layer (1) and release sheet. The heat shrinkable film has a heat shrinkage ratio in the main shrinkage direction of 70% or more at 100 °C.

The acrylic pressure-sensitive adhesive layer (elastic layer) has a shear modulus (80 ° C) of 0.126 × 10 ⁶ Newtons per square meter, and a product of shear modulus and thickness of 13.2 Newtons per meter. The pressure-sensitive adhesive layer (50 ° C) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 4.9 Newtons/10 mm.

The PET film layer (rigid film layer) has a Young's modulus at 80 ° C of 3.72 × 10 ⁹ Newtons / square meter, and a product of Young's modulus of 1.41 × 10 ⁵ Newtons / meter and thickness.

The value of r/L is 0.06.

[Embodiment 2]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the PET film of Example 1 was replaced with "Lumirror S10" (trade name) having a thickness of 25 μm, manufactured by Toray Industries, Inc.

The PET film layer (rigid film layer) has a Young's modulus at 80 ° C of 3.72 × 10 ⁹ Newtons / square meter, and a product of Young's modulus of 0.93 × 10 ⁵ Newtons / meter and thickness.

The value of r/L is 0.06.

[Example 3]

Dissolving 100 parts by weight of acrylic polymer in toluene (by making 1 part by weight of 2-hydroxyethyl acrylate, 70 parts by weight of butyl acrylate, 30 parts by weight of ethyl acrylate, and 5 parts by weight of acrylic acid copolymerized) And obtained, 10 parts by weight of dipentaerythritol hexaacrylate, 1 part by weight of "Tetrad C" (crosslinking agent, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2 parts by weight of "Coronate L" (crossed) A binder solution, manufactured by Nippon Polyurethane Industry Co., Ltd., and 3 parts by weight of "Irgacure 651" (photoinitiator, manufactured by Ciba-Geigy Ltd.), which was coated on a rigid film layer. On the surface of one of the ethylene terephthalate film (PET film, thickness: 38 μm, trade name “Lumirror S10”, manufactured by Toray Industries, Inc.), and “Space Clean S5630” (trade name) having a thickness of 60 μm The manufactured by Toyobo Co. (uniaxially stretched polyester film) was superposed thereon and laminated by hand roll to obtain a laminated sheet (thickness of the acrylic pressure-sensitive adhesive layer: 30 μm).

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (1) produced in Example 1 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer)], energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The heat shrinkable film has a heat shrinkage ratio in the main shrinkage direction of 70% or more at 100 °C.

The acrylic pressure-sensitive adhesive layer (elastic layer) has a shear modulus (80 ° C) of 0.689 × 10 ⁶ Newtons per square meter, and a product of shear modulus and thickness of 20.67 Newtons per meter. The pressure-sensitive adhesive layer (50 ° C) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 4.9 Newtons/10 mm.

The value of r/L is 0.055.

[Example 4]

100 parts by weight of an acrylic polymer (trade name "Rheocote R1020S", manufactured by Dai-ichi Lace Mfg. Co.) and 10 parts by weight of pentaerythritol-denatured acrylate were dissolved in methyl ethyl ketone. Co-agent (trade name "DPHA40H", manufactured by Nippon Kayaku Co., Ltd.), 0.25 part by weight of "Tetrad C" (crosslinking agent, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 2 parts by weight of "Coronate L" (crosslinking agent, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 3 parts by weight of "Irgacure 651" (photoinitiator, manufactured by Ciba-Geigy Ltd.), which was applied as a rigid film. a polyethylene terephthalate film (PET film, thickness: 38 μm, trade name "Lumirror S10", manufactured by Toray Industries, Inc.) on one surface, and a heat shrinkable film (uniaxial stretching) Polyester film, thickness: 60 μm, trade name "Space Clean S5630", manufactured by Toyobo Co.) was superposed thereon and laminated by hand roll to obtain a laminated sheet (thickness of acrylic pressure-sensitive adhesive layer: 30 μm) .

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (1) produced in Example 1 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer)], energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The acrylic pressure-sensitive adhesive layer (elastic layer) has a shear modulus (80 ° C) of 0.72 × 10 ⁶ Newtons per square meter, and a product of shear modulus and thickness of 21.6 Newtons per meter. The pressure-sensitive adhesive layer (elastic layer) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer (at 50 ° C) was 4.4 N/10 mm.

The value of r/L is 0.0045.

[Example 5]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 4 except that the polyethylene terephthalate film as the rigid film layer in Example 4 had a thickness of 50 μm. The PET film layer (rigid film layer) had a Young's modulus at 80 ° C of 3.72 × 10 ⁹ Newtons / square meter, and the product of Young's modulus and thickness was 1.86 × 10 ⁵ Newtons / meter.

The value of r/L is 0.06.

[Embodiment 6]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 4 except that the polyethylene terephthalate film as the rigid film layer in Example 4 had a thickness of 75 μm. The PET film layer (rigid film layer) had a Young's modulus at 80 ° C of 3.72 × 10 ⁹ Newtons / square meter, and the product of Young's modulus and thickness was 2.79 × 10 ⁵ Newtons / meter.

The value of r/L is 0.095.

[Embodiment 7]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 5 except that the energy ray-curable pressure-sensitive adhesive layer (2) of Production Example 2 was used in Example 5.

The value of r/L is 0.065.

[Embodiment 8]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 7, except that the polyethylene terephthalate film as the rigid film layer in Example 7 had a thickness of 75 μm.

The value of r/L is 0.1.

[Embodiment 9]

100 parts by weight of an acrylic polymer (manufactured by Dai-ichi Lace Mfg. Co., trade name "Rheocote R1020S") and 10 parts by weight of pentaerythritol-denatured acrylate were dissolved in methyl ethyl ketone. Colinking agent (manufactured by Nippon Kayaku Co., Ltd., trade name "DPHA40H"), 0.25 part by weight of "Tetrad C" (crosslinking agent, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 2 parts by weight of "Coronate L" (crosslinking agent, manufactured by Nippon Polyurethane Industry, Co., Ltd.) and 3 parts by weight of "Irgacure 651" (photoinitiator, manufactured by Ciba-Geigy, Ltd.) were coated with a polymer solution. As a rigid film layer of a polyethylene terephthalate film (PET film, thickness: 38 μm, manufactured by Toray Industries, Inc., trade name "Lumirror S10"), and a heat shrinkable film (single) The axially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name “Space Clean S7053”, was superposed thereon and laminated by hand roll to obtain a laminated sheet (thickness of the acrylic pressure-sensitive adhesive layer: 30 microns).

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (3) obtained in Production Example 3 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining an adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / PET film layer ( A rigid film layer), an energy ray-curable pressure-sensitive adhesive layer (3) and a release sheet.

The pressure-sensitive adhesive force (50 ° C) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 4.4 N/10 mm.

The value of r/L is 0.05.

[Embodiment 10]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 9, except that the polyethylene terephthalate film as the rigid film layer in Example 9 had a thickness of 50 μm.

The value of r/L is 0.045.

[Example 11]

100 parts by weight of an acrylic polymer (manufactured by Dai-ichi Lace Mfg. Co., trade name "Rheocote R1020S") and 10 parts by weight of pentaerythritol-denatured acrylate were dissolved in methyl ethyl ketone. Colinking agent (manufactured by Nippon Kayaku Co., Ltd., trade name "DPHA40H"), 0.25 part by weight of "Tetrad C" (crosslinking agent, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 2 parts by weight of "Coronate L" (crosslinking agent, manufactured by Nippon Polyurethane Industry, Co., Ltd.) and 3 parts by weight of "Irgacure 651" (photoinitiator, manufactured by Ciba-Geigy, Ltd.), which was coated with a coater. Releaseable sheet (manufactured by Mitsubishi Polyester Film Co., trade name "MRF38"), and dried to remove volatile substances such as solvents to obtain an acrylic system having a thickness of 30 μm on the release sheet. The layer of pressure-sensitive adhesive layer.

An ethylene-vinyl acetate copolymer (EVA)-containing film having a thickness of 115 μm as a rigid film bonded to the sheet by a manual roll, and after being peeled off the sheet, a heat shrinkable film (Uniaxially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name "Space Clean S5630") was superposed on the side of the acrylic pressure-sensitive adhesive layer by a hand roller.

The side of the laminated non-energy ray-curable pressure-sensitive adhesive layer (1) obtained in Production Example 4 was laminated on the side of the rigid film layer of the laminated sheet prepared above.

The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, and a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / EVA film Layer (rigid film layer), non-energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The Young's modulus of the EVA film layer (rigid film layer) at 80 ° C was 1.08 × 10 ⁷ Newtons / square meter, and the product of Young's modulus and thickness was 1.24 × 10 ³ Newtons / meter.

The pressure-sensitive adhesive force (50 ° C) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 4.4 N/10 mm.

The non-energy ray-curable pressure-sensitive adhesive layer has a pressure-sensitive adhesive force of 0.38 Newtons/10 mm on the silicon wafer.

The value of r/L is 0.055.

[Embodiment 12]

100 parts by weight of acrylic polymer (90 parts by weight of 2-ethylhexyl acrylate and 10 parts by weight of acrylic acid), 10 parts by weight of dipentaerythritol hexaacrylate, and 3 parts by weight in ethyl acetate A polymer solution obtained by weighing "Irgacure 651" (photoinitiator, manufactured by Ciba-Geigy Ltd.) was applied to a polyethylene terephthalate film (PET film, thickness: 38) as a rigid film layer. Micron, trade name "Lumirror S10", manufactured by Toray Industries, Inc.), and a heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, trade name "Space Clean S5630", Toyobo Co., Ltd.) was superposed thereon and laminated by hand-rolling to obtain a laminated sheet (the thickness of the acrylic pressure-sensitive adhesive layer was 30 μm).

The side of the laminated energy ray-curable pressure-sensitive adhesive layer produced in Example 1 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer)], energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The acrylic pressure-sensitive adhesive layer (elastic layer) has a shear modulus of 4.79 × 10 ⁴ Newtons per square meter and a product of shear modulus and thickness of 1.44 Newtons per meter. The pressure-sensitive adhesive (50 ° C) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 11.4 Newtons/10 mm.

The value of r/L is 0.055.

[Example 13]

100 parts by weight of an ester polymer (a polymer obtained from 100 parts by weight of PLACCEL CD220PL manufactured by Daicel Chemical Industries, Ltd. and 10 parts by weight of sebacic acid), and 4 parts by weight of "Coronate L" (crossed) A polymer solution obtained by a binder, manufactured by Nippon Polyurethane Industry, Co., Ltd., was applied to a polyethylene terephthalate film (PET film, thickness: 50 μm, Toray Industries) as a rigid film layer. , manufactured by Inc., trade name "Lumirror S10"), and a heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name "Space Clean S5630") The laminate was superposed thereon and laminated by hand-rolling to obtain a laminate (the thickness of the ester-based pressure-sensitive adhesive layer was 30 μm).

The side of the laminated non-energy ray-curable pressure-sensitive adhesive layer (1) obtained in Production Example 4 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [ester-based pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer), non-energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The ester-based pressure-sensitive adhesive layer (elastic layer) had a shear modulus of 2.88 × 10 ⁵ Newtons per square meter, and the product of shear modulus and thickness was 8.64 N/m. The pressure-sensitive adhesive layer (50 ° C) of the ester-based pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 13 Newtons/10 mm.

The value of r/L is 0.05.

[Embodiment 14]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 13 except that the polyethylene terephthalate film (PET film, thickness: 38 μm, Toray Industries, Inc.) as the rigid film layer of Example 13 was used. Manufactured under the trade name "Lumirror S10").

The value of r/L is 0.045.

[Example 15]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 13 except that the energy ray-curable pressure-sensitive adhesive layer (3) obtained in Production Example 3 was used as the pressure-sensitive adhesive layer in Example 13.

The value of r/L is 0.05.

[Example 16]

100 parts by weight of an ester polymer (a polymer obtained from 100 parts by weight of PLACCEL CD220PL manufactured by Daicel Chemical Industries, Ltd. and 10 parts by weight of sebacic acid), and 4 parts by weight of "Coronate L" (crossed) A polymer solution obtained by a binder, manufactured by Nippon Polyurethane Industry, Co., Ltd., was applied to a polyethylene terephthalate film (PET film, thickness: 50 μm, Toray Industries) as a rigid film layer. , manufactured by Inc., trade name "Lumirror S10"), and a heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name "Space Clean S7053") The laminate was laminated thereon and laminated by hand-rolling to obtain a laminate (the thickness of the ester-based adhesion layer was 30 μm).

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (1) obtained in Production Example 1 was laminated on the side of the rigid film layer of the laminated sheet prepared above.

The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [ester-based pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer), energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The pressure-sensitive adhesive layer (50 ° C) of the ester-based pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 13 Newtons/10 mm.

The value of r/L is 0.06.

[Example 17]

100 parts by weight of an ester polymer (a polymer obtained from 100 parts by weight of PLACCEL CD220PL manufactured by Daicel Chemical Industries, Ltd. and 10 parts by weight of sebacic acid), and 10 parts by weight of "Coronate L" (crossed) The solution obtained by the Nippon Polyurethane Industry, manufactured by Co., Ltd., was applied to a polyethylene terephthalate film (PET film, thickness: 50 μm, Toray Industries, Inc.) as a rigid film layer. Made on the surface of one of the products, "Lumirror S10", and a heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name "Space Clean S5630") A laminate (the thickness of the ester-based pressure-sensitive adhesive layer was 30 μm) was obtained thereon by manual roll lamination.

The side of the laminated non-energy ray-curable pressure-sensitive adhesive layer (1) obtained in Production Example 4 was laminated on the side of the rigid film layer of the laminated sheet prepared above.

The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [ester-based pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer), non-energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The ester-based pressure-sensitive adhesive layer (elastic layer) had a shear modulus of 6.5 × 10 ⁵ N/m 2 and a product of shear modulus and thickness of 19.5 N/m. The pressure-sensitive adhesive layer (50 ° C) of the ester-based pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 8.2 N/10 mm.

The value of r/L is 0.05.

[Embodiment 18]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 14 except that the non-energy ray-curable pressure-sensitive adhesive layer (2) obtained in Production Example 5 was used as the pressure-sensitive adhesive layer in Example 14. .

The non-energy ray-curable pressure-sensitive adhesive layer has a pressure-sensitive adhesive force of 5.68 Newtons/10 mm on the wafer.

The value of r/L is 0.05.

[Embodiment 19]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 14 except that the non-energy ray-curable pressure-sensitive adhesive layer (3) obtained in Production Example 6 was used as the pressure-sensitive adhesive layer in Example 14. .

The non-energy ray-curable pressure-sensitive adhesive layer has a pressure-sensitive adhesive force of 3.17 Newtons/10 mm on the wafer.

The value of r/L is 0.045.

[Comparative Example 1]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that "Merinex" (trade name) having a thickness of 100 μm, manufactured by Teijin-Dupont Film Co., was used as the PET film of Example 1.

The PET film layer (rigid film layer) has a Young's modulus of 3.38 × 10 ⁹ Newtons per square meter at 80 ° C, and a product of Young's modulus and thickness of 3.38 × 10 ⁵ Newtons / meter.

After measuring r/L, the shrinkable substrate was peeled off from the elastic layer (the attachment point was broken), so that the tubular roll could not be obtained. The reason is considered to be due to the rigidity of the rigid film being too high.

[Comparative Example 2]

Mix 45 parts by weight of acrylic acid Ester, 45 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of acrylic acid, 0.1 part by weight of hexanediol diacrylate, 0.05 part by weight of "Irgacure 651" (photoinitiator, Ciba-Geigy, Ltd.). Manufactured, 0.05 parts by weight of "Irgacure 184" (photoinitiator, manufactured by Ciba-Geigy, Ltd.), and 8 parts by weight of 2-isocyanatoacrylate (manufactured by Showa Denko Co., Ltd., trade name) "Karenz AOI"), and the mixture was irradiated with ultraviolet light for 1 hour to produce a prepolymer. The prepolymer was applied onto one surface of a polyethylene terephthalate film (PET film, thickness: 38 μm, manufactured by Toray Industries, Ltd., trade name "Lumirror S10") as a rigid film layer, and A heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name "Space Clean S7053") was superposed thereon and laminated by hand roll. The final curing was carried out from both sides by ultraviolet irradiation, thereby obtaining a laminated sheet (the thickness of the acrylic adhesive layer was 105 μm).

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (1) obtained in Production Example 1 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, and a limiting layer [acrylic pressure-sensitive adhesive layer (elastic layer) / PET film Layer (rigid film layer), energy ray curable pressure-sensitive adhesive layer (1) and release sheet.

The heat shrinkable film has a heat shrinkage ratio in the main shrinkage direction of 70% or more at 100 °C.

The acrylic pressure-sensitive adhesive layer (elastic layer) had a shear modulus (80 ° C) of 1.8 × 10 ⁶ N/m 2 and a product of shear modulus and thickness of 189 N/m. The pressure-sensitive adhesive (50 ° C) of the acrylic pressure-sensitive adhesive layer (elastic layer) to the heat-shrinkable film layer was 0.3 Newton/10 mm.

When the r/L was measured, the shrinkable substrate was peeled off from the elastic layer (the attachment point was broken), so that the tubular roll could not be obtained because the rigidity of the rigid film was too high.

[Comparative Example 3]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 4 except that "Merinex" (trade name) having a thickness of 100 μm, manufactured by Teijin-Dupont Film CO., was used as the PET film of Example 4.

When the r/L was measured, the shrinkable substrate was peeled off from the elastic layer (the attachment point was broken), so that the tubular roll could not be obtained because the rigidity of the rigid film was too high.

[Comparative Example 4]

The polyester-based adhesive "Vylon 63SS" manufactured by Toyobo Co., Ltd. was coated on a polyethylene terephthalate film (PET film, thickness: 100 μm, Teijin-Dupont) as a rigid film layer by an applicator. Film Co., manufactured under the trade name "Merinex", has a thickness of 5 μm on the surface, and a heat shrinkable film (uniaxially stretched polyester film, thickness: 60 μm, manufactured by Toyobo Co., trade name "Space" Clean S7053") is overlaid and laminated to it using a hand roller.

The side of the laminated energy ray-curable pressure-sensitive adhesive layer (3) produced in Production Example 3 was laminated on the side of the rigid film layer of the laminated sheet prepared above. The laminated layer is closely adhered by a laminating machine, thereby obtaining a pressure-sensitive adhesive sheet comprising a heat-shrinkable film layer laminated in sequence, a limiting layer [polyester-based adhesive layer (elastic layer) / PET film layer (rigid film layer)], energy ray curable pressure-sensitive adhesive layer (3) and release sheet.

The polyester-based adhesive layer (elastic layer) had a shear modulus (80 ° C) of 1.41 × 10 ⁵ N/m 2 and a product of shear modulus and thickness of 0.71 N/m. The pressure-sensitive adhesive force (50 ° C) of the polyester-based adhesive layer (elastic layer) to the heat-shrinkable film layer was 7.9 N/10 mm.

After measuring r/L, the shrinking substrate is peeled off from the elastic layer (the point of attachment is broken), so that the tubular roll cannot be obtained because the rigidity of the rigid film is too high, or the elasticity of the elastic layer (shear modulus × Insufficient thickness).

[Comparative Example 5]

A pressure-sensitive adhesive sheet was produced in the same manner as in Example 19 except that the non-energy ray-curable pressure-sensitive adhesive (4) of Production Example 7 was used as the adhesive layer in Example 19.

The non-energy ray-curable pressure-sensitive adhesive layer has a pressure-sensitive adhesive force of 6.93 Newtons/10 mm on the wafer.

The value of r/L is 0.05.

The outlines of the above examples and comparative examples are as described in Table 1, and the measured values of r/L are as described in Table 2.

[Pee Test] The pressure-sensitive adhesive sheets obtained in each of the above examples and comparative examples were cut into a circular shape of the same size as a 4-inch wafer, and then bonded to a 4-inch wafer (thickness 525). Micron), the back side of the wafer is ground to a thickness of 100 microns. The pressure-sensitive adhesive sheet having the energy ray-curable pressure-sensitive adhesive layer as the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive sheet of Example 11 having a strength of 500 mJ/cm 2 by the pressure-sensitive adhesive sheet side (if An ultraviolet ray having an energy ray-curable pressure-sensitive adhesive layer as a pressure-sensitive adhesive layer and comprising an ultraviolet light-reactive crosslinking agent in the elastic layer, but the ultraviolet ray is also cured by a crosslinking agent when the ultraviolet ray is not irradiated The irradiation cures the energy ray-curable pressure-sensitive adhesive layer (the elastic layer of the pressure-sensitive adhesive sheet of Embodiment 11), and the pressure-sensitive adhesive sheet is placed in contact with the heating table to be placed in a suction chuck. The stage is heated and heated to a predetermined temperature, thereby inducing heat shrinkage of the heat-shrinkable film layer constituting the pressure-sensitive adhesive sheet.

The pressure-sensitive adhesive sheet is rolled up from the outer edge portion (one end portion) toward the outer edge portion on the opposite side in a tubular shape under heating, and is quickly peeled off from the wafer without cracking the wafer (one-way The case of scrolling is rated as "A". Further, the pressure-sensitive adhesive sheet is rolled up from the opposite end portions toward the center to form two tubular reels, and is quickly peeled off from the wafer without rupturing the wafer (two-way scrolling) as "B"; The pressure-sensitive adhesive sheet was evaluated as "C" when it was broken or unrolled between the heat-shrinkable film layer and the elastic layer to form a tubular shape.

In all of the above-mentioned cases evaluated as "A" or "B", the diameter of the tubular reel is regarded as r [mm] of r/101.6 [mm] (the diameter of the circular sheet) is 0.001 To the extent of 0.333.

The results of the peel test are shown in Table 2. In Table 2, "D" means that there is no change under heating, and "-" means that no measurement is made (the same applies to Table 3).

[Grinding Test of Thickness 25 μm Wafer (8 Inch)] In the above peeling test, these pressure sensitive adhesive sheets which exhibited good results were used for the rubbing test of a thickness of 25 μm by the following method.

The pressure-sensitive adhesive tapes shown in Examples 1, 2, 4, 5, 7 and 8 were prepared using a precision coating apparatus to increase the accuracy of the thickness.

Each of the prepared pressure-sensitive adhesive tapes was bonded to a 9-inch mirror wafer using DR8500II manufactured by Nitto Seiki Co., Ltd., and ground to a thickness of 25 μm using a wafer grinding apparatus DFG8560 manufactured by Disco Corporation. After grinding, those having no crack on a wafer and having an edge crack size of 30 μm or less were rated as “1”; those having no crack on the wafer and having an edge crack size of 30 μm or more were rated as “2”; Those with cracks on the wafer are rated as "3".

Next, the warpage of the polished wafer is checked. If the polishing result is "1" or "2", the wafer is mounted to a molding platform, and the two farthest positions of the self-molding platform are measured. The distance from the far wafer.

The pressure-sensitive adhesive sheet has a grinding ability of "1" and the amount of warpage is good, and the maximum is 7 mm. The results of this grinding test are shown in Table 3.

In order to confirm the function of the easy peeling ability by the self-rolling property, Examples 4, 5 and 7 were used to examine the peeling of the pressure-sensitive adhesive sheet from the grinding to the 25 μm wafer, and the wafer was returned to a pure body. After exposing the pressure-sensitive adhesive tape to ultraviolet light (about 500 mJ/m2), a wafer attached to the pressure-sensitive adhesive tape was placed on a suction heating stage heated to 100 °C. Results In all of the tests, the pressure-sensitive adhesive tape was peeled off by self-winding in 1 second, and the wafer was reversible without any cracking. If it is performed manually, it usually takes 10 minutes or more to confirm that it can be easily performed without using a specific instrument (the table is indicated by "good"). The results are shown in Table 3.

[Comparison of the amount of residual wafer adhesive (wafer contamination ability) after the pressure-sensitive adhesive sheet was peeled off] The difference between the peeling of the tubular reel (rolling peeling) and the peeling by manual operation was investigated by the following method.

Each of the pressure-sensitive adhesive tapes of Examples 4, 7 and 19 was bonded to a 4-inch mirror-finished wafer (manufactured by Shin-Etsu Semiconductor Co., Ltd., trade name "CZ-N") for evaluation of pollution ability. And the combination is treated at 40 ° C in an autoclave to increase the adhesion. For the samples produced, the pressure-sensitive adhesive sheets used in the respective Examples 4 and 7 were exposed to ultraviolet light (about 500 mJ/m 2 ), and then the wafer was heated under self-winding. Stripping, and the wafer was manually stripped at room temperature or heated until the degree of self-winding, and Particle Counter Surfscan 6200 (manufactured by KLA-Tencor Corporation) was used to measure particles derived from residual glue on the surface of the wafer. Number (these have a size of 0.2 microns or more).

As a result, it was found that in all of the tests, the trace of the glue in the test by the tubular reel was small, and the results of the wafer contamination ability are shown in Table 3.

[Evaluation of Self-rolling Pressure-sensitive Adhesive Tape Application] In order to evaluate the applicability of current wafer grinding methods, the following evaluations were made.

In the above-mentioned 25 nm micron wafer polishing test, one of the pressure sensitive adhesive sheets was obtained by adhering the pressure sensitive adhesive sheet of the seventh embodiment to a thickness of 25 micrometers and 8 inches of the wafer, and was irradiated with ultraviolet light ( About 500 mJ/m2, and then, in order to determine the applicability of the actual method, the peeling and recovery test of a dicing tape bond and the pressure-sensitive adhesive sheet of Example 7 were manufactured by using Nitto Seiki Co., Ltd. The cutting is carried out with a bonding/back grinding belt stripping device "MA3000II". For the functional display of the self-rolling peeling capability, a heating source (industrial dryer) for displaying the self-rolling property is attached to the strip peeling/recovering device component, and the heating source is adjusted to heat the twin crystal Round to about 80 ° C to 100 ° C.

Using the device "MA3000II", a dicing tape, manufactured by Nitto Denko Corporation, under the trade name "EM500M2A", is bonded to the side of the grinding surface of an 8-inch wafer and is provided with a cutting ring. When the dicing tape is bonded, the wafer is heated to 50 ° C to 60 ° C, but the pressure-sensitive adhesive sheet of Example 7 is not spontaneously peeled off under the heating, and there is no difficulty (for example, peeling tape is conveyed The main method is completed by being stuck in the path, etc.). Therefore, when the sample was transferred to the stripping/recovering apparatus "MA3000II", hot air was blown from the heating source to the pressure-sensitive adhesive sheet side of Example 7 to heat the edge portion of the wafer. As a result, the pressure-sensitive adhesive sheet of Example 7 was peeled off from the wafer by the tape peeling apparatus "MA3000II". Here, the wafer does not cause any cracking or cracking. In addition, there is any adverse effect on the heating of the dicing tape during peeling (for example, an increase in pressure-sensitive adhesive force, etc.), and the dicing tape of the sample is also peeled off. Functional assessment, but without any problems.

From these results, it can be confirmed that the pressure-sensitive adhesive sheet of the present invention can be applied to an actual method.

While the invention has been described with reference to the specific embodiments of the embodiments of the invention

The present application is based on Japanese Patent Application No. 2006-305671, filed on Nov. 10, 2006, and Japanese Patent Application No. 2007-260077, filed on Oct. 3, 2007, This article is a reference.

Moreover, the entire contents of all of the references cited herein are incorporated herein by reference.

1. . . Shrinkable film

2. . . Restricted layer

3. . . Pressure sensitive adhesive layer

twenty one. . . Elastic layer

twenty two. . . Rigid film

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a self-rolling laminated sheet of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of the self-rolling pressure-sensitive adhesive sheet of the present invention.

3A to 3D are diagrams (perspective views) illustrating a self-rolling mode of a self-rolling laminated sheet or a pressure-sensitive adhesive sheet of the present invention, wherein FIG. 3A illustrates the provision of a self-rolling laminated sheet or a pressure-sensitive adhesive sheet. The pattern before the stimulation of the contraction of the shrinkable film; FIG. 3B illustrates the self-rolling laminated sheet or the pressure-sensitive adhesive sheet provided by the stimulation of the shrinkage of the shrinkable film layer (the pressure-sensitive adhesive force on the pressure-sensitive adhesive layer) A pressure-sensitive adhesive sheet which has been lowered or lost) starts from a state in which a state is rolled up from the outer edge portion in a direction (generally along the main shrinkage axis of the shrinkable film); FIG. 3C illustrates the completion of scrolling of the sheet. And a pattern in which a tubular reel (unidirectional rolling) is formed; and FIG. 3D illustrates that the sheet is spontaneously rolled up from the opposite ends toward the center (generally along the main shrinking axis of the shrinkable film), thereby forming A diagram of the state of two tubular reels (two-way scrolling).

1. . . Shrinkable film

2. . . Restricted layer

3. . . Pressure sensitive adhesive layer

twenty one. . . Elastic layer

twenty two. . . Rigid film

Claims (20)

A self-rolling laminated sheet comprising: a shrinkable film layer that can be shrunk in at least one axial direction; and a restraining layer that limits shrinkage of the shrinkable film layer, the restraining layer being disposed on one side of the shrinkable film layer Above, wherein the shrinkable film layer has a heat shrinkable film that shrinks in a temperature range of 70 to 180 ° C, and when the self-rolling laminated sheet is thermally stimulated to induce shrinkage of the shrinkable film layer, the self-rolling type The laminated sheet is rolled up from one end in one direction to form a tubular reel or rolled up from the opposite ends toward the center of the opposite ends to form two tubular reels. The self-rolling laminated sheet according to claim 1, wherein the heat shrinkable film has a heat shrinkage ratio of 30 to 90% in a main shrinkage direction in a temperature range of 70 to 180 °C. A self-rolling laminated sheet according to claim 1, wherein the limiting layer comprises an elastic layer on the side of the shrinkable film layer and a rigid film layer on the side opposite to the side of the shrinkable film layer. A self-rolling laminated sheet according to claim 3, wherein the elastic layer has a thickness of 15 to 150 μm and a shear modulus of 1 × 10 ⁴ Pa to 5 × 10 ⁶ Pa at 80 °C. The self-rolling laminated sheet of claim 3, wherein the elastic layer has a product of a shear modulus at 80 ° C and a thickness in the range of 1 to 1000 Newtons per meter. A self-rolling laminated sheet according to claim 3, wherein the rigid film layer has a product of Young's modulus and thickness at 80 ° C of 3.0 × 10 ⁵ Newtons / meter or less. The self-rolling laminated sheet according to claim 3, wherein the elastic layer is formed of a crosslinked acrylic pressure sensitive adhesive. The self-rolling laminated sheet of claim 1, wherein the self-rolling laminated sheet is rolled up to form a tubular reel after stimulating shrinkage of the shrinkable film layer by the self-rolling laminated sheet. The formed tubular reel has a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-based tubular reel and the length of the L-series self-rolling laminated sheet in the rolling direction. The self-rolling laminated sheet of claim 1, wherein the self-rolling laminated sheet is rolled up to form two tubular reels after stimulating shrinkage of the shrinkable film layer by the self-rolling laminated sheet, The tubular reels formed each have a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-type tubular reel and the length of the L-series self-rolling laminated sheet in the rolling direction. A self-rolling pressure-sensitive adhesive sheet comprising: a shrinkable film layer that can be contracted in at least one axial direction; a limiting layer that limits shrinkage of the shrinkable film layer, the limiting layer being disposed on one of the shrinkable film layers And a pressure-sensitive adhesive layer disposed on a side of the limiting layer opposite to a side on which the shrinkable film layer is disposed, wherein the self-rolling pressure-sensitive adhesive sheet is a releasable pressure-sensitive adhesive sheet, wherein The pressure-sensitive adhesive layer or the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer after the adhesive treatment is reduced (180° peeling on the mirror wafer, tensile speed: 300 mm/min) is 6.5 Newtons/10 mm or less. And wherein the shrinkable film layer has a temperature in the range of 70 to 180 ° C a shrinkable heat-shrinkable film, and when the self-rolling pressure-sensitive adhesive sheet is thermally stimulated to induce shrinkage of the shrinkable film layer, the self-rolling pressure-sensitive adhesive sheet is rolled up from one end in one direction to form a tubular roll The canister, or rolled up from the opposite ends toward the center of the opposite ends, forms two tubular reels. The self-rolling pressure-sensitive adhesive sheet according to claim 10, wherein the heat-shrinkable film has a heat shrinkage ratio of 30 to 90% in a main shrinkage direction in a temperature range of 70 to 180 °C. The self-rolling pressure-sensitive adhesive sheet of claim 10, wherein the limiting layer comprises an elastic layer on the side of the shrinkable film layer and a rigid film on a side opposite to the side of the shrinkable film layer. Floor. The self-rolling pressure-sensitive adhesive sheet of claim 12, wherein the elastic layer has a thickness of 15 to 150 μm and a shear modulus of 1 × 10 ⁴ Pa to 5 × 10 ⁶ Pa at 80 °C. The self-rolling pressure-sensitive adhesive sheet of claim 12, wherein the elastic layer has a product of a shear modulus at 80 ° C and a thickness in the range of 1 to 1000 N/m. A self-rolling pressure-sensitive adhesive sheet according to claim 12, wherein the rigid film layer has a product of a Young's modulus at 80 ° C and a thickness of 3.0 × 10 ⁵ Newtons/meter or less. A self-rolling pressure-sensitive adhesive sheet according to claim 12, wherein the elastic layer is formed of a crosslinked acrylic pressure sensitive adhesive. The self-rolling pressure-sensitive adhesive sheet of claim 10, wherein the pressure-sensitive adhesive layer is formed of an energy ray-curable pressure-sensitive adhesive. The self-rolling pressure-sensitive adhesive sheet according to claim 10, wherein the self-rolling pressure-sensitive adhesive sheet is rolled up to form a shrinkage after stimulating the shrinkage of the shrinkable film layer by the self-rolling pressure sensitive adhesive sheet In the case of a tubular reel, the tubular reel formed has a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-shaped tubular reel and the length of the L-series self-rolling pressure-sensitive adhesive sheet in the rolling direction . The self-rolling pressure-sensitive adhesive sheet according to claim 10, wherein the self-rolling pressure-sensitive adhesive sheet is rolled up to form two after the shrinkage of the shrinkable film layer is induced by the self-rolling pressure sensitive adhesive sheet. In the case of a tubular reel, the tubular reels each have a ratio (r/L) in the range of 0.001 to 0.333, wherein the diameter of the r-shaped tubular reel and the L-series self-rolling pressure-sensitive adhesive sheet are in the rolling direction. length. A method of processing an object, comprising: adhering a self-rolling pressure-sensitive adhesive sheet of claim 10 to an object to temporarily fix the object, and then processing the object; and reducing the pressure of the pressure-sensitive adhesive sheet Adhesive force and the pressure sensitive adhesive sheet provide a stimulus for inducing shrinkage of the shrinkable film layer, whereby the pressure sensitive adhesive sheet spontaneously rolls up from one end in one direction to form a tubular roll, or from opposite ends Two tubular reels are formed rolled up toward the center of the opposite ends, and thus are peeled from the article; and a finished article is obtained.