TWI791424B - Adhesive sheet for glass cutting and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide an adhesive sheet for glass cutting capable of effectively cutting a glass plate while suppressing chipping, and a method for producing the same.

The solution of the present invention is an adhesive sheet for glass cutting, which is an adhesive sheet for glass cutting including a base material and an adhesive layer laminated on at least one surface of the base material, wherein the thickness of the base material is 30 μm or more and less than 130 μm, and the storage elastic modulus at 100° C. of the adhesive layer is 6 to 50 kPa.

Description

Adhesive sheet for glass cutting and manufacturing method thereof

The present invention relates to an adhesive sheet for glass cutting used for cutting a glass plate to obtain a glass wafer, and a manufacturing method thereof.

Microscopic pieces of glass are required in the manufacture of camera modules for mobile phones and smartphones. Such a glass sheet is obtained by cutting a glass sheet using a cutting sheet. That is, after attaching a glass plate to a sheet for dicing, the glass is cut with a dicing blade to obtain individualized glass (hereinafter sometimes referred to as "glass wafer"). In recent years, due to the reduction in thickness of smartphones and the miniaturization of camera modules mounted therein, it is necessary to manufacture thinner fine glass chips (hereinafter sometimes referred to as "chiplets").

Chipping is prone to occur when cutting brittle materials such as glass. Here, the term "notch" means that the edge or cut surface of the glass wafer is missing during dicing. The thinner the thickness of the glass plate, the more conspicuously chipped corners occur.

Patent Document 1 discloses an adhesive sheet for dicing a glass substrate in which an adhesive layer is provided on a base film. In this patent document 1, it is disclosed that a film having a thickness of 130 μm or more and a tensile modulus of 1 GPa or more is used as the base film, and the thickness of the adhesive layer is further reduced to 9 μm or less, so that the pressure of the adhesive sheet due to the cutting blade can be reduced. Deformation can suppress the occurrence of chipped corners and wafer flying (paragraph 0010 of Patent Document 1)

[Prior Art Literature]

[Patent Document]

[Patent Document 1] Japanese Patent No. 3838637

In recent years, with the miniaturization of camera modules, the size of the required glass wafers has also become very small. The adhesive sheet disclosed in Patent Document 1 cannot sufficiently suppress chipped corners of such a very small-sized glass wafer.

This invention was made in view of the said actual situation, and it aims at providing the adhesive sheet for glass cutting which can suppress chipping, and can cut a glass plate efficiently, and its manufacturing method.

In order to achieve the above object, firstly, the present invention provides an adhesive sheet for glass cutting, which is an adhesive sheet for glass cutting provided with: a base material and an adhesive layer laminated on at least one surface of the base material, It is characterized in that the thickness of the substrate is 30 μm or more and less than 130 μm, and the storage elastic modulus of the adhesive layer at 100° C. is 6 to 50 kPa (Invention 1).

In the said invention (invention 1), when a base material has the said thickness, the handleability of the adhesive sheet for glass cutting can be made favorable. Furthermore, since the adhesive layer exhibits the aforementioned storage modulus of elasticity at 100°C, when the temperature of the adhesive layer is set to a high temperature of about 100°C due to frictional heat during cutting, the result of shaking during cutting can be sufficiently suppressed, even It suppresses chipping when cutting thin glass sheets into small wafers. By controlling the thickness of the substrate and the modulus of elasticity of the adhesive layer as above, small chips can be efficiently obtained from thin glass plates.

In the above invention (Invention 1), the thickness of the adhesive layer is preferably 5-25 μm (Invention 2).

In the above inventions (Inventions 1 and 2), the storage elastic modulus of the adhesive layer at 23° C. is preferably 30 to 100 kPa (Invention 3).

In the above inventions (Inventions 1 to 3), the surface of the above-mentioned adhesive layer on the opposite side to the above-mentioned base material is pasted on the non-alkali glass, and after standing for 20 minutes, the above-mentioned glass cutting adhesive sheet is attached to the above-mentioned non-alkali glass. The best adhesion is 8000~25000mN/25mm (invention 4).

In the above-mentioned inventions (Inventions 1-4), the above-mentioned adhesive layer is changed to a peeling speed of 1mm/min by the method described in JIS Z0237:1991, and the energy measured by the viscosity of the probe is 0.01-5mJ/5mm. ψ is preferred (invention 5).

In the above inventions (Inventions 1 to 5), it is preferable that the adhesive layer is composed of an energy ray curable adhesive (Invention 6).

In the above invention (Invention 6), the above-mentioned adhesive layer is preferably composed of an adhesive composed of an adhesive composition containing a (meth)acrylate copolymer (A) having a side chain introducing energy ray curable group ( Invention 7).

In the above invention (Invention 7), it is preferable that the adhesive composition further contains an energy ray-curable compound (B) other than the above (meth)acrylate copolymer (A) (Invention 8).

In the above inventions (Inventions 7 and 8), it is preferable that the adhesive composition further contains a bridging agent (C) (Invention 9).

In the above inventions (Inventions 1-9), the storage elastic modulus of the base material at 23° C. is preferably 100-8000 MPa (Invention 10).

Second, the present invention provides a method for manufacturing an adhesive sheet for glass cutting, which is the method for manufacturing the above-mentioned adhesive sheet for glass cutting (Invention 7), which is characterized in that it comprises: making at least (meth)acrylic acid alkyl An acrylic copolymer (AP) in which an ester monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group are copolymerized, and a functional group having a functional group that can be combined with the above-mentioned functional group-containing monomer (A2) Reaction of the energy ray curable group-containing compound (A3) with an energy ray curable carbon-carbon double bond bonded functional group to prepare a (meth)acrylate copolymer in which an energy ray curable group is introduced into the side chain (A); and a step of laminating an adhesive layer on at least one surface of a base material using an adhesive composition containing the (meth)acrylate copolymer (A) (Invention 11).

In the above-mentioned invention (Invention 11), the above-mentioned acrylic copolymer (AP) is reacted with the above-mentioned energy ray-curable group-containing compound (A3) to be selected from an organic compound containing zirconium, an organic compound containing titanium, and an organic compound containing It is preferably carried out in the presence of at least one organometallic catalyst (D) which is an organic compound of tin (Invention 12).

According to the adhesive sheet for glass cutting concerning this invention, and the adhesive sheet for glass cutting manufactured by the manufacturing method of this invention, a glass plate can be efficiently cut|disconnected while suppressing chipping.

Embodiments of the present invention will be described below.

The adhesive sheet for cutting glass of this embodiment (hereinafter, sometimes simply referred to as "adhesive sheet") includes: a base material; and one surface laminated on the base material. composed of an adhesive layer.

In the adhesive sheet for glass cutting concerning this embodiment, the thickness of a base material is 30 micrometers or more and less than 130 micrometers. In addition, the storage elastic modulus of the adhesive layer at 100° C. is 6-50 kPa.

The base material has the said thickness about the adhesive sheet sheet for glass cutting of this embodiment, and workability|operativity regarding glass cutting can be made favorable. In addition, by making the storage elastic modulus at 100°C of the adhesive layer within the above range, even when the temperature of the adhesive layer becomes as high as about 100°C due to frictional heat during cutting, shaking of the adhesive sheet can be suppressed. Thereby, glass wafers are suppressed from colliding with each other, or unintended collisions of a glass plate or a cut surface of a glass wafer and a dicing blade are suppressed, thereby suppressing generation of chipped corners. From these results, small wafers can be efficiently obtained from thin glass plates.

1. Substrate

In the adhesive sheet for glass cutting of this embodiment, the thickness of the base material is not less than 30 μm and not less than 130 μm, preferably not less than 50 μm and not more than 120 μm, and particularly preferably not less than 70 μm and not more than 110 μm. When the thickness of the base material is less than 30 μm, the adhesive sheet tends to vibrate during the cutting step, and as a result, the glass plate tends to displace on the adhesive sheet, resulting in chipping and push-out (die). shift). Furthermore, the so-called push crystal means that the glass plate deviates from the original position on the adhesive sheet during cutting. If further dicing is performed in a state where push-out has occurred, the glass plate cannot be cut at the intended position, and as a result, a glass wafer having a desired shape cannot be obtained. Moreover, when the thickness of a base material is less than 30 micrometers, it becomes easy to break when handling an adhesive sheet or an expansion process. On the other hand, when the thickness of the base material is more than 130 μm, the flexibility of the adhesive sheet as a whole will be reduced. When sticking to the ring frame or jig for cutting, the adhesive sheet becomes easy to fall off from the ring frame or jig when cutting the glass plate.

Regarding the adhesive sheet for glass cutting in this embodiment, the storage elastic modulus of the substrate at 23° C. is preferably 100-8000 MPa, particularly preferably 1500-7000 MPa, and further preferably 2000-6000 MPa. By making the storage elastic modulus of the substrate at 23°C more than 100MPa, it can reduce the shaking of the adhesive sheet during the cutting process, and restrain the displacement of the glass plate on the adhesive sheet, and can more effectively suppress the occurrence of chipped corners. , can also inhibit crystal push. In addition, the storage elastic modulus of the substrate at 23° C. is below 8000 MPa, which ensures the flexibility of the substrate and makes the substrate excellent in extensibility (expandability). Thereby, at the time of an expansion process, the adhesive sheet shows excellent expandability, and pick-up of the glass wafer after dicing can be performed favorably. In addition, the storage elastic modulus of a base material at 23 degreeC was measured using the dynamic elastic modulus measuring apparatus (manufactured by TA Instruments, product name "DMA Q800") under the following conditions.

Test start temperature: 0°C

Test end temperature: 200°C

Heating rate: 3°C/min

Frequency: 11Hz

Amplitude: 20μm

As for the base material of the adhesive sheet sheet for glass cutting of this embodiment, as long as it has the said thickness, its constituent material will not be specifically limited. The substrate may be a film (resin film) mainly composed of a resin-based material. It is preferable that the base material consists only of a resin film. Specific examples of resin films include ethylene-vinyl acetate copolymer films, ethylene-(meth)acrylic acid copolymer films, ethylene-(meth) Ethylene-based copolymer films such as acrylate copolymer films; polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, ethylene-norbornene copolymer films, norbornene Polyolefin-based films such as vinyl resin films; polyvinyl chloride-based films such as polyvinyl chloride films and vinyl chloride copolymer films; polyethylene terephthalate films, polybutylene terephthalate films, etc. Polyester film; Polyurethane film; Polyimide film; Polystyrene film; Polycarbonate film; Fluorine resin film, etc. Examples of polyethylene films include low-density polyethylene (LDPE) films, linear low-density polyethylene (LLDPE) films, and high-density polyethylene (HDPE) films. In addition, denatured films such as these bridging films and ionomer films can also be used. The base material may be a film composed of one of these types, or a film obtained by laminating two or more of these types in combination. Among these, it is preferable to use a polyethylene terephthalate film from the viewpoint of being easy to achieve the aforementioned storage modulus. In addition, "(meth)acrylic acid" in this specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.

Various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, smoothing agents, and fillers may be contained in the base material and the above-mentioned film. Pigments include, for example, titanium dioxide, carbon black, and the like. In addition, examples of fillers include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of these additives is not particularly limited, but it is preferably within a range that can exhibit desired functions on the substrate without losing smoothness and flexibility.

When ultraviolet rays are used as energy rays for irradiation to harden the adhesive layer, it is preferable that the base material is transparent to ultraviolet rays. In addition, when electron beams are used as the energy rays, it is preferable that the base material is permeable to the electron beams.

Surface treatment such as primer treatment, corona treatment, plasma treatment, roughening treatment (matte treatment) and the like may be applied to the surface of the base material on the side of the adhesive layer in order to improve the adhesion with the adhesive layer. The roughening treatment includes, for example, an embossing method, a blasting method, and the like. In addition, various coating films may be provided on the surface opposite to the base material and the adhesive layer.

2. Adhesive layer

(1) Thickness and physical properties of the adhesive layer

The storage elastic modulus of the adhesive layer at 100°C is 6-50kPa, preferably 7-40kPa, particularly preferably 10-30. Generally, adhesive sheets are used for glass cutting. Frictional heat is generated during cutting, and the adhesive layer becomes a high temperature state of about 100°C. In such a high temperature state, if the adhesive layer shows a low storage elastic modulus of less than 6kPa, the adhesive sheet will shake during cutting, and the glass plate or glass wafer will easily shift on the adhesive sheet, resulting in chipped corners. . In addition, when the storage elastic modulus is higher than 50kPa, the storage elastic modulus at 23°C is accompanied by the storage elastic modulus at 23°C. number) is also likely to become high, and it is difficult to obtain good adhesion. As a result, it is difficult to hold the glass plate or glass wafer well on the adhesive sheet, and it is impossible to sufficiently suppress chipped corners during dicing. In addition, in this specification, when an adhesive layer consists of the energy-beam curable adhesive mentioned later, this storage elastic modulus is the value measured before energy-beam irradiation. In addition, the method of measuring the storage modulus of elasticity at 100° C. before energy ray irradiation of the adhesive layer is as shown in the test example described later.

The storage elastic modulus of the adhesive layer at 23°C is preferably 30-100kPa, particularly preferably 40-90kPa, and further preferably 50-80kPa. By setting the modulus of elasticity within the above range, the adhesive sheet for glass cutting can exhibit good performance. Adhesive force, whereby the glass wafer can be well kept on the adhesive plate, which can effectively suppress the chipped corner during cutting, and can also suppress the chip push and chip flying. In addition, in this specification, when an adhesive layer consists of the energy-beam curable adhesive layer mentioned later, this storage elastic modulus is the value measured before energy-beam irradiation. In addition, the method of measuring the storage modulus of elasticity at 23° C. before energy ray irradiation of the adhesive layer is as shown in the test example described later.

Regarding the adhesive sheet for glass cutting of this embodiment, the thickness of the adhesive layer is preferably 5-25 μm, more preferably 7-20 μm, particularly preferably 8-19 μm, further preferably 9-15 μm, and further preferably 9-15 μm. 10~12μm is better. By making the thickness of the adhesive layer more than 5 μm, it is easy to control the adhesive force, effectively suppress chipping, and suppress chip push and chip flying. In addition, by making the thickness of the adhesive layer less than 25 μm, the shaking of the adhesive layer during cutting can be further reduced, and the displacement of the glass sheet on the adhesive sheet can be effectively suppressed, which can effectively suppress chipped corners. , can also inhibit crystal push.

In the adhesive layer, use the probe tack to measure the energy (referred to as "viscosity value" in this manual.), preferably 0.01~5mJ/5mmψ, especially preferably 0.13~4mJ/5mmψ, further 0.18~3.5mJ/5mmψ is better. When the viscosity value is within the above range, the glass wafer can be held favorably on the adhesive sheet for glass dicing, and it is possible to suppress wafer scattering during dicing. In addition, in this specification, when an adhesive layer consists of the energy-beam curable adhesive layer mentioned later, this viscosity value is the value measured before energy-beam irradiation. In addition, in this specification, the viscosity value was measured by the method described in JIS Z0237:2009, and the peeling speed was changed to 1 mm/min. The detail is shown in the test example mentioned later.

When the adhesive layer is composed of the energy ray hardening adhesive described later, the tensile elastic modulus of the adhesive layer at 23°C after energy ray irradiation is preferably 15~70MPa, particularly preferably 50~60MPa, Further, 23~50MPa is better. Picking up of the glass wafer after energy-beam irradiation can be performed favorably by making this tensile elastic modulus 15 MPa or more. Moreover, the expansibility of the adhesive sheet sheet for glass cutting can be made favorable by making this tensile elastic modulus 70 MPa or less, and it can pick up favorably. In addition, the measuring method of the tensile elastic modulus at 23 degreeC of an adhesive layer before energy-beam irradiation is shown in the test example mentioned later.

The gel fraction of the adhesive constituting the adhesive layer is preferably 12.5-100%, particularly preferably 37.5-100%, and further preferably 50-95%. When the gel fraction of the adhesive is within the above range, it is easy to satisfy the above physical properties of the adhesive layer. In addition, by setting the gel fraction of the adhesive to 12.5% or more, the cohesive force of the adhesive can be improved, and the durability of the adhesive layer can be maintained.

(2) Adhesive constituting the adhesive layer

The adhesive constituting the adhesive layer may be a non-hardening adhesive or a hardening adhesive. In addition, the curable adhesive may be in a state before or after curing. When the adhesive layer is composed of multiple layers, it may also be a combination of a non-hardening adhesive and a hardening adhesive. Non-hardening adhesives include, for example, acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, polyester adhesives, and polyvinyl ether adhesives. Curable adhesives include, for example, energy ray curable adhesives, thermosetting adhesives, and the like.

Regarding the adhesive sheet for glass cutting of this embodiment, the adhesive layer is preferably composed of an energy ray hardening adhesive, especially an energy ray hardening adhesive. Chemical acrylic adhesive composition is preferred. By forming the adhesive layer with an energy ray-curable adhesive, the adhesive layer can be irradiated with energy rays before the pick-up step to harden the adhesive layer. Thereby, the adhesive force of the adhesive sheet to the glass wafer can be moderately reduced, and the pick-up can be performed well.

In general, an energy ray-curable acrylic adhesive consists of a (meth)acrylate copolymer (A) containing a side chain-introduced energy ray-curable group, and does not contain the (meth)acrylate copolymer Formation of an adhesive composition of an energy ray-curable compound (B) other than (A) (hereinafter sometimes referred to as "X-type" for convenience.); composed of an acrylic polymer that does not have energy-ray-curable properties (N) and an adhesive composition formed of an energy ray-curable compound (B) other than the above-mentioned (meth)acrylate copolymer (A) (hereinafter, sometimes referred to as "Y type" for convenience.); And an adhesive comprising a (meth)acrylate copolymer (A) containing a side chain-introduced energy ray-curable group and an energy ray-curable compound (B) other than the (meth)acrylate copolymer (A) Those who form the composition (hereinafter sometimes referred to as "Z type" for convenience.).

In the adhesive sheet for cutting glass of this embodiment, the adhesive layer may consist of any of these adhesives. In particular, since the X-type adhesive exhibits a high modulus of elasticity at high temperature, it is better to use the X-type adhesive from the viewpoint of effectively suppressing chipped corners during dicing and further suppressing push-out. In addition, it is preferable to use a Y-type adhesive because it is easy to obtain excellent adhesiveness, and especially from the viewpoint of suppressing wafer scattering during dicing. Furthermore, when a Z-type adhesive is used, since the elastic modulus of the adhesive layer becomes higher after energy ray irradiation, it is preferable to use a Z-type adhesive from the viewpoint of good pick-up.

The above-mentioned (meth)acrylate copolymer (A) having an energy ray curable group introduced into the side chain and the acrylic polymer (N) not having energy ray curability can be directly contained in the adhesive layer, or can be mixed with A bridging agent (C) to be described later is contained in a bridging substance through a bridging reaction.

(2-1) (Meth)acrylate copolymer (A) having an energy ray-curable group introduced into the side chain

The (meth)acrylate copolymer (A) into which an energy ray-curable group is introduced into a side chain is preferably obtained by reacting an acrylic copolymer (AP) with a compound (A3) containing an energy ray-curable group.

The acrylic copolymer (AP) preferably copolymerizes at least an alkyl (meth)acrylate monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group.

The alkyl (meth)acrylate monomer (A1) preferably has 1 to 18 carbon atoms in the alkyl group, and particularly preferably has 1 to 4 carbon atoms. Specific examples of alkyl (meth)acrylate monomers (A1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate ester, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, ( Lauryl methacrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

The ratio of the mass of the structural portion derived from the above-mentioned alkyl (meth)acrylate monomer (A1) to the mass of the entire acrylic copolymer (AP) is preferably 50 to 98% by mass, particularly 60 to 95% by mass. preferably, more preferably 70 to 90% by mass.

As the functional group-containing monomer (A2), a reactive functional group capable of reacting with the functional group of the energy ray-curable group-containing compound (A3) is used. The functional group contained in the functional group-containing monomer (A2) includes, for example, hydroxyl group, carboxyl group, amino group, substituted amino group, epoxy group, etc. Among them, hydroxyl group and carboxyl group are preferred, and hydroxyl group is particularly preferred. Furthermore, when using a bridging agent (C) described later, the reactive functional group contained in the functional group-containing monomer (A2) can also react with the bridging agent (C).

When a monomer having a hydroxyl group (containing a hydroxyl group monomer) is used as the functional group-containing monomer (A2), an example thereof is hydroxyalkyl (meth)acrylate, and a specific example thereof is (meth)acrylic acid 2-Hydroxyethyl ester, 2-Hydroxypropyl (meth)acrylate, 3-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 3-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, etc. Among them, 2-hydroxyethyl (meth)acrylate is preferable in view of the reactivity of hydroxyl groups and copolymerizability. These may be used alone or in combination of two or more.

When using a carboxyl group-containing monomer (carboxyl group-containing monomer) as the functional group-containing monomer (A2), examples thereof include ethylenically unsaturated carboxylic acids, and specific examples thereof include acrylic acid, methacrylic acid, and crotonic acid. , maleic acid, itaconic acid, citraconic acid, etc. Among them, acrylic acid is preferable in terms of carboxyl group reactivity and copolymerizability. These may be used alone or in combination of two or more.

Furthermore, different types of functional group-containing monomers (A2) can also be used in combination. For example, it is also possible to use in combination the monomer containing the hydroxyl group mentioned above, and the monomer containing a carboxyl group.

The ratio of the mass of the structural portion derived from the functional group-containing monomer (A2) to the mass of the entire acrylic copolymer (AP) is preferably 5 to 40% by mass, particularly preferably 7 to 35% by mass, and further preferably 10% by mass. ~30% by mass is preferred. by making The ratio by mass of the structural portion of the functional group-containing monomer (A2) is within the above range, and the (meth)acrylate copolymer that introduces energy ray-curable groups to side chains from the energy ray-curable group-containing compound (A3) can be copolymerized The introduced amount of the substance (A) was in a good range. In addition, when the bridging agent (C) described later is used to react the functional group-containing monomer (A2) with the bridging agent (C), the bridging degree of the bridging agent (C), that is, the gel fraction can be kept at a good level. The physical properties such as the cohesion of the adhesive layer can be controlled.

The acrylic copolymer (AP) may contain other monomers in addition to the above-mentioned alkyl (meth)acrylate monomer (A1) and functional group-containing monomer (A2) to the monomers constituting it.

The other monomers include, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxy (meth)acrylate Alkoxyalkyl-containing acrylates such as ethyl esters; (meth)acrylates with aliphatic rings such as cyclohexyl (meth)acrylate; aromatic rings such as phenyl (meth)acrylate (Meth)acrylates; non-bridging acrylamides such as acrylamide and methacrylamide; N,N-dimethylaminoethyl (meth)acrylate, N,(meth)acrylate (Meth)acrylates with non-bridging tertiary amino groups such as N-dimethylaminopropyl; vinyl acetate; styrene, etc. These may be used alone or in combination of two or more.

The polymerization form of the acrylic copolymer (AP) may be a random copolymer or a block copolymer. In addition, the polymerization method is not particularly limited, and it can be polymerized by a general polymerization method.

The energy ray curable group-containing compound (A3) has a functional group capable of reacting with the functional group of the functional group-containing monomer (A2) and an energy ray curable carbon-carbon double bond.

The functional groups reacted with the functional groups of the functional group-containing monomer (A2) include, for example, isocyanate groups and epoxy groups, among which isocyanate groups with high reactivity with hydroxyl groups are preferred.

The carbon-carbon double bond curable group having energy ray curability (energy ray curable group) is preferably a (meth)acryl group or the like. Furthermore, the presence of energy ray-curable carbon-carbon double bonds is preferably 1 to 5, and particularly preferably 1 to 3, in one molecule of the energy ray-curable group-containing compound (A3).

Examples of the compound (A3) containing an energy ray curable group include 2-methacryloxyethyl isocyanate, o-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryl isocyanate, Allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; diisocyanate compound or polyisocyanate compound, acryl monoisocyanate compound obtained by reacting with hydroxyethyl (meth)acrylate; Diisocyanate compound, polyisocyanate compound, acryl monoisocyanate compound obtained by reaction with polyol compound, and hydroxyethyl (meth)acrylate, etc. Among them, 2-methacryloxyethyl isocyanate is particularly preferable. In addition, the compound (A3) containing an energy ray curable group may be used individually or in combination of 2 or more types.

In the preparation of the (meth)acrylate copolymer (A) with an energy ray-curable group introduced into the side chain, the preparation of the acrylic copolymer (AP) and the combination of the acrylic copolymer (AP) and the energy ray-curable group The reaction of the compound (A3) can be carried out by a conventional method. In this reaction step, the reactive functional group derived from the functional group-containing monomer (A2) in the acrylic copolymer (AP) reacts with the functional group in the energy ray-curable group-containing compound (A3). Thereby, the (meth)acrylate copolymer (A) which introduced the energy ray curable group into a side chain was obtained. Furthermore, as described later, propylene The reaction between the acid-based copolymer (AP) and the energy ray-curable group-containing compound (A3) is preferably carried out in the presence of an organometallic catalyst (D).

Reactivity of the amount of energy ray-curable group-containing compound (A3) with respect to functional group-containing monomer (A2) in the (meth)acrylate copolymer (A) having energy ray-curable group-introduced side chains The amount of functional groups is preferably 30-100 mol%, particularly preferably 40-95 mol%, and further preferably 50-90 mol%.

The weight average molecular weight (Mw) of (meth)acrylate copolymer (A) having an energy ray hardening group introduced into the side chain is preferably 100,000 to 2.5 million, particularly preferably 150,000 to 2 million, and further preferably 300,000 ~1.5 million is better. In addition, the weight average molecular weight in this specification is the standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method. By setting the weight average molecular weight (Mw) of the (meth)acrylate copolymer (A) having a side chain into an energy ray-curable group within the above range, the coating property of the adhesive composition can be ensured, and the adhesion can be achieved. The cohesion of the agent layer is good, so physical properties suitable for cutting can be obtained.

(2-2) Acrylic polymer (N) not having energy ray curability

As the non-energy ray-curable acrylic polymer (N), conventionally known acrylic polymers can be used as long as they do not have energy-ray-curable properties. The acrylic polymer may be a single polymer formed from one type of acrylic monomer, or a copolymer formed from multiple types of acrylic monomers, or may be formed from one or more types of acrylic monomers. A copolymer formed of monomers and monomers other than acrylic monomers.

Specific types of compounds used as acrylic monomers are not particularly limited, and specific examples thereof include (meth)acrylic acid, (meth)acrylate esters, and derivatives thereof (acrylonitrile, itaconic acid, etc.). More specific example, the above-mentioned alkyl acrylate Monomer (A1) and functional group-containing monomer (A2), others include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxy (meth)acrylate Alkoxyalkyl-containing (meth)acrylates such as methyl ester and ethoxyethyl (meth)acrylate; (meth)acrylates having an aliphatic ring such as cyclohexyl (meth)acrylate ; (meth)acrylic esters with aromatic rings such as phenyl (meth)acrylate; non-bridging acrylamides such as acrylamide and methacrylamide; (meth)acrylic acid N,N- (Meth)acrylates with non-bridging tertiary amino groups such as dimethylaminoethyl ester, N,N-dimethylaminopropyl (meth)acrylate; vinyl acetate; styrene, etc. .

When the non-energy ray-curable acrylic polymer (N) has a reactive functional group derived from the functional group-containing monomer (A2), from the viewpoint of making the degree of bridging within a good range, the reactive functional group derived from the functional group-containing monomer (A2) The ratio of the mass of the structural portion of the body (A2) to the mass of the entire acrylic polymer is preferably about 1 to 20% by mass, more preferably 2 to 10% by mass.

The weight average molecular weight (Mw) of the non-energy-ray-curable acrylic polymer (N) is preferably 100,000 to 2.5 million, particularly preferably 150,000 to 2 million, and further preferably 200,000 to 1.5 million. By setting the weight average molecular weight (Mw) of the non-energy ray-curable acrylic polymer (N) within the above-mentioned range, the cohesiveness of the adhesive layer can be improved while ensuring the coatability of the adhesive composition. Since it is good, physical properties suitable for cutting can be obtained.

(2-3) Energy ray curable compound (B)

The energy ray-curable compound (B) refers to a compound that polymerizes and hardens when irradiated with energy rays such as ultraviolet rays or electron beams. Examples of the energy ray curable compound (B) include low molecular weight compounds (monofunctional or multifunctional monomers and oligomers), specifically, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, neopentylthritol triacrylate, dipenteoerythritol monohydroxypentaacrylate , di-neopentadiol hexaacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate and other acrylates, dicyclopentadiene dimethoxy diacrylate, iso Cyclic aliphatic skeleton-containing acrylates such as bornyl acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate, Acrylate-based compounds such as conic acid oligomers. Such compounds have energy-line hardening double bonds in the molecule, and usually have a molecular weight of 100-30,000, preferably about 300-10,000.

When the adhesive layer of this embodiment is composed of the above-mentioned Y-type adhesive, the content of the energy ray-curable compound (B) in the adhesive composition is lower than that of the non-energy-ray-curable acrylic polymer (N ) 100 parts by mass, preferably 20 to 200 parts by mass, particularly preferably 40 to 160 parts by mass, and further preferably 40 to 150 parts by mass.

When the adhesive layer of this embodiment is composed of the above-mentioned Z-type adhesive, the content of the energy ray-curable compound (B) in the adhesive composition is such that the (methyl) group that introduces the energy ray-curable group to the side chain 100 parts by mass of the acrylate copolymer (A), preferably 3 to 60 parts by mass, particularly preferably 5 to 50 parts by mass, further preferably 10 to 40 parts by mass.

(3) Bridging agent (C)

The adhesive composition forming the adhesive layer of this embodiment contains a (meth)acrylate copolymer (A) capable of introducing energy ray curable groups into side chains or an acrylic polymer that does not have energy ray curability. (N) The bridging agent (C) for bridging is good. In this case, the adhesive of this embodiment contains a bridging substance obtained by bridging the (meth)acrylate copolymer (A) or the acrylic polymer (N) with the bridging agent (C). . By using this bridging agent (C), the gel fraction of the adhesive forming the adhesive layer can be easily adjusted to a favorable range, and physical properties suitable for dicing can be obtained.

The type of bridging agent (C) can be, for example, polyimine (polyimine) compounds such as epoxy compounds, polyisocyanate compounds, metal chelate compounds, ethyleneimine compounds, melamine resins, and urea resins. , dialdehydes, methylol polymers, metal alkoxylates, metal salts, etc. Among these, it is preferable to use an epoxy-based compound or a polyisocyanate-based compound, and it is particularly preferable to use a polyisocyanate-based compound for reasons such as easy control of a bridging reaction.

Epoxy compounds, such as 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl m-xylene Amines, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine, etc.

The polyisocyanate compound is a compound having two or more isocyanate groups per molecule. Specifically, aromatic polyisocyanates such as cresyl diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate, Alicyclic polyisocyanate, such as hydrogen xylyl diisocyanate, etc. Further examples thereof include biurets, isocyanurates, adducts, and the like. The adducts include reactants with compounds containing low-molecular active hydrogen such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.

The bridging agent (C) may be used alone or in combination of two or more.

When the adhesive is X-type or Z-type, the content of the bridging agent (C) in the adhesive composition forming the adhesive layer, the (meth)acrylate copolymer (A) with energy ray-curable group introduced into the side chain 100 parts by mass, preferably 0.01 to 15 parts by mass, particularly preferably 0.05 to 10 parts by mass, further preferably 0.1 to 2 parts by mass. In addition, when the adhesive is Y-type, the content of the bridging agent (C) of the adhesive composition forming the adhesive layer is 3 to 20 parts by mass relative to the acrylic polymer (N) that does not have energy ray curing properties. Preferably, 5-17 parts by mass is particularly preferred, and further preferably 7-14 parts by mass.

(4)Organometallic catalyst (D)

In order to obtain a (meth)acrylate copolymer (A) having an energy ray-curable group introduced into the side chain, when the acrylic copolymer (AP) is reacted with a compound (A3) containing an energy ray-curable group, the reaction, It is preferably carried out in the presence of an organometallic catalyst (D). The organometallic catalyst (D) is particularly preferably at least one selected from the group consisting of zirconium-containing organic compounds, titanium-containing organic compounds, and tin-containing organic compounds. By reacting in the presence of such an organometallic catalyst (D), the adhesive composition containing the (meth)acrylate copolymer (A) can be obtained, and an adhesive layer with better adhesion can be formed. Effectively suppress wafer flying. The organometallic catalyst (D) is preferably at least one of an organic compound containing zirconium and an organic compound containing titanium among the above-mentioned three kinds of organic compounds, and an organic compound containing zirconium is particularly preferable.

Examples of the forms of the above-mentioned organic compounds include alkoxy compounds, chelate compounds, acyl compounds, etc. Among them, chelate compounds are good.

Specific examples of the organometallic catalyst (D) include zirconium alkoxy compounds, zirconium chelate compounds, titanium alkoxy compounds, titanium chelate compounds, tin alkoxy compounds, tin chelate compounds, and the like. Among these, zirconium chelates are preferred. The organometallic catalyst (D) may consist of one kind of these compounds, or may consist of two or more kinds of these compounds.

The usage-amount of the organometallic catalyst (D) used for the reaction for obtaining the (meth)acrylate copolymer (A) which introduce|transduces an energy-ray curable group into a side chain is not limited. The amount used is preferably 0.001 to 10 parts by mass in terms of metal, particularly preferably 0.01 to 5 parts by mass, and further preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the solid content of the (meth)acrylate copolymer (A). 3 parts by mass is better. Furthermore, in the present invention, the so-called metal amount conversion refers to the compounding amount or compounding ratio calculated only by the mass of the metal in the organometallic catalyst (D) by removing the mass corresponding to the molecular weight of the structure of the organic substance.

(5) Other ingredients

The adhesive composition forming the adhesive layer of this embodiment may contain, in addition to the above-mentioned components, a photopolymerization initiator, a bridging accelerator, a coloring material such as a dye or a pigment, a flame retardant, a filler, and an antistatic agent. and other additives.

Photopolymerization initiators include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, amines or quinones, etc. photosensitizers, etc. Specifically, α-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethylthiuram sulfide, azobisisobutyronitrile, Bibenzyl, diacetyl, β-chloroanthraquinone, 2,4,6-trimethyl Base benzoyl diphenyl phosphine oxide and so on. When using ultraviolet rays as energy rays, the irradiation time and the amount of irradiation can be reduced by preparing a photopolymerization initiator.

When the adhesive composition forming the adhesive layer of this embodiment contains a bridging agent (C), it may contain a suitable bridging accelerator according to the type of the bridging agent (C).

(6) Irradiation of energy rays

Regarding the adhesive sheet for glass cutting of this embodiment, when the adhesive layer is composed of an energy ray-curable adhesive, the energy ray used to harden the adhesive includes ionizing radiation, that is, ultraviolet rays, electrons, etc. Beams, X-rays, etc. Among them, ultraviolet rays, which are relatively easy to introduce by irradiation equipment, are preferable.

When ultraviolet rays are used as the ionizing radiation, it is preferable to use near ultraviolet rays including ultraviolet rays with a wavelength of about 200 to 380 nm in terms of ease of handling. The amount of light can be appropriately selected according to the type of energy ray-curable components contained in the adhesive composition or the thickness of the adhesive layer, usually about 50~500mJ/ ^cm2 , preferably 100~450mJ/ ^cm2 , 200~400mJ/ ^cm2 is better. In addition, the ultraviolet illuminance is usually about 50~500mW/cm ² , preferably 100~450mW/cm ² , more preferably 200~400mW/cm ² . The ultraviolet source is not particularly limited, and for example, high-pressure mercury lamps, metal halide lamps, UV-LEDs, and the like can be used.

When electron beams are used as ionizing radiation, the accelerating voltage may be appropriately selected according to the type of energy ray-curing components contained in the adhesive composition or the thickness of the adhesive layer. Generally, the accelerating voltage is about 10 to 1000 kV. better. In addition, the irradiation dose may be set within a range in which the adhesive can be properly cured, and is usually selected within a range of 10 to 1000 krad. The electron beam source is not particularly limited, and for example Cockrov-Walton can be used (Cockcroft-Walton) type, Van de Graaff type, resonant transformer type, wire core transformer type, or various electron beam accelerators such as linear type, Dynamitron type, and high frequency type.

3. Peel off the film

Regarding the adhesive sheet for glass cutting according to this embodiment, a peeling film may be laminated on the surface for the purpose of protecting the side of the adhesive layer opposite to the base material for a period of time until the adhered body is attached. The structure of the peeling film is arbitrary, and a plastic film that is peeled with a release agent or the like can be exemplified. Specific examples of plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyester films such as polypropylene or polyethylene. Polyolefin film. As the release agent, silicone-based release agents, fluorine-based release agents, long-chain alkyl-based release agents, and the like can be used. Among them, a silicone-based release agent that can provide inexpensive and stable performance is preferable. The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.

4. Physical properties of adhesive sheets for glass cutting

Stick the surface of the adhesive layer on the side opposite to the base material to the non-alkali glass, and after standing for 20 minutes, the adhesive force of the adhesive sheet for glass cutting of this embodiment to the non-alkali glass is 8000~25000mN /25mm is better, 9000~22000mN/25mm is better, and 10000~19000mN/25mm is better. By making this adhesive force into the said range, a glass wafer can be hold|maintained favorably by the adhesive sheet|seat at the time of dicing. Thereby, collisions of the glass wafers caused by misalignment of the glass wafers on the adhesive sheet, and unintended collisions between the cut surfaces of the glass plates or glass wafers and the dicing blade can be suppressed, thereby effectively suppressing chipped corners. In addition, as a result of holding the glass wafer well on the adhesive plate during dicing, it is possible to suppress the occurrence of wafer flying and push-out. Furthermore, in this specification, the adhesive layer is composed of the above-mentioned When the energy ray curable adhesive layer is composed, the viscosity value is the value measured before the energy ray is irradiated.

When the adhesive layer is composed of the above-mentioned energy ray curable adhesive, the surface of the adhesive layer opposite to the substrate is pasted with non-alkali glass, and the adhesive layer is irradiated with energy rays. Regarding this embodiment, The adhesive force of the glass cutting adhesive sheet to the alkali-free glass is preferably 50~250mN/25mm, especially 60~160mN/25mm, and 70~130mN/25mm. By setting the adhesive force after energy ray irradiation to 50mN/25mm or more, it is possible to suppress unintended peeling or shifting of the glass wafer from the adhesive sheet before the glass wafer is picked up from the adhesive sheet, enabling better pickup . On the other hand, by setting the adhesive force after energy ray irradiation to 250mN/25mm or less, for example, when picking up glass wafers individually, the glass wafers can be picked up well without being damaged, and the occurrence of adhesive residue can be suppressed.

Furthermore, the adhesive force in this specification refers to the adhesive force (mN/25mm) measured by the 180° peeling and tearing method in accordance with JIS Z0237:2009, using non-alkali glass as the substrate. The details of the measurement method are as follows shown in the test example.

5. Manufacturing method of adhesive sheet for glass cutting

The method for producing the adhesive sheet for glass cutting is not particularly limited as long as the adhesive layer formed from the above adhesive composition can be laminated on one side of the substrate.

As an example of the manufacturing method of the adhesive sheet for glass cutting, first, the coating composition which contains the said adhesive composition, and further contains a solvent or a dispersing agent as desired is prepared. Next, the coating composition is applied on one side of the base material by a die coater, curtain coater, spray coater, or slit coater. Coating machine, knife coater, etc. to form a coating film. Furthermore, an adhesive layer can be formed by drying this coating film. The properties of the coating composition are not particularly limited as long as it can be applied. The components for forming the adhesive layer may be contained in the coating composition as a solute, or may be contained as a dispersoid.

When the coating composition contains a bridging agent (C), in order to form a bridging structure at a desired density, the above-mentioned drying conditions (temperature, time, etc.) may be changed, or heat treatment may be performed separately. In order to fully carry out the bridging reaction, after the adhesive layer is laminated on the base material by the above method, the obtained adhesive sheet for glass cutting, for example, at 23°C and in an environment with a relative humidity of 50%, is allowed to stand for 1 week to 2 Wait for about a week to mature.

Another example of the manufacturing method of the adhesive sheet for glass cutting first applies the composition for coatings on the peeling-processed surface of the above-mentioned peeling film, and forms a coating film. Next, this coating film is dried, and the laminated body which consists of an adhesive layer and a peeling film is formed. Furthermore, the surface of the laminate on the side opposite to the release film of the adhesive layer was bonded to the base material. By the above method, a laminate of the adhesive sheet for glass cutting and the release film can be obtained. The peeling film of this laminate can be peeled off as an engineering material, and can also protect the adhesive layer until a certain period of time before sticking to the object to be adhered.

6. How to use adhesive sheets for glass cutting

The adhesive sheet for glass cutting of this embodiment can be used for cutting a glass plate. In addition, about the adhesive sheet for glass cutting of this embodiment, it can also be used for a series of steps including the cutting of a glass plate, the pick-up after it, and the like.

When used in a series of steps including cutting and subsequent pick-up, the adhesive for the adhesive sheet for glass cutting of this embodiment is initially The surface of the layer opposite to the substrate (hereinafter sometimes referred to as "adhesive surface") is bonded to the glass plate. When the release film is laminated on the adhesive surface, the release film is peeled off and the glass plate is attached to the exposed adhesive surface. On the other hand, the peripheral portion of the adhesive surface is pasted to a ring-shaped jig called a ring frame for transporting or fixing the device. Furthermore, between the bonding of the glass plate and the subsequent cutting steps, it is better to stand still for 10 minutes to 120 minutes, especially better to stand still for 15 minutes to 60 minutes, and to stand still for 20 minutes to 40 minutes is more preferable. By standing still for such a period, the adhesion between the glass plate and the adhesive plate can be made sufficient.

Next, a cutting step is performed. That is, the glass plate stuck to the adhesive sheet for glass cutting is cut|disconnected with the cutting blade. Thereby, a plurality of glass wafers bonded to the adhesive sheet for glass cutting are obtained. In the adhesive sheet for glass cutting of this embodiment, the base material has the said thickness, and the handleability of an adhesive sheet is favorable. Furthermore, by making the storage modulus of elasticity at 100°C of the adhesive layer within the above range, when the temperature of the adhesive layer is set to a high temperature of about 100°C due to frictional heat during cutting, it is possible to sufficiently control the occurrence of shaking during cutting. As a result, chipping can be suppressed from occurring even when a thin glass plate is cut into small wafers. As a result, small wafers can be efficiently obtained from a thin glass plate.

When the adhesive layer is composed of the above-mentioned energy ray curable adhesive, after the dicing step is completed, energy rays are irradiated from the surface on the glass wafer side or the surface on the substrate side to the adhesive sheet to which a plurality of glass wafers are attached. Thereby, the energy ray curable group which the (meth)acrylate copolymer (A) has is polymerized and adhesiveness is reduced, and the subsequent pick-up process becomes easy.

The pick-up step can be performed by a general means such as a vacuum chuck. At this time, for easy pick-up, separate the target glass wafer from the adhesive layer on the substrate side. On the opposite side, it is better to use push pins or needles. In the adhesive sheet for glass cutting of this embodiment, the adhesive sheet has favorable flexibility by making the thickness of a base material into the said range. Thereby, pickup can be performed favorably.

Furthermore, it is preferable to perform the expansion step before the picking step. At this time, the adhesive sheet for glass cutting is extended in a plane direction. Thereby, the space|interval between glass wafers is enlarged, and it becomes easy to pick up. The degree of elongation may be appropriately set in consideration of a preferable interval, the tensile strength of the base material, and the like. Furthermore, the expanding step can also be performed before the irradiation of energy rays.

In addition, when cutting a glass plate using the adhesive sheet for glass cutting according to this embodiment, the area of the plane of the obtained glass wafer is preferably 1×10 ^-6 mm ² to 1 mm ² , preferably 1×10 ^-4 mm 2 to 1 mm ² . 0.25mm ² is more preferable, 2.5×10 ^-3 mm ² to 0.09mm ² is particularly preferable, and 0.01mm ² to 0.03mm ² is more preferable. According to the adhesive sheet for glass cutting according to this embodiment, by setting the storage elastic modulus of the adhesive layer at 100°C within the above-mentioned range, it is possible to suppress the vibration of the adhesive sheet during cutting even if it has an area within the above-mentioned range. Small glass wafers can also be obtained by suppressing chipping.

When cutting a glass plate using the adhesive sheet for glass cutting according to this embodiment, the thickness of the glass plate as a workpiece is preferably 50-10000 μm, particularly preferably 100-5000 μm, and further preferably 300-800 μm. In addition, in this specification, a "workpiece" means the object stuck to the adhesive sheet for glass cutting concerning this embodiment, or the to-be-processed object processed using this adhesive sheet. According to the adhesive sheet for glass cutting according to this embodiment, by making the storage elastic modulus of the adhesive layer at 100°C within the above-mentioned range, it is possible to suppress the vibration of the adhesive sheet during cutting, even if it is a thin adhesive sheet with a thickness of 50 μm. glass plate, can also suppress Cutting occurs in case of missing corners.

The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above-mentioned embodiments is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

For example, another layer may be interposed between the base material and the adhesive layer of the adhesive sheet for glass cutting.

[Example]

Hereinafter, although an Example etc. demonstrate this invention more concretely, this invention is not limited to these Examples. In addition, the description of the following parts by mass is described by the conversion value of a solid content.

[Example 1]

(1) Preparation of (meth)acrylate copolymer (A)

Acrylic copolymer (AP) was obtained by copolymerizing 75 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of methyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate. As a result of measuring the molecular weight of the obtained acrylic copolymer (AP), the weight average molecular weight (Mw) was 700,000. In addition, the weight average molecular weight (Mw) in this Example is the weight average molecular weight of standard polystyrene conversion using the gel permeation chromatography (GPC) measurement (GPC measurement).

Next, the obtained acrylic copolymer (AP), 2-methacryloxyethyl isocyanate (MOI) as an energy ray-curable group-containing compound (A3), and 2-methacryloxyethyl isocyanate (MOI) as an organometallic catalyst (D) The reaction was carried out in the presence of a zirconium chelate catalyst (manufactured by Matsumoto Fine Chemical Co., Ltd., product name "ZC-700"). In this way, a (methyl) group having an energy ray hardening group (methacryl group) introduced into the side chain is obtained. Acrylate Copolymer (A). At this time, both were reacted so that the MOI may be 60 mol (60 mol %) to 100 mol equivalents of the 2-hydroxyethyl acrylate unit of the acrylic copolymer (AP). Moreover, the compounding quantity of an organometallic catalyst (D) was 0.1 mass parts with respect to 100 mass parts of acrylic-type copolymers (AP).

(2) Preparation of adhesive composition

100 parts by mass of the (meth)acrylate copolymer (A) obtained in the above step (1), 3.0 parts by mass of α-hydroxycyclohexyl phenone (manufactured by BASF Corporation, product name "IRGACURE 184") as a photopolymerization initiator ), and 0.2 parts by mass of trimethylolpropane-denatured toluene diisocyanate (manufactured by TOSO, product name "CORONATE L") as a bridging agent (C) were mixed in a solvent to obtain a coating solution of an adhesive composition. Furthermore, an X-type adhesive was obtained by using this adhesive composition.

(3) Production of adhesive sheets for glass cutting

Apply the coating solution of the adhesive composition obtained in the above step (2) to a release film of polyethylene terephthalate film (LINTEC Manufactured by the company, product name "SP-PET381031", thickness: 38μm) on the peeled surface. Next, it was processed at 100 degreeC for 1 minute, and bridging reaction progressed while drying a coating film. In this way, a laminate composed of a release film and an adhesive layer having a thickness of 10 μm was obtained. Furthermore, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "A-4100", thickness: 100 μm) was attached as a base material to the surface of the laminate on the side of the adhesive layer. ). Thereby, the adhesive sheet sheet for glass cutting which laminated|stacked a base material, an adhesive layer, and a peeling film sequentially was obtained.

[Example 2~12]

The material of the substrate, the thickness of the substrate, the amount of 2-methacryloxyethyl isocyanate (MOI) used to form the adhesive layer, and the type of organometallic catalyst (D) used to form the adhesive layer , and the thickness of the adhesive layer were changed to those shown in Table 1, and an adhesive sheet sheet for glass cutting was produced in the same manner as in Example 1.

[Comparative example 1]

The thickness of the base material was changed to other than those shown in Table 1, and the adhesive sheet sheet for glass cutting was manufactured similarly to Example 1.

[Comparative example 2]

(1) Preparation of adhesive composition

90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid were copolymerized to obtain an acrylic polymer (N) not having energy ray curability. As a result of measuring the molecular weight of the obtained polymer (N), the weight average molecular weight (Mw) was 600,000.

100 parts by mass of the non-energy ray-curable acrylic polymer (N) obtained above, and 127 parts by mass of a trifunctional urethane acrylate oligomer (Dainichi Seika Kogyo Co., Ltd.) as the energy ray-curable compound (B) manufactured, product name "EXL810TL", Mw=5000), 4 parts by mass of α-hydroxycyclohexyl phenone (manufactured by BASF Corporation, product name "IRGACURE184") as a photopolymerization initiator, 11 parts by mass of α-hydroxycyclohexyl phenone as a bridging agent Methylolpropane-denatured toluene diisocyanate (manufactured by TOSO Corporation, product name "CORONATE L") was mixed in a solvent to obtain a coating solution of an adhesive composition. Furthermore, by using this adhesive composition, the Y-shaped adhesive was obtained.

(2) Production of adhesive sheets for glass cutting

Except having used the coating solution of the adhesive composition obtained in the said process (1), it carried out similarly to Example 1, and produced the adhesive sheet for glass cutting.

[Comparative example 3]

(1) Preparation of adhesive composition

50 parts by mass of 2-ethylhexyl acrylate, 40 parts by mass of methyl acrylate, and 10 parts by mass of acrylic acid were copolymerized to obtain an acrylic polymer (N) not having energy ray curability. As a result of measuring the molecular weight of the obtained polymer (N), the weight average molecular weight (Mw) was 800,000.

100 parts by mass of the non-energy ray-curable acrylic polymer (N) obtained above, and 40 parts by mass of 10-functional urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name "UV-1700B", molecular weight: 1700), 0.1 parts by mass of α-hydroxycyclohexyl phenone (manufactured by BASF Corporation, product name "IRGACURE184") as a photopolymerization initiator, 10 parts by mass of trihydroxycyclohexyl phenone as a bridging agent Methylpropane-denatured toluene diisocyanate (manufactured by TOSO Corporation, product name "CORONATE L") was mixed in a solvent to obtain a coating solution of an adhesive composition. Furthermore, by using this adhesive composition, the Y-shaped adhesive was obtained.

(2) Production of adhesive sheets for glass cutting

Except having used the coating solution of the adhesive composition obtained in the said process (1), it carried out similarly to Example 1, and produced the adhesive sheet for glass cutting.

[Comparative Examples 3 and 4]

The thickness of the adhesive layer was changed to other than those shown in Table 1, and the adhesive sheet sheet for glass cutting was manufactured similarly to the comparative example 3.

The details of the abbreviations listed in Table 1 are as follows.

[material of the base material]

PET (thickness 100μm): Polyethylene terephthalate film (Toyobo Co., Ltd. system, product name "A-4100")

PET (thickness: 50 μm): Polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "A-4100")

PET (thickness 188 μm): Polyethylene terephthalate film (manufactured by Toyokyu Co., Ltd., product name "A-4100")

PO: Polyolefin film (manufactured by Rikenteehnos, product name "ADN09-100T-M8")

PP: Polypropylene film (manufactured by DiaPlus Film, product name "PL109")

PI: polyimide film (manufactured by MPRTECH, product name "Mordohar PIF100")

[Organometallic catalyst]

Zr: Zirconium chelate catalyst (manufactured by Matsumoto Fine Chemical, product name "ZC-700")

Sn: dibutyltin laurate catalyst (manufactured by TOYOCHEM Corporation, "BXX-3778")

[Test Example 1] (Measurement of Storage Modulus of Base Material)

Regarding the substrates used in Examples and Comparative Examples, the storage elastic modulus at 23° C. was measured with the following apparatus and conditions. The results are shown in Table 1.

Measuring device: Dynamic elastic modulus measuring device, manufactured by TA Instruments, product name "DMA Q800"

Test start temperature: 0°C

Test end temperature: 200°C

Heating rate: 3°C/min

Frequency: 11Hz

Amplitude: 20μm

[Test Example 2] (Measurement of Storage Elastic Modulus of Adhesive Layer Before Ultraviolet Irradiation)

The coating solution of the adhesive composition used in Examples and Comparative Examples was coated on the release-treated surface of a first release film (manufactured by Lintec Corporation, product name "SP-PET381031") with a thickness of 38 μm. The obtained coating film was held at 100° C. for 1 minute to dry the coating film. Thereby, an adhesive layer with a thickness of 40 μm was formed on the first release film. Furthermore, the surface of the adhesive layer opposite to the first release film was attached to the release-treated surface of a second release film (manufactured by LINTEC, product name "SP-PET381031") with a thickness of 38 μm to obtain sequential A laminate including a first release film, an adhesive layer with a thickness of 40 μm, and a second release film. The adhesive layer obtained by the above procedures was laminated in multiple layers to have a thickness of 800 μm. A circular shape with a diameter of 10 mm was punched out from this laminated body with a thickness of 800 μm, and was used as a sample for measurement. Using a viscoelasticity measurement device (manufactured by TA Instruments, product name "ARES"), the sample is deformed at a frequency of 1 Hz, and the storage elastic modulus at -50 to 150°C is measured, and the storage elastic modulus at 23°C and 100°C are obtained. The value of the number. The results are shown in Table 1. In addition, when laminating|stacking a plurality of adhesive agent layers, after forming an adhesive agent layer, what was left to stand for 1 week in the environment of temperature 23 degreeC and humidity 50% was used as the said laminated body.

[Test Example 3] (Measurement of Tensile Elastic Modulus of Adhesive Layer After Ultraviolet Irradiation)

In the same procedure as in Test Example 2, multiple layers of the adhesive layer were laminated so as to have a thickness of 200 μm.

Next, ultraviolet (UV) irradiation (illuminance: 230 mW/cm ² , light intensity: 190 mJ/cm ² ) was performed using an ultraviolet irradiation device (manufactured by Lintec Corporation, product name "RAD-2000") to harden the adhesive layer. Further, it was cut into 15 mm×140 mm to obtain a test piece.

The release film was peeled off from the obtained test piece, and the tensile elastic modulus at 23° C. of the cured adhesive layer was measured in accordance with JIS K7161: 1994 and JIS K7127: 1999. Specifically, a tensile tester (manufactured by Shimadzu Corporation, product name "Autograph AG-IS 500N") was used to perform a tensile test at a speed of 200 mm/min after setting the distance between the clamps to 100 mm, and to measure the tensile modulus of elasticity. (Pa). The results are shown in Table 1.

[Test Example 4] (Measurement of Viscosity Value)

Regarding the surface of the adhesive layer side of the adhesive sheets manufactured in the examples and comparative examples, use a probe with a diameter of 5 mm (5 mm ψ) and measure it with a probe tack tester (manufactured by Rhesca, product name "RPT-100") sticky value. The measurement method is the method described in JIS Z0237:2009, changing the peeling speed to 1 mm/min, and on the other hand, the load is 100 gf/cm ² , and the contact time is 1 second, as described in the above-mentioned JIS regulations. Calculate the measured energy (integrated peak value), and use this as the viscosity value (unit: mJ/5mm ψ). The results are shown in Table 1. In addition, in the said measurement, the adhesive board piece which was left to stand for 1 week in the environment of temperature 23 degreeC and humidity 50% after forming an adhesive layer was used.

[Test Example 5] (Measurement of adhesive force before and after ultraviolet irradiation)

At room temperature, the adhesive sheets for glass cutting manufactured by Examples and Comparative Examples were placed in an environment with a temperature of 23°C and a humidity of 50% for one week, and the release film was peeled off. Laminate the surface where the adhesive layer was exposed and one surface of the 6-inch non-alkali glass plate, apply a load back and forth with a 2 kg roller, and stick together, and leave it for 20 minutes. After that, use the 180° peeling and tearing method in accordance with JIS Z0237:2009, from the non-alkali glass For the glass plate, the peeling speed is 300mm/min, the peeling angle is 180°, and the adhesive sheet for glass cutting is peeled off, and the adhesive force (mN/25mm) is measured. Let this measured value be the adhesive force before ultraviolet-ray irradiation. The results are shown in Table 1.

In addition, in the same manner as above, the adhesive sheets for glass cutting produced in Examples and Comparative Examples were bonded to a 6-inch non-alkali glass plate, and after standing for 20 minutes, ultraviolet light was applied from the substrate side of the adhesive sheet for glass cutting. An irradiation device (manufactured by Lintec Corporation, product name "RAD-2000") irradiates ultraviolet rays (UV) (illuminance: 200 mW/cm ² , light intensity: 180 mJ/cm ² ) to harden the adhesive layer. Thereafter, the adhesive force (mN/25mm) was measured in the same manner as above. This measured value was made into the adhesive force after ultraviolet-ray irradiation. The results are shown in Table 1.

[Test Example 6] (evaluation of chipped corners and pushed crystals)

The adhesive sheets for glass cutting manufactured by Examples and Comparative Examples were placed in an environment with a temperature of 23° C. and a humidity of 50% for one week, and the release film was peeled off. 12"), on the exposed surface of the adhesive layer, paste a 6-inch non-alkali glass plate with a thickness of 550 μm and a ring frame for cutting. Next, cut the adhesive sheet for glass cutting according to the outer diameter of the ring frame. Furthermore, using a dicing device (manufactured by DISCO, product name "DFD-651"), dicing was performed from the glass plate side under the following dicing conditions to obtain a 0.6 mm square glass wafer.

<Cutting conditions>

‧Cutting device: DISCO DFD-651

‧Blade: DISCO NBC-2H 2050 27HECC

‧Blade width: 0.025~0.030mm

‧Infeed amount: 0.640~0.760mm

‧Blade rotation speed: 30000rpm

‧Cutting speed: 80mm/sec

‧Substrate penetration depth: 20μm

‧Cutting water volume: 1.0L/min

‧Cutting water temperature: 20℃

‧Cutting size: 0.6mm square (plane area 0.36mm ² )

After the cutting is completed, observe whether there is any defect and shape at the end of the glass wafer located in the center of the adhesive sheet for glass cutting and its vicinity. The specific method is to use an electron microscope (manufactured by KEYENCE, product name "VHZ-100, magnification: 300 times) to observe the sides of 50 wafers in the flow direction (MD direction) during the production of the substrate and to observe the sides perpendicular to the MD direction. The edge of 50 wafers in the direction (CD direction). Then, the defects with a width or depth of 20 μm or more are judged as chipped corners, and the number thereof is counted. With this result, the chipped corners are evaluated based on the following criteria. The evaluation results are shown in Table 1.

⊚: The number of chipped wafers was less than five.

◯: The number of chipped wafers was 5 or more and less than 50.

x: The number of wafers in which chipped corners occurred was 50 or more.

[Test Example 7] (operability evaluation)

The adhesive sheets for glass cutting manufactured by Examples and Comparative Examples were placed in an environment with a temperature of 23° C. and a humidity of 50% for one week, and the release film was peeled off, and a cutting tape machine (manufactured by Lintec Corporation, product name “RAD2500F/ 8"), on the exposed surface of the adhesive layer, paste a 6-inch non-alkali glass plate with a thickness of 550 μm and a cut ring frame. This operation was repeated 50 times, and the workability of the adhesive sheet was evaluated based on the following criteria

○: There is no special problem, and 50 times of continuous pasting is possible.

×: An error occurred midway and the operation was interrupted, and 50 consecutive pastings were not possible.

[Table 1]

As can be seen from Table 1, according to the adhesive sheets related to the examples, the occurrence of chipped corners can be suppressed. Furthermore, it turned out that the adhesive sheet of the Example was excellent in handleability.

【Industrial Profitability】

The adhesive sheet for glass cutting of this invention can be used for the cutting process of glass, and can be used favorably especially for the cutting process of thin glass.

Claims (11)

An adhesive sheet for glass cutting, which is an adhesive sheet for glass cutting comprising a base material and an adhesive layer directly laminated on at least one surface of the base material, wherein the base material is a single layer , the base material is polypropylene film, polyethylene terephthalate film or polyimide film, the thickness of the base material is more than 30 μm and less than 130 μm, and the thickness of the adhesive layer is 7-25 μm, The storage elastic modulus of the above adhesive layer at 100° C. is 6-50 kPa. The adhesive sheet for glass cutting described in item 1 of the scope of the patent application, wherein the storage modulus of elasticity of the adhesive layer at 23°C is 30-100kPa. The adhesive sheet for glass cutting as described in item 1 of the patent scope of the application, wherein the surface of the above-mentioned adhesive layer opposite to the above-mentioned base material is pasted on the non-alkali glass, and after standing for 20 minutes, the above-mentioned glass cutting The adhesion force of the adhesive sheet to the above-mentioned alkali-free glass is 8000~25000mN/25mm. The adhesive sheet for glass cutting as described in claim 1, wherein the above-mentioned adhesive layer is changed to a peeling speed of 1mm/min in accordance with the method described in JIS Z0237:1991, using a probe viscosity tester The measured energy is 0.01~5mJ/5mmψ. The adhesive sheet for glass cutting as described in claim 1 of the patent application, wherein the above-mentioned adhesive layer is composed of an energy-ray-curable adhesive. The adhesive sheet for glass cutting as described in item 5 of the scope of the patent application, wherein the above-mentioned adhesive layer is made of (methyl) It consists of an adhesive formed from an adhesive composition of an acrylate copolymer (A). The adhesive sheet for glass cutting according to claim 6, wherein the adhesive composition further contains an energy ray-curable compound (B) other than the (meth)acrylate copolymer (A). The adhesive sheet for glass cutting as described in claim 6 of the patent application, wherein the above-mentioned adhesive composition further contains a bridging agent (C). The adhesive sheet for glass cutting described in item 1 of the scope of the patent application, wherein the storage elastic modulus of the base material at 23°C is 100-8000 MPa. A method for manufacturing an adhesive sheet for glass cutting, which is a method for manufacturing the adhesive sheet for glass cutting described in item 6 of the scope of the patent application, which is characterized in that it comprises: making at least an alkyl (meth)acrylate The acrylic copolymer (AP) in which the body (A1) and the monomer (A2) containing a functional group with a reactive functional group are copolymerized, and the acrylic copolymer (AP) having a functional group that can react with the monomer (A2) containing a functional group A functional group and an energy ray curable group-containing compound (A3) reacted with an energy ray curable carbon-carbon double bond to prepare a (meth)acrylate copolymer (A3) in which an energy ray curable group is introduced into a side chain ); and a step of laminating an adhesive layer on at least one surface of the substrate using an adhesive composition containing the (meth)acrylate copolymer (A). The method for producing an adhesive sheet for glass cutting as described in Claim 10 of the patent application, wherein the above-mentioned acrylic copolymer (AP) is reacted with the above-mentioned compound (A3) containing an energy ray curable group to form zirconium-containing organic compound, an organic compound containing titanium, and an organic compound containing tin in the presence of at least one organometallic catalyst (D).