JP2017179029A - Adhesive sheet for glass dicing and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet for glass dicing that hardly causes chip scattering during dicing, suppresses generation of chipping and die shift, is capable of good pick up and further hardly causes adhesive residues, and a manufacturing method therefor.SOLUTION: There is provided an adhesive sheet for glass dicing having a substrate and an adhesive layer laminated on at least one surface of the substrate and having thickness of the substrate of 30 μm or more and less than 130 μm and thickness of the adhesive layer of over 9 μm and 40 μm or less.SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive sheet for glass dicing used for dicing a glass plate to obtain a glass chip, and a method for producing the same.

  In order to manufacture a camera module mounted on a mobile phone or a smartphone, a fine glass piece is required. Such a glass piece can be obtained by dicing one glass plate using a dicing sheet. That is, after pasting a glass plate on a dicing sheet, the glass plate is cut with a dicing blade, whereby an individualized glass (hereinafter sometimes referred to as “glass chip”) can be obtained. In recent years, as smartphones and the like have become thinner and the mounted camera modules have become smaller, it has become necessary to manufacture thinner and finer glass chips (hereinafter sometimes referred to as “small chips”).

  When dicing a brittle material such as glass, chipping is likely to occur. Here, the chipping means that the end portion or the cut surface of the glass chip is missing during dicing. The occurrence of chipping becomes more prominent as the glass plate becomes thinner.

  Further, the above-described dicing sheet is required not to cause a phenomenon that the formed glass chip is peeled off and scattered from the sheet (hereinafter sometimes referred to as “chip scattering”) when dicing.

  Patent Document 1 discloses a pressure-sensitive adhesive sheet for glass substrate dicing in which a pressure-sensitive adhesive layer is provided on a base film. In this Patent Document 1, a film having a thickness of 130 μm or more and a tensile elastic modulus of 1 GPa or more is used as a base film, and the thickness of the pressure-sensitive adhesive layer is 9 μm or less. It is disclosed that the deformation can be reduced and the occurrence of chipping and chip scattering can be suppressed (paragraph 0010 of Patent Document 1).

Japanese Patent No. 3838637

  In recent years, the miniaturization of camera modules has progressed, and the required glass chip size has become very small. The pressure-sensitive adhesive sheet disclosed in Patent Document 1 cannot sufficiently suppress the chip scattering of such small chips.

  In addition, with the miniaturization of the glass chip, a problem called die shift is likely to occur. This is because when a small chip is manufactured, the contact area between the glass chip and the pressure-sensitive adhesive sheet is reduced, and the glass plate or the glass chip is likely to be displaced on the pressure-sensitive adhesive sheet due to vibration of dicing or the like. When die shift occurs, dicing cannot be performed at an intended position, and a glass chip having a desired shape cannot be obtained. Therefore, it is required that die shift does not occur in the manufacture of small chips.

  By the way, in manufacture of a glass chip, a pick-up process may be performed in the state where the glass chip was stuck on the dicing sheet following the dicing process mentioned above. In this step, it is required that the glass chip can be favorably picked up without failing to pick up the glass chip or damaging the glass chip when picking up. Furthermore, it is required that the pressure-sensitive adhesive derived from the dicing sheet does not adhere to the picked-up glass chip (hereinafter, sometimes referred to as “glue residue”).

  The present invention has been made in view of the above-described actual situation. Chip scattering is less likely to occur during dicing, chipping and die shift are suppressed, good pickup is possible, and adhesive residue is generated. It is an object to provide a pressure-sensitive adhesive sheet for glass dicing and a method for producing the same.

  In order to achieve the above object, first, the present invention is a pressure-sensitive adhesive sheet for glass dicing comprising a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material, wherein the base material A glass dicing pressure-sensitive adhesive sheet is provided wherein the thickness of the pressure-sensitive adhesive layer is 30 μm or more and less than 130 μm, and the pressure-sensitive adhesive layer has a thickness of more than 9 μm and 40 μm or less (Invention 1).

  In the said invention (invention 1), the handling property as an adhesive sheet for glass dicing becomes favorable because a base material has the above-mentioned thickness. In addition, since the pressure-sensitive adhesive layer has the above-described thickness, the pressure-sensitive adhesive layer exhibits excellent tack, and the glass chip is well held by the pressure-sensitive adhesive sheet for glass dicing, so that chip scattering is suppressed during dicing. Is done. Further, since the pressure-sensitive adhesive layer and the base material have the above-described thicknesses, the occurrence of chipping and die shift is suppressed, good pickup can be performed, and adhesive residue is hardly generated. In particular, when the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer is an X-type pressure-sensitive adhesive to be described later, the effects relating to chipping, die shift, pickup, and adhesive residue become remarkable.

  In the said invention (invention 1), it is preferable that the said adhesive layer consists of energy-beam curable adhesives (invention 2).

  In the said invention (invention 2), the said adhesive layer is the adhesive formed from the adhesive composition containing the (meth) acrylic acid ester copolymer (A) by which the energy-beam curable group was introduce | transduced into the side chain. It is preferable to consist of an agent (Invention 3).

  In the said invention (invention 1-3), the energy amount measured using the probe tack on the conditions which changed the peeling rate into 1 mm / min in the method described in JIS Z0237: 1991 in the said adhesive layer is 0.00. It is preferably 01 to 5 mJ / 5 mmφ (Invention 4).

  In the said invention (invention 1-4), it is preferable that the storage elastic modulus in 23 degreeC of the said adhesive layer is 30-100 kPa (invention 5).

  In the said invention (invention 1-5), after sticking the surface on the opposite side to the said base material of the said adhesive layer on an alkali free glass, and leaving still for 20 minutes, the said alkali free of the said adhesive sheet for glass dicing The adhesive strength to glass is preferably 8000 to 25000 mN / 25 mm (Invention 6).

  In the said invention (invention 2 and 3), the glass dicing after sticking the surface on the opposite side to the said base material of the said adhesive layer on an alkali free glass, and irradiating an energy ray with respect to the said adhesive layer It is preferable that the adhesive force of the pressure-sensitive adhesive sheet to the alkali-free glass is 50 to 250 mN / 25 mm (Invention 7).

  In the said invention (invention 2, 3, 7), it is preferable that the tensile elasticity modulus in 23 degreeC after the energy ray irradiation of the said adhesive layer is 15-1500 Mpa (invention 8).

  In the said invention (invention 1-8), it is preferable that the storage elastic modulus in 23 degreeC of the said base material is 100-8000 MPa (invention 9).

  In the said invention (invention 3), it is preferable that the said adhesive composition contains a crosslinking agent (C) further (invention 10).

In the above invention (invention 1 to 10), a glass plate, it is preferable plane is for dicing glass tip having an area of ^{1 × 10 -6 mm 2 ~1mm 2} ( invention 11).

  2ndly this invention is a method of manufacturing the said adhesive sheet for glass dicing (invention 3), Comprising: The functional group containing monomer ((meth) acrylic-acid alkylester monomer (A1) and a reactive functional group) ( Acrylic copolymer (AP) copolymerized with A2), functional group capable of reacting with functional group of functional group-containing monomer (A2), and energy beam curing having energy beam curable carbon-carbon double bond A step of preparing a (meth) acrylate copolymer (A) in which an energy ray-curable group is introduced into the side chain by reacting with the functional group-containing compound (A3), and the (meth) acrylate ester For glass dicing, comprising a step of laminating a pressure-sensitive adhesive layer on at least one surface of a substrate using a pressure-sensitive adhesive composition containing a copolymer (A) To provide a method of manufacturing a landing sheet (invention 12).

  In the said invention (invention 12), reaction of the said acrylic copolymer (AP) and the said energy-beam curable group containing compound (A3) is made into the organic compound containing zirconium, the organic compound containing titanium, and tin. It is preferable to carry out in the presence of at least one organometallic catalyst (D) selected from organic compounds containing (Invention 13).

  According to the pressure-sensitive adhesive sheet for glass dicing according to the present invention and the pressure-sensitive adhesive sheet for glass dicing manufactured by the manufacturing method according to the present invention, chip scattering is less likely to occur during dicing, and generation of chipping and die shift is suppressed. Pick-up is possible, and adhesive residue is hardly generated.

Hereinafter, embodiments of the present invention will be described.
A glass dicing pressure-sensitive adhesive sheet according to the present embodiment (hereinafter sometimes simply referred to as “pressure-sensitive adhesive sheet”) includes a base material and a pressure-sensitive adhesive layer laminated on one surface of the base material. .

  In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the substrate is 30 μm or more and less than 130 μm. Moreover, the thickness of an adhesive layer is more than 9 micrometers and 40 micrometers or less.

  In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the handling property relating to glass dicing becomes good because the base material has the above thickness.

  Moreover, in the adhesive sheet for glass dicing which concerns on this embodiment, the adhesive layer exhibits the tack | tuck which was excellent because an adhesive layer has the said thickness. Thereby, the glass chip formed by dicing is hold | maintained favorably on an adhesive sheet. As a result, even when the glass chip receives an impact during dicing, the glass chip is prevented from falling off the adhesive sheet. That is, chip scattering is prevented.

  Furthermore, in the adhesive sheet for glass dicing which concerns on this embodiment, as above-mentioned, a glass chip is hold | maintained on an adhesive sheet favorably at the time of dicing because an adhesive sheet exhibits the outstanding tack. As a result, the collision between the glass chips due to the displacement of the glass chip on the adhesive sheet and the unintended collision between the cut surface of the glass plate or the glass chip and the dicing blade are suppressed. In addition to this, the occurrence of chipping can be suppressed even when a thin glass plate is diced into small chips because the thickness of the base material is in the above range.

  Furthermore, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, as described above, the pressure-sensitive adhesive sheet exhibits excellent tack, and the glass plate is well held on the pressure-sensitive adhesive sheet during dicing, so that The movement of the glass plate is suppressed. In addition to this, when the thickness of the base material is in the above range, even when a thin glass plate is diced into small chips, the occurrence of die shift can be suppressed.

  Furthermore, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer has a pressure-sensitive adhesive force that can easily pick up a glass chip because the thickness of the pressure-sensitive adhesive layer is in the above range. Become. In addition to this, when the thickness of the base material is in the above range, the pressure-sensitive adhesive sheet has good flexibility, so that the pickup can be performed well.

  Furthermore, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, since the pressure-sensitive adhesive layer and the substrate each have the above-described thickness, the glue derived from the pressure-sensitive adhesive layer hardly remains on the picked-up glass chip. In particular, when the pressure-sensitive adhesive layer is composed of an X-type pressure-sensitive adhesive described later, the X-type pressure-sensitive adhesive does not contain a low-molecular compound such as an energy ray-curable compound (B), so that the compound is on the glass chip. Will not remain. Moreover, when forming X type adhesive from an adhesive composition, the said adhesive composition is easy to progress uniform bridge | crosslinking, and the obtained adhesive becomes what was bridge | crosslinked uniformly uniformly. By the above, generation | occurrence | production of adhesive residue can be suppressed effectively.

1. Substrate In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the substrate is 30 μm or more and less than 130 μm, preferably 50 μm or more and 120 μm or less, and particularly preferably 70 μm or more and 110 μm or less. preferable. When the thickness of the substrate is less than 30 μm, the adhesive sheet is likely to sway during the dicing process, and the glass plate is likely to move on the adhesive sheet. As a result, chipping and die shift are likely to occur. Furthermore, it becomes easy to fracture when handling the adhesive sheet or during the expanding step. On the other hand, if the thickness of the base material is 130 μm or more, the flexibility of the entire pressure-sensitive adhesive sheet is lowered, and the pressure-sensitive adhesive sheet is ringed when it is attached to a ring frame or a dicing jig or when a glass plate is diced. It becomes easy to drop off from the frame or jig.

In the pressure-sensitive adhesive sheet for glass dicing according to this embodiment, the storage elastic modulus of the substrate at 23 ° C. is preferably 100 to 8000 MPa, particularly preferably 1500 to 7000 MPa, and more preferably 2000 to 6000 MPa. Is preferred. Since the storage elastic modulus of the substrate at 23 ° C. is 100 MPa or more, the occurrence of shaking of the pressure-sensitive adhesive sheet in the dicing process is reduced, and the movement of the glass plate on the pressure-sensitive adhesive sheet is suppressed, resulting in the occurrence of chipping and die shift. It can be effectively suppressed. Moreover, the softness | flexibility of a base material is ensured because the storage elastic modulus in 23 degreeC of a base material is 8000 Mpa or less, and the extendability (expanding property) of a base material becomes more excellent. Thereby, at the time of an expanding process, the adhesive sheet shows the more excellent expandability, and can pick up the glass chip after dicing more favorably. In addition, the storage elastic modulus at 23 ° C. of the base material was measured under the following conditions using a dynamic elastic modulus measuring device (manufactured by TA Instruments, product name “DMA Q800”). is there.
Test start temperature: 0 ° C
Test end temperature: 200 ° C
Temperature increase rate: 3 ° C / min Frequency: 11Hz
Amplitude: 20 μm

  As long as the base material of the adhesive sheet for glass dicing which concerns on this embodiment has the thickness mentioned above, the constituent material is not specifically limited. The base material may include a film (resin film) whose main material is a resin-based material. Preferably, a base material consists only of a resin film. Specific examples of the resin film include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid ester copolymer films; polyethylene Polyolefin films such as films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, ethylene-norbornene copolymer films and norbornene resin films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films Film; Polyester film such as polyethylene terephthalate film and polybutylene terephthalate film; Polyurethane film; Polyimide film; Polystyrene film; Polycarbonate Irumu; and fluororesin films. Examples of the polyethylene film include a low density polyethylene (LDPE) film, a linear low density polyethylene (LLDPE) film, and a high density polyethylene (HDPE) film. In addition, modified films such as these crosslinked films and ionomer films are also used. The base material may be a film made of one of these, or a laminated film in which two or more of these are combined. Among these, it is preferable to use a polyethylene terephthalate film from the viewpoint of easily achieving the aforementioned storage elastic modulus. In addition, “(meth) acrylic acid” in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.

  In the base material, various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers, and the like may be included in the film. Examples of the pigment include titanium dioxide and carbon black. Examples of the filler 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 preferable that the base material exhibits a desired function and does not lose smoothness and flexibility.

  When ultraviolet rays are used as energy rays to be irradiated to cure the pressure-sensitive adhesive layer, it is preferable that the substrate has transparency to the ultraviolet rays. Moreover, when using an electron beam as the said energy beam, it is preferable that a base material has the transparency with respect to an electron beam.

  The surface on the pressure-sensitive adhesive layer side of the substrate may be subjected to a surface treatment such as primer treatment, corona treatment, plasma treatment, or roughening treatment (matte treatment) in order to enhance the adhesion to the pressure-sensitive adhesive layer. . Examples of the roughening treatment include an embossing method and a sandblasting method. Various coating films may be provided on the surface of the substrate opposite to the pressure-sensitive adhesive layer.

2. Pressure-sensitive adhesive layer (1) Thickness and physical properties of pressure-sensitive adhesive layer In the pressure-sensitive adhesive sheet for glass dicing according to this embodiment, the thickness of the pressure-sensitive adhesive layer is more than 9 μm and not more than 40 μm, and more than 9 μm and not more than 30 μm. It is preferable that it is more than 9 micrometers and 20 micrometers or less especially. When the thickness of the pressure-sensitive adhesive layer is 9 μm or less, the tackiness of the pressure-sensitive adhesive layer becomes insufficient, the glass chip cannot be sufficiently held on the pressure-sensitive adhesive sheet during dicing, and as a result, chip scattering can be prevented. Can not. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 40 μm, the adhesive strength becomes too strong and the glass chip cannot be picked up well. Furthermore, the pressure-sensitive adhesive layer is likely to sway during dicing, and as a result, chipping and die shift are likely to occur.

  The amount of energy measured using probe tack in the pressure-sensitive adhesive layer (also referred to herein as “tack value”) is preferably 0.01 to 5 mJ / 5 mmφ, and particularly 0.13 to 4 mJ / 5 mmφ. It is preferable that it is 0.18-3.5mJ / 5mmφ. When the tack value is in the above range, the occurrence of chip scattering during dicing can be effectively suppressed. In addition, in this specification, when an adhesive layer consists of energy-beam curable adhesive mentioned later, let the said tack value be the value measured before energy-beam irradiation. Further, in this specification, the tack value is measured under the method described in JIS Z0237: 2009 under the condition that the peeling speed is changed to 1 mm / min, and the details are as shown in the test examples described later.

  The storage elastic modulus at 23 ° C. of the pressure-sensitive adhesive layer is preferably 30 to 100 kPa, particularly preferably 40 to 90 kPa, and further preferably 50 to 80 kPa. When the storage elastic modulus is in the above range, the pressure-sensitive adhesive sheet for glass dicing can exhibit better adhesive force, whereby the glass chip is better retained by the pressure-sensitive adhesive sheet, and the chip scattering is effectively prevented. Can be suppressed. In addition, in this specification, when an adhesive layer consists of an energy-beam curable adhesive mentioned later, the said storage elastic modulus shall be the value measured before energy-beam irradiation. Moreover, the measuring method of the storage elastic modulus in 23 degreeC before energy ray irradiation of an adhesive layer is as showing in the test example mentioned later.

  The storage elastic modulus at 100 ° C. of the pressure-sensitive adhesive layer is preferably 3 to 50 kPa, particularly preferably 3 to 30 kPa, and further preferably 10 to 30 kPa. In general, in a pressure-sensitive adhesive sheet for glass dicing, frictional heat is generated during dicing, and the pressure-sensitive adhesive layer is in a high temperature state of about 100 ° C. Even in such a high temperature state, the pressure-sensitive adhesive layer exhibits a storage elastic modulus of 3 kPa or more, so that the occurrence of shaking during dicing is suppressed, and the movement of the glass plate on the pressure-sensitive adhesive sheet is further suppressed. In addition, die shift is less likely to occur. Moreover, when the storage elastic modulus is 50 kPa or less, the elastic modulus of the pressure-sensitive adhesive layer is not extremely high, and good adhesiveness can be obtained. As a result, chip scattering during dicing can be effectively suppressed. can do. In addition, in this specification, when an adhesive layer consists of an energy-beam curable adhesive mentioned later, the said storage elastic modulus shall be the value measured before energy-beam irradiation. Moreover, the measuring method of the storage elastic modulus in 100 degreeC before the energy ray irradiation of an adhesive layer is as showing in the test example mentioned later.

  When the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive, which will be described later, the tensile elastic modulus at 23 ° C. after irradiation of the energy ray of the pressure-sensitive adhesive layer is preferably 15 to 1500 MPa, particularly 20 to 1000 MPa. It is preferable that it is 20-500 MPa. When the tensile elastic modulus is 15 MPa or more, the glass chip can be picked up after irradiation with energy rays more favorably. Moreover, when the said tensile elasticity modulus is 1500 Mpa or less, the expandability of the adhesive sheet for glass dicing becomes more excellent, and a pickup can be performed more favorably. In addition, the measuring method of the tensile elasticity modulus in 23 degreeC before energy ray irradiation of an adhesive layer is as showing in the test example mentioned later.

  The gel fraction of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably 12.5 to 100%, particularly preferably 37.5 to 100%, and more preferably 50 to 95%. . When the gel fraction of the pressure-sensitive adhesive is within the above range, the physical properties of the pressure-sensitive adhesive layer described above are easily satisfied. Moreover, when the gel fraction of the pressure-sensitive adhesive is 12.5% or more, the cohesive force of the pressure-sensitive adhesive becomes favorable, and the durability of the pressure-sensitive adhesive layer is maintained.

(2) Pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may be a non-curable pressure-sensitive adhesive or a curable pressure-sensitive adhesive. Moreover, the state before hardening may be sufficient as a curable adhesive, and the state after hardening may be sufficient as it. When the pressure-sensitive adhesive layer is composed of multiple layers, a combination of a non-curable pressure-sensitive adhesive and a curable pressure-sensitive adhesive may be used. Examples of the non-curable adhesive include acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, polyester adhesives, and polyvinyl ether adhesives. Examples of the curable pressure-sensitive adhesive include an energy beam curable pressure-sensitive adhesive and a thermosetting pressure-sensitive adhesive.

  In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer is preferably made of an energy ray-curable pressure-sensitive adhesive, and particularly preferably made of an energy ray-curable acrylic pressure-sensitive adhesive. When the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive, it is possible to cure the pressure-sensitive adhesive by irradiating the pressure-sensitive adhesive layer with energy rays before the pickup step. Thereby, the adhesive force with respect to the glass chip of an adhesive sheet falls moderately, and it becomes possible to perform a pick-up favorably.

  Generally, the energy ray curable acrylic pressure-sensitive adhesive contains a (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain, and the (meth) acrylic acid. Those formed from a pressure-sensitive adhesive composition containing no energy ray-curable compound (B) other than the ester copolymer (A) (hereinafter sometimes referred to as “X type” for convenience) and energy ray curing Formed from a pressure-sensitive adhesive composition containing an energy ray-curable compound (B) other than the acrylic polymer (N) and the (meth) acrylic ester copolymer (A), (It may be referred to as “Y-type” for convenience.) And (meth) acrylate copolymer (A) in which an energy ray-curable group is introduced into the side chain, and the (meth) acrylate copolymer (A) other than energy ray-curable compound (B) which was formed from the pressure-sensitive adhesive composition containing a (hereinafter, conveniently be referred to as "Z-type".) And are present.

  In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer may be composed of any of these types of pressure-sensitive adhesives. In particular, the X-type pressure-sensitive adhesive exhibits a higher elastic modulus at a high temperature, and therefore can effectively suppress chipping and die shift during dicing. In addition, since the X-type pressure-sensitive adhesive does not contain a low-molecular compound such as the energy ray-curable compound (B), the compound does not remain on the glass chip, and when a crosslinking agent described later is used. , The whole is uniformly crosslinked. For this reason, generation | occurrence | production of adhesive residue can be suppressed effectively. Furthermore, in the X-type pressure-sensitive adhesive, since the component involved in curing by energy ray irradiation is only one component of the (meth) acrylic acid ester copolymer (A), a component that occurs in the case of a plurality of components It is difficult to cause poor curing due to the imbalance of the ratios and can be cured well. Thereby, since it is easy to reduce adhesive force by energy ray irradiation, a more favorable pick-up becomes possible. From the above, it is preferable to use an X-type pressure-sensitive adhesive.

  The (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain described above and the acrylic polymer (N) having no energy ray-curable property are contained as they are in the pressure-sensitive adhesive layer. Or may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent (C) described later.

(2-1) (Meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain
The (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced into the side chain is obtained by reacting the acrylic copolymer (AP) with the energy ray curable group-containing compound (A3). Is preferably obtained.

  The acrylic copolymer (AP) is preferably a copolymer of at least a (meth) acrylic acid alkyl ester monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group.

  As the (meth) acrylic acid alkyl ester monomer (A1), those having an alkyl group having 1 to 18 carbon atoms are preferable, and those having 1 to 4 carbon atoms are particularly preferable. Specific examples of the (meth) acrylic acid alkyl ester monomer (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (meth). N-pentyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, (meth) Examples include myristyl acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  The proportion of the mass of the structural portion derived from the (meth) acrylic acid alkyl ester monomer (A1) in the total mass of the acrylic copolymer (AP) is preferably 50 to 98 mass%, particularly 60 to 95. It is preferable that it is mass%, and it is further preferable that it is 70-90 mass%.

  As the functional group-containing monomer (A2), a monomer having a reactive functional group capable of reacting with the functional group of the energy ray-curable group-containing compound (A3) is used. Examples of the functional group contained in the functional group-containing monomer (A2) include a hydroxyl group, a carboxy group, an amino group, a substituted amino group, and an epoxy group. Among them, a hydroxyl group and a carboxy group are preferable, and a hydroxyl group is particularly preferable. In addition, when using the crosslinking agent (C) mentioned later, the reactive functional group which a functional group containing monomer (A2) has may react with the said crosslinking agent (C).

  In the case where a monomer having a hydroxyl group (hydroxyl group-containing monomer) is used as the functional group-containing monomer (A2), examples thereof include (meth) acrylic acid hydroxyalkyl ester, and specific examples thereof include (meth) acrylic acid 2 -Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic acid 4 -Hydroxybutyl etc. are mentioned. Among these, 2-hydroxyethyl (meth) acrylate is preferable from the viewpoint of hydroxyl reactivity and copolymerization. These may be used alone or in combination of two or more.

  When a monomer having a carboxy group (carboxy group-containing monomer) is used as the functional group-containing monomer (A2), examples thereof include ethylenically unsaturated carboxylic acids. Specific examples thereof include acrylic acid, methacrylic acid, Examples include crotonic acid, maleic acid, itaconic acid, citraconic acid, and the like. Among these, acrylic acid is preferable from the viewpoint of the reactivity and copolymerization of the carboxy group. These may be used alone or in combination of two or more.

  Different types of functional group-containing monomers (A2) may be used in combination. For example, the above-mentioned hydroxyl group-containing monomer and carboxy group-containing monomer may be used in combination.

  The proportion of the mass of the structural portion derived from the functional group-containing monomer (A2) in the total mass of the acrylic copolymer (AP) is preferably 5 to 40% by mass, particularly 7 to 35% by mass. Is more preferable, and it is preferable that it is 10-30 mass%. Energy to the (meth) acrylic acid ester copolymer (A) in which the energy ray-curable group is introduced into the side chain when the proportion of the mass of the structural portion derived from the functional group-containing monomer (A2) is in the above range. The amount of the linear curable group-containing compound (A3) introduced can be adjusted to a suitable range. Moreover, when making a functional group containing monomer (A2) and a crosslinking agent (C) react using the crosslinking agent (C) mentioned later, the degree of bridge | crosslinking by the said crosslinking agent (C), ie, gel fraction, It is possible to control the physical properties such as cohesive force of the pressure-sensitive adhesive layer.

  In addition to the (meth) acrylic acid alkyl ester monomer (A1) and the functional group-containing monomer (A2) described above, the acrylic copolymer (AP) may contain other monomers as monomers constituting the acrylic copolymer (AP).

  Examples of the other monomers include alkoxyalkyl group-containing (meth) acrylic such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Acid esters; (meth) acrylic acid esters having an aliphatic ring such as cyclohexyl (meth) acrylate; (meth) acrylic acid esters having an aromatic ring such as phenyl (meth) acrylate; non-acrylamide such as acrylamide and methacrylamide Crosslinkable acrylamide; (meth) acrylic acid ester having non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; acetic acid Vinyl; styrene and the like. These may be used alone or in combination of two or more.

  The polymerization mode of the acrylic copolymer (AP) may be a random copolymer or a block copolymer. Moreover, it does not specifically limit regarding the polymerization method, It can superpose | polymerize 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.

  As a functional group which can react with the functional group of a functional group containing monomer (A2), an isocyanate group, an epoxy group, etc. are mentioned, for example, Among them, an isocyanate group with high reactivity with a hydroxyl group is preferable.

  As the curable group having an energy ray curable carbon-carbon double bond (energy ray curable group), a (meth) acryloyl group or the like is preferable. In addition, it is preferable that 1-5 energy beam curable carbon-carbon double bonds exist in 1 molecule of energy beam curable group containing compound (A3), and it is especially preferable that 1-3 exist.

  Examples of the energy ray curable group-containing compound (A3) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl). ) Ethyl isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound and hydroxyethyl (meth) acrylate; reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth) acrylate And acryloyl monoisocyanate compound obtained by the above method. Among these, 2-methacryloyloxyethyl isocyanate is particularly preferable. In addition, an energy-beam curable group containing compound (A3) may be used independently, and may be used in combination of 2 or more type.

  In preparing the (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain, the acrylic copolymer (AP) is prepared, and the acrylic copolymer (AP) is prepared. And the energy ray-curable group-containing compound (A3) can be reacted 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). To do. Thereby, the (meth) acrylic acid ester copolymer (A) by which the energy-beam curable group was introduce | transduced into the side chain is obtained. As will be described later, the reaction between the acrylic copolymer (AP) and the energy ray-curable group-containing compound (A3) is preferably performed in the presence of the organometallic catalyst (D).

  In the (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain, the energy ray-curable group content relative to the amount of the reactive functional group of the functional group-containing monomer (A2) The amount of the compound (A3) is preferably 30 to 100 mol%, particularly preferably 40 to 95 mol%, and further preferably 50 to 90 mol%.

  The weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain is preferably 100,000 to 2,500,000, particularly 150,000 to 2,000,000. Preferably, it is preferably 300,000 to 1,500,000. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method. When the weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain is in the above range, the coating property of the pressure-sensitive adhesive composition is secured. In addition, since the cohesiveness of the pressure-sensitive adhesive layer becomes good, physical properties suitable for dicing can be obtained.

(2-2) Acrylic polymer having no energy beam curability (N)
As the acrylic polymer (N) having no energy beam curability, conventionally known acrylic polymers can be used as long as they do not have energy beam curability. The acrylic polymer may be a homopolymer formed from one type of acrylic monomer, or may be a copolymer formed from a plurality of types of acrylic monomers, It may be a copolymer formed from a plurality of types of acrylic monomers and monomers other than acrylic monomers.

  Specific types of the compound that becomes the acrylic monomer are not particularly limited, and specific examples include (meth) acrylic acid, (meth) acrylic acid ester, and derivatives thereof (acrylonitrile, itaconic acid, and the like). More specific examples include the above-mentioned (meth) acrylic acid alkyl ester monomer (A1) and functional group-containing monomer (A2). In addition, (meth) acrylic acid methoxymethyl, (meth) acrylic acid methoxy (Meth) acrylic acid ester containing an alkoxyalkyl group such as ethyl, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate; (meth) acrylic acid ester having an aliphatic ring such as cyclohexyl (meth) acrylate; (Meth) acrylic acid ester having an aromatic ring such as phenyl (meth) acrylate; non-crosslinkable acrylamide such as acrylamide and methacrylamide; N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid Non-crosslinking tertiary amino group such as N, N-dimethylaminopropyl A (meth) acrylic acid ester; and the like styrene; vinyl acetate.

  In the case where the non-energy ray curable acrylic pressure-sensitive adhesive (N) has a reactive functional group derived from the functional group-containing monomer (A2), an acrylic polymer is used from the viewpoint of setting the degree of crosslinking in a favorable range. The ratio of the mass of the structural portion derived from the functional group-containing monomer (A2) in the total mass is preferably about 1 to 20% by mass, and more preferably 2 to 10% by mass.

  The weight average molecular weight (Mw) of the acrylic polymer (N) having no energy beam curability is preferably 100,000 to 2,500,000, particularly preferably 150,000 to 2,000,000, and more preferably 200,000. It is preferably ˜1.5 million. When the weight average molecular weight (Mw) of the acrylic polymer (N) having no energy ray curability is in the above range, the coating property of the pressure-sensitive adhesive composition is ensured and the cohesiveness of the pressure-sensitive adhesive layer is ensured. Therefore, physical properties suitable for dicing can be obtained.

(2-3) Energy ray curable compound (B)
The energy ray curable compound (B) is a compound that is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams. Examples of the energy ray curable compound (B) include low molecular weight compounds having an energy ray polymerizable group (monofunctional or polyfunctional monomers and oligomers), specifically, trimethylolpropane triacrylate, Tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, acrylates such as 1,6-hexanediol diacrylate, dicyclopentadiene dimethoxy Cyclic aliphatic skeleton-containing acrylates such as diacrylate and isobornyl acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate Rate oligomer, epoxy-modified acrylates, polyether acrylates, acrylate compounds such as itaconic acid oligomer is used. Such a compound has an energy ray-curable double bond in the molecule, and usually has a molecular weight of about 100 to 30,000, preferably about 300 to 10,000.

  When the pressure-sensitive adhesive layer in the present embodiment is composed of the above-described Y-type pressure-sensitive adhesive, the content of the energy ray-curable compound (B) in the pressure-sensitive adhesive composition is an acrylic polymer having no energy ray-curable property ( N) It is preferable that it is 20-200 mass parts with respect to 100 mass parts, It is especially preferable that it is 40-160 mass parts, Furthermore, it is preferable that it is 40-150 mass parts.

  When the pressure-sensitive adhesive layer in the present embodiment is composed of the above-described Z-type pressure-sensitive adhesive, the content of the energy ray-curable compound (B) in the pressure-sensitive adhesive composition is such that an energy ray-curable group is introduced into the side chain. It is preferable that it is 3-60 mass parts with respect to 100 mass parts of (meth) acrylic acid ester copolymer (A), It is especially preferable that it is 5-50 mass parts, Furthermore, it is 10-40 mass parts. It is preferable.

(3) Crosslinking agent (C)
The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in this embodiment is a (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain, or an acrylic type that does not have energy ray-curable properties. It is preferable to contain a crosslinking agent (C) capable of crosslinking the polymer (N). In this case, the pressure-sensitive adhesive layer in this embodiment is a crosslinked product obtained by a crosslinking reaction between the (meth) acrylic acid ester copolymer (A) or the acrylic polymer (N) and the crosslinking agent (C). Containing. By using such a crosslinking agent (C), it becomes easy to adjust the gel fraction of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer to a suitable range, and physical properties suitable for dicing can be obtained.

  Examples of the crosslinking agent (C) include, for example, epoxy compounds, polyisocyanate compounds, metal chelate compounds, polyimine compounds such as aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides. And metal salts. 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, because it is easy to control the crosslinking reaction.

  Examples of the epoxy compound include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, and ethylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.

  A polyisocyanate compound is a compound having two or more isocyanate groups per molecule. Specific examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate. . Furthermore, these biuret bodies, isocyanurate bodies, adduct bodies and the like can be mentioned. Examples of the adduct include a reaction product with a low molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like.

  A crosslinking agent (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  When the pressure-sensitive adhesive is of the X type or the Z type, the content of the crosslinking agent (C) in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer is (meth) acrylic acid having an energy ray-curable group introduced in the side chain. It is preferable that it is 0.01-15 mass parts with respect to 100 mass parts of ester copolymers (A), It is especially preferable that it is 0.05-10 mass parts, Furthermore, it is 0.1-2 mass parts. Preferably there is. Moreover, when an adhesive is Y type, content of the crosslinking agent (C) of the adhesive composition which forms an adhesive layer is 3 with respect to the acrylic polymer (N) which does not have energy-beam sclerosis | hardenability. It is preferably -20 parts by mass, particularly preferably 5-17 parts by mass, and more preferably 7-14 parts by mass.

(4) Organometallic catalyst (D)
In order to obtain a (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain, an acrylic copolymer (AP) and an energy ray curable group-containing compound (A3) are used. When making it react, it is preferable that the said reaction is performed in presence of an organometallic catalyst (D). As the organometallic catalyst (D), it is particularly preferable to use at least one selected from an organic compound containing zirconium, an organic compound containing titanium, and an organic compound containing tin. The pressure-sensitive adhesive composition containing the (meth) acrylic acid ester copolymer (A) obtained by reacting in the presence of such an organometallic catalyst (D) has a more excellent tack. A layer can be formed, and chip scattering during dicing can be effectively suppressed. The organometallic catalyst (D) is preferably at least one of an organic compound containing zirconium and an organic compound containing titanium among the above three kinds of organic compounds, and in particular, an organic compound containing zirconium. Is preferred.

  Examples of the form of the organic compound include alkoxide compounds, chelate compounds, acylate compounds, and the like. Among these, chelate compounds are preferable.

  Specific examples of the organometallic catalyst (D) include zirconium alkoxide, zirconium chelate, titanium alkoxide, titanium chelate, tin alkoxide, tin chelate and the like. Among these, zirconium chelate is preferable. The organometallic catalyst (D) may be composed of one of these compounds, or may be composed of two or more of these compounds.

  The usage-amount of the organometallic catalyst (D) used in reaction for obtaining the (meth) acrylic acid ester copolymer (A) by which the energy-beam curable group was introduce | transduced into the side chain is not limited. The amount used is preferably 0.001 to 10 parts by mass, in particular 0.01 to 10 parts by mass in terms of the amount of metal with respect to 100 parts by mass of the solid content of the (meth) acrylic acid ester copolymer (A). The amount is preferably 5 parts by mass, and more preferably 0.05 to 3 parts by mass. In the present invention, the metal amount conversion means the compounding amount or the compounding ratio calculated by the mass of the metal only, excluding the mass corresponding to the molecular weight of the structure composed of the organic substance in the organometallic catalyst (D). Say.

(5) Other components In addition to the above components, the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in this embodiment is a photopolymerization initiator, a crosslinking accelerator, a coloring material such as a dye or pigment, a flame retardant, and a filler. In addition, various additives such as an antistatic agent may be contained.

  Examples of the photopolymerization initiator include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds and peroxide compounds, and photosensitizers such as amines and quinones. Specifically, α-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, β-chlore Examples include anthraquinone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.

  When the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment contains a crosslinking agent (C), an appropriate crosslinking accelerator may be contained depending on the type of the crosslinking agent (C).

(6) Irradiation of energy rays In the pressure-sensitive adhesive sheet for glass dicing according to this embodiment, when the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive, the energy rays for curing the pressure-sensitive adhesive are ionizing radiation. That is, ultraviolet rays, electron beams, X-rays and the like can be mentioned. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.

When ultraviolet rays are used as the ionizing radiation, it is preferable to use near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm for ease of handling. What is necessary is just to select suitably according to the kind of energy-beam curable component contained in an adhesive composition and the thickness of an adhesive layer as a light quantity, Usually, it is about 50-500 mJ / cm < ² >, 100-450 mJ / cm ² is preferable, and 200 to 400 mJ / cm ² is more preferable. Moreover, ultraviolet illuminance is about 50-500 mW / cm < ² > normally, 100-450 mW / cm < ² > is preferable and 200-400 mW / cm < ² > is more preferable. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a metal halide lamp, UV-LED etc. are used.

  When an electron beam is used as the ionizing radiation, the acceleration voltage may be appropriately selected according to the type of energy ray-curable component contained in the pressure-sensitive adhesive composition and the thickness of the pressure-sensitive adhesive layer. The voltage is preferably about 10 to 1000 kV. Moreover, what is necessary is just to set the irradiation dose to the range which an adhesive hardens | cures appropriately, and is normally selected in the range of 10-1000 krad. The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

3. Release Film In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, a release film is laminated on the surface for the purpose of protecting the surface of the pressure-sensitive adhesive layer opposite to the base material until the adherend is applied. It may be. The structure of a peeling film is arbitrary and what peeled the plastic film with the peeling agent etc. is illustrated. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, a silicone release agent, a fluorine release agent, a long-chain alkyl release agent, or the like can be used. Among these, a silicone-based release agent that can provide inexpensive and stable performance is preferable. Although there is no restriction | limiting in particular in the thickness of a peeling film, Usually, it is about 20-250 micrometers.

4). Physical properties of pressure-sensitive adhesive sheet for glass dicing The non-alkali glass of the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment after the surface opposite to the base material of the pressure-sensitive adhesive layer is pasted on alkali-free glass and allowed to stand for 20 minutes. Is preferably 8000 to 25000 mN / 25 mm, particularly preferably 9000 to 22000 mN / 25 mm, and more preferably 10000 to 19000 mN / 25 mm. When the adhesive force is within the above range, the glass plate and the glass chip can be better retained on the adhesive sheet during dicing. As a result, chip scattering is effectively suppressed. In addition, since the glass plate and the glass chip are better held on the pressure-sensitive adhesive sheet, the shift of the glass plate and the glass chip on the pressure-sensitive adhesive sheet is suppressed, and die shift and chipping hardly occur. In the present specification, when the pressure-sensitive adhesive layer is composed of the above-described energy ray-curable pressure-sensitive adhesive, the pressure-sensitive adhesive force is a value measured before energy beam irradiation.

  When the pressure-sensitive adhesive layer is made of the above-mentioned energy ray-curable pressure-sensitive adhesive, the surface of the pressure-sensitive adhesive layer opposite to the base material is pasted on non-alkali glass, and the pressure-sensitive adhesive layer is irradiated with energy rays The adhesive strength of the glass dicing pressure-sensitive adhesive sheet according to this embodiment to an alkali-free glass is preferably 50 to 250 mN / 25 mm, particularly preferably 60 to 160 mN / 25 mm, and more preferably 70 to 130 mN / It is preferably 25 mm. The adhesive strength after irradiation with energy rays is 50 mN / 25 mm or more, so that it is possible to prevent the glass chip from being unintentionally peeled off from the adhesive sheet or shifted before the glass chip is picked up from the adhesive sheet. , Pickup can be performed better. On the other hand, when the adhesive strength after energy beam irradiation is 250 mN / 25 mm or less, for example, when individually picking up glass chips, it is possible to pick up well without damaging the glass chips and to generate adhesive residue. Can be effectively suppressed.

  The adhesive strength in the present specification is an adhesive strength (mN / 25 mm) measured by a 180 ° peeling method according to JIS Z0237: 2009, using an alkali-free glass as an adherend, and details of the measuring method will be described later. As described in the test method.

5). Manufacturing method of adhesive sheet for glass dicing The manufacturing method of the adhesive sheet for glass dicing will not be specifically limited if the adhesive layer formed from the above-mentioned adhesive composition can be laminated | stacked on one surface of a base material.

  As an example of the manufacturing method of the adhesive sheet for glass dicing, first, the coating composition containing the above-mentioned adhesive composition and the solvent or a dispersion medium further as needed is prepared. Next, this coating composition is applied onto one surface of the substrate by a die coater, curtain coater, spray coater, slit coater, knife coater or the like to form a coating film. Furthermore, an adhesive layer can be formed by drying the said coating film. The properties of the coating composition are not particularly limited as long as it can be applied. The component for forming the pressure-sensitive adhesive layer may be contained as a solute in the coating composition, or may be contained as a dispersoid.

  When the coating composition contains a crosslinking agent (C), the above drying conditions (temperature, time, etc.) may be changed or heat treatment may be performed in order to form a crosslinked structure at a desired density. It may be provided separately. In order to sufficiently advance the crosslinking reaction, after the pressure-sensitive adhesive layer is laminated on the substrate by the above-described method, the obtained pressure-sensitive adhesive sheet for glass dicing is subjected to, for example, an environment of 23 ° C. and a relative humidity of 50% for 1 week. Curing may be performed by leaving it for about 2 weeks.

  As another example of the method for producing the pressure-sensitive adhesive sheet for glass dicing, first, the coating composition is applied on the release-treated surface of the release film as described above to form a coating film. Next, the said coating film is dried and the laminated body which consists of an adhesive layer and a peeling film is formed. Furthermore, the surface on the opposite side to the peeling film in the adhesive layer of this laminate is affixed to the substrate. By the above, the laminated body of the adhesive sheet for glass dicing and a peeling film can be obtained. The release film in this laminate may be peeled off as a process material, or the adhesive layer may be protected until it is attached to the adherend.

6). Method of using pressure-sensitive adhesive sheet for glass dicing The pressure-sensitive adhesive sheet for glass dicing according to this embodiment can be used for dicing a glass plate. Moreover, the adhesive sheet for glass dicing which concerns on this embodiment can be used also for a series of processes including the dicing of a glass plate and the subsequent pickup.

  When used in a series of steps including dicing and subsequent pickup, first, the surface opposite to the substrate in the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment (hereinafter referred to as “pressure-sensitive surface”). A) may be affixed to the glass plate. When a release film is laminated on the adhesive surface, a glass plate is attached to the adhesive surface exposed by peeling the release film. On the other hand, the peripheral edge of the adhesive surface is affixed to an annular jig called a ring frame for transportation and fixation to the apparatus. In addition, it is preferable to leave still for 10 minutes-120 minutes after sticking a glass plate until it implements the subsequent dicing process, It is especially preferable to leave still for 15 minutes-60 minutes, Furthermore, 20 minutes- It is preferable to stand for 40 minutes. By leaving still for such a period, the adhesiveness of a glass plate and an adhesive sheet can be made sufficient.

  Next, a dicing process is performed. That is, the glass plate affixed on the glass dicing adhesive sheet is cut using a dicing blade. Thereby, the several glass chip stuck on the adhesive sheet for glass dicing is obtained. In the adhesive sheet for glass dicing which concerns on this embodiment, since the thickness of an adhesive layer is comparatively thick as mentioned above, a tack becomes a favorable thing. Thereby, a glass chip is favorably hold | maintained at an adhesive sheet and chip | tip scattering is suppressed. Further, in addition to the glass chip being favorably held by the pressure-sensitive adhesive sheet due to the thickness of the pressure-sensitive adhesive layer, chipping and die shift are suppressed by the thickness of the base material being in the above-described range.

  When the pressure-sensitive adhesive layer is composed of the above-mentioned energy ray-curable pressure-sensitive adhesive, after the dicing process is completed, energy rays are applied from the glass chip side surface or the substrate side surface to the pressure sensitive adhesive sheet to which a plurality of glass chips are attached. Irradiate. Thereby, the polymerization reaction of the energy ray curable group of the (meth) acrylic acid ester copolymer (A) proceeds to lower the adhesiveness, and the subsequent pick-up process can be easily performed.

  The pick-up process can be performed by general-purpose means such as a suction collet. At this time, in order to facilitate the pickup, it is preferable to push up the target glass chip with a pin, a needle, or the like from the surface of the substrate opposite to the pressure-sensitive adhesive layer. In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive sheet has good flexibility because the thickness of the substrate is in the above range. Furthermore, when the thickness of the pressure-sensitive adhesive layer is in the above range, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet becomes a size suitable for glass chip pickup. With these, good pickup can be performed. Moreover, in the adhesive sheet for glass dicing which concerns on this embodiment, the glue derived from an adhesive layer does not remain on the picked-up glass chip. In particular, when the pressure-sensitive adhesive layer is composed of an X-type pressure-sensitive adhesive, the X-type pressure-sensitive adhesive does not contain a low molecular compound such as the energy ray-curable compound (B), so that the compound may remain on the glass chip. Absent. In addition, the pressure-sensitive adhesive composition for forming the X-type pressure-sensitive adhesive easily proceeds with uniform crosslinking. As described above, generation of adhesive residue is effectively suppressed.

  In addition, it is preferable to perform an expanding process before a pick-up process. In this case, the adhesive sheet for glass dicing is extended in the plane direction. Thereby, the space | interval between glass chips spreads 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 substrate, and the like. In addition, you may perform an expanding process before energy beam irradiation.

In the case of dicing the glass plate using a glass dicing pressure-sensitive adhesive sheet according to the present embodiment, the area of the plane of the resulting glass tip is preferably ^{1 × 10 -6 mm 2 ~1mm 2} , 1 × more preferably 10 ^-4 mm ² ~0.25mm ^2, it is preferably particularly ^{2.5 × 10 -3 mm 2 ~0.09mm 2} , more in 0.01mm ² ~0.03mm ² Preferably there is. According to the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, since the thickness of the pressure-sensitive adhesive layer is relatively thick and can exhibit a good tack, even a small glass chip having an area in the above range, Generation of chip scattering, chipping and die shift can be suppressed.

  When dicing a glass plate using the pressure-sensitive adhesive sheet for glass dicing according to this embodiment, the thickness of the glass plate as a workpiece is preferably 50 to 10,000 μm, particularly preferably 100 to 5000 μm, and further Is preferably 300 to 800 μm. In the present specification, the “workpiece” refers to an adherend to which the glass dicing adhesive sheet according to the present embodiment is attached, or a workpiece to be processed using the adhesive sheet. According to the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the pressure-sensitive adhesive layer is relatively large and can exhibit a good tack. Therefore, even a thin glass plate having a thickness of 50 μm Dicing can be performed while suppressing the occurrence.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment 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 substrate and the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet for glass dicing.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc. In addition, description of the mass part in the following is described as a solid content conversion value.

[Example 1]
(1) Preparation of (meth) acrylic ester copolymer (A) 75 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of methyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate were copolymerized. An acrylic copolymer (AP) was obtained. When the molecular weight of the obtained acrylic copolymer (AP) was measured, the weight average molecular weight (Mw) was 700,000. In addition, the weight average molecular weight (Mw) in a present Example is a weight average molecular weight of standard polystyrene conversion measured (GPC measurement) using gel permeation chromatography (GPC).

  Subsequently, the obtained acrylic copolymer (AP) and 2-methacryloyloxyethyl isocyanate (MOI) as the energy ray-curable group-containing compound (A3) are converted into a zirconium chelate catalyst as the organometallic catalyst (D). (Matsumoto Fine Chemical Co., Ltd., product name “ZC-700”). This obtained the (meth) acrylic acid ester copolymer (A) by which the energy-beam curable group (methacryloyl group) was introduce | transduced into the side chain. At this time, both were made to react so that MOI might be 60 mol (60 mol%) per 100 mol of 2-hydroxyethyl acrylate units of an acrylic copolymer (AP). Moreover, the compounding quantity of the organometallic catalyst (D) was 0.1 mass part with respect to 100 mass parts of acrylic copolymers (AP).

(2) Preparation of pressure-sensitive adhesive composition 100 parts by mass of the (meth) acrylic acid ester copolymer (A) obtained in the above step (1) and α-hydroxycyclohexyl phenyl ketone (BASF) as a photopolymerization initiator Manufactured, product name “Irgacure 184”) and 3.0 parts by mass of trimethylolpropane-modified tolylene diisocyanate (product name “Coronate L” manufactured by Tosoh Corporation) as a crosslinking agent (C) It mixed in and the coating solution of the adhesive composition was obtained. In addition, X type adhesive is obtained by using this adhesive composition.

(3) Production of pressure-sensitive adhesive sheet for glass dicing A release film (product of Lintec, manufactured by Lintec Co., Ltd.) from the coating solution of the pressure-sensitive adhesive composition obtained in the above step (2). A name “SP-PET 381031” (thickness: 38 μm) was applied to the release-treated surface by a die coater. Next, the film was treated at 100 ° C. for 1 minute to dry the coating film and advance the crosslinking reaction. Thereby, the laminated body which consists of a peeling film and a 10-micrometer-thick adhesive layer was obtained. Furthermore, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “A-4100”, thickness: 100 μm) as a base material was bonded to the surface on the pressure-sensitive adhesive layer side of the laminate. Thereby, the adhesive sheet for glass dicing which the base material, the adhesive layer, and the peeling film were laminated | stacked in order was obtained.

[Examples 2 to 11]
The material of the substrate, the thickness of the substrate, the amount of 2-methacryloyloxyethyl isocyanate (MOI) used to form the pressure-sensitive adhesive layer, the organometallic catalyst (D) used to form the pressure-sensitive adhesive layer A glass dicing pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the type and the thickness of the pressure-sensitive adhesive layer were changed as shown in Table 1.

[Comparative Examples 1-3]
Except for changing the thickness of the base material, the type of organometallic catalyst (D) used to form the pressure-sensitive adhesive layer, and the thickness of the pressure-sensitive adhesive layer as shown in Table 1, the same manner as in Example 1 was performed. A pressure-sensitive adhesive sheet for glass dicing was produced.

[Comparative Example 4]
A glass dicing pressure-sensitive adhesive sheet was produced in the same manner as in Example 12 except that the thickness of the pressure-sensitive adhesive layer was changed as shown in Table 1.

Details of abbreviations and the like described in Table 1 are as follows.
[Base material]
PET (thickness: 100 μm): polyethylene terephthalate film (manufactured by Toyobo, product name “A-4100”)
PET (thickness 50 μm): polyethylene terephthalate film (product name “A-4100” manufactured by Toyobo Co., Ltd.)
PET (thickness: 188 μm): polyethylene terephthalate film (manufactured by Toyobo, product name “A-4100”)
PO: Polyolefin film (manufactured by Riken Technos, product name “ADN09-100T-M8”)
PP: Polypropylene film (Diaplus Film, product name “PL109”)
PI: Polyimide film (manufactured by MPRTECH, product name “Mordhar PIF100”)
[Organic metal catalyst]
Zr: Zirconium chelate catalyst (manufactured by Matsumoto Fine Chemical Co., Ltd., product name “ZC-700”)
Sn: Dibutyltin laurate catalyst (manufactured by Toyochem, product name “BXX-3778”)

[Test Example 1] (Measurement of storage elastic modulus of substrate)
About the base material used by the Example and the comparative example, the storage elastic modulus in 23 degreeC 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
Temperature increase rate: 3 ° C / min Frequency: 11Hz
Amplitude: 20 μm

[Test Example 2] (Measurement of storage elastic modulus of adhesive layer before UV irradiation)
The coating solution of the pressure-sensitive adhesive composition used in the examples and comparative examples was coated on the release-treated surface of a first release film (product name “SP-PET 381031”, manufactured by Lintec Corporation) having a thickness of 38 μm. The obtained coating film was dried at 100 ° C. for 1 minute to dry the coating film. As a result, an adhesive layer having a thickness of 40 μm was formed on the first release film. Furthermore, on the surface opposite to the first release film in the pressure-sensitive adhesive layer, a release treatment surface of a second release film having a thickness of 38 μm (product name “SP-PET381031” manufactured by Lintec Corporation) is bonded, The 1st peeling film, the 40-micrometer-thick adhesive layer, and the 2nd peeling film obtained the laminated body laminated | stacked in this order. A plurality of pressure-sensitive adhesive layers obtained by the above procedure were laminated so as to have a thickness of 800 μm. This laminate having a thickness of 800 μm was punched out into a circle having a diameter of 10 mm to obtain a sample for measurement. Using a viscoelasticity measuring device (TA Instruments, product name “ARES”), the sample was strained at a frequency of 1 Hz, measured at −50 to 150 ° C., and stored at 23 ° C. and 100 ° C. Got the value. The results are shown in Table 1. In addition, when laminating a plurality of pressure-sensitive adhesive layers, the above laminate was used after being formed for 1 week in an environment of a temperature of 23 ° C. and a humidity of 50% after the formation of the pressure-sensitive adhesive layer.

[Test Example 3] (Measurement of tensile modulus of adhesive layer after UV irradiation)
By the same procedure as in Test Example 2, a plurality of pressure-sensitive adhesive layers were laminated so as to have a thickness of 200 μm.

Subsequently, an ultraviolet ray (UV) irradiation (illuminance: 230 mW / cm ² , light amount: 190 mJ / cm ² ) is performed using an ultraviolet irradiation device (product name “RAD-2000”, manufactured by Lintec Corporation), whereby the pressure-sensitive adhesive layer Was cured. Furthermore, it cut | judged to 15 mm x 140 mm, and obtained the test piece.

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

[Test Example 4] (Measurement of tack value)
About the surface of the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheets produced in Examples and Comparative Examples, the tack value was measured with a probe tack tester (product name “RPT-100” manufactured by Reska Co.) using a probe having a diameter of 5 mm (5 mmφ) Was measured. The measurement method was the method described in JIS Z0237: 2009, while changing the peeling speed to 1 mm / min, while the load was 100 gf / cm ² and the contact time was 1 second, as described in the above JIS regulations. The measured energy amount (peak integrated value) was determined and used as the tack value (unit: mJ / 5 mmφ). The results are shown in Table 1. For the measurement, a pressure-sensitive adhesive sheet was used after forming the pressure-sensitive adhesive layer and left for 1 week in an environment of a temperature of 23 ° C. and a humidity of 50%.

[Test Example 5] (Measurement of adhesive strength before and after UV irradiation)
The release film was peeled from the pressure-sensitive adhesive sheet for glass dicing produced in Examples and Comparative Examples at room temperature and allowed to stand for 1 week in an environment at a temperature of 23 ° C. and a humidity of 50%. The exposed surface of the pressure-sensitive adhesive layer was superposed on one surface of a 6-inch non-alkali glass plate, and was pasted by applying a load by reciprocating a 2 kg roller, and left for 20 minutes. Thereafter, the pressure-sensitive adhesive sheet for glass dicing is peeled off from the alkali-free glass plate at a peeling speed of 300 mm / min and a peeling angle of 180 ° by a 180 ° peeling method according to JIS Z0237: 2009, and the adhesive strength (mN / 25 mm). Was measured. This measured value was taken as the adhesive strength before ultraviolet irradiation. The results are shown in Table 1.

Moreover, after sticking the adhesive sheet for glass dicing and the 6-inch non-alkali glass plate which were manufactured in the Example and the comparative example similarly to the above, and leaving it to stand for 20 minutes, from the base material side of the adhesive sheet for glass dicing Then, ultraviolet ray irradiation (illuminance: 200 mW / cm ² , light amount: 180 mJ / cm ² ) was performed using an ultraviolet ray irradiation device (product name “RAD-2000” manufactured by Lintec Corporation) to cure the adhesive layer. . Thereafter, the adhesive strength (mN / 25 mm) was measured in the same manner as described above. This measured value was taken as the adhesive strength after UV irradiation. The results are shown in Table 1.

[Test Example 6] (Evaluation of chip scattering, chipping, and die shift)
The release film was peeled off from the pressure-sensitive adhesive sheet for glass dicing produced in Examples and Comparative Examples and allowed to stand for 1 week in an environment of a temperature of 23 ° C. and a humidity of 50%, and a tape mounter (product name “Adwill RAD 2500 m / 12 ”), a 550 μm-thick 6-inch alkali-free glass plate and a dicing ring frame were attached to the exposed surface of the pressure-sensitive adhesive layer. Subsequently, the glass dicing adhesive sheet was cut according to the outer diameter of the ring frame. Furthermore, the dicing which cut | disconnects from the glass plate side was performed on the following dicing conditions using the dicing apparatus (the product name "DFD-651" by Disco Corporation), and the 0.6 mm square glass chip was obtained.

<Dicing conditions>
・ Dicing machine: DFD-651 manufactured by DISCO
・ Blade: NBC-2H 2050 27HECC manufactured by Disco Corporation
・ Blade width: 0.025 to 0.030 mm
・ Blade tip: 0.640 to 0.760 mm
・ Blade rotation speed: 30000 rpm
・ Cutting speed: 80 mm / sec
・ Base material cutting depth: 20 μm
・ Cutting water volume: 1.0 L / min
・ Cutting water temperature: 20 ℃
・ Dicing size: 0.6 mm square (plane area is 0.36 mm ² )

The pressure-sensitive adhesive sheet to which the glass chips obtained by the dicing process are adhered is visually observed, the number of glass chips that have dropped from the pressure-sensitive adhesive sheet during the dicing process is counted, and the number is divided by the number of divisions in the dicing process. Then, the chip scattering rate (unit:%) was obtained. Based on this calculation result, chip scattering was evaluated based on the following. The evaluation results are shown in Table 1.
A: Chip scattering rate is less than 0.1%.
○: Chip scattering rate is 0.1% or more and less than 5%.
Δ: Chip scattering rate is 5% or more and less than 10%.
X: Chip scattering rate is 10% or more.

Moreover, the presence or absence and shape of the edge part were observed about the glass chip located in the center part and the vicinity of the adhesive sheet for glass dicing after the said dicing. Specifically, using an electron microscope (manufactured by KEYENCE, product name “VHZ-100”, magnification: 300 ×), the flow direction (MD direction) during manufacture of the base material is equivalent to 50 chips and in the MD direction. Fifty chip sides were observed in the orthogonal direction (CD direction). And the chip | tip which has a width | variety or depth of 20 micrometers or more was determined to be chipping, and the number was counted. Based on this result, chipping was evaluated based on the following. The evaluation results are shown in Table 1.
A: The number of chips in which chipping occurred is less than 5.
A: The number of chips in which chipping has occurred is 5 or more and less than 50.
X: The number of chips in which chipping occurred is 50 or more.

Further, for all glass chips obtained by dicing, the lengths of the four sides in a plan view are measured, and the difference between the maximum value and the minimum value is 10% or more of the maximum value (hereinafter “NG”). The number of “chips” may be counted. Based on this result, the die shift was evaluated based on the following. The evaluation results are shown in Table 1.
A: The number of NG chips is less than 50.
○: The number of NG chips is 50 or more and less than 500.
X: The number of NG chips is 500 or more.

[Test Example 7] (Evaluation of pickup)
100 glass chips were picked up from the glass dicing pressure-sensitive adhesive sheet diced in Test Example 6. At this time, push-up with a needle was performed from the surface opposite to the surface to which the glass chip was attached in the pressure-sensitive adhesive sheet for glass dicing (number of needles: 4, push-up speed: 0.3 mm / second, push-up height: 1.5 mm). About the glass chip obtained by picking up, the number (NG number) of the glass chip which was damaged was counted, and the pickup was evaluated according to the following criteria. The results are shown in Table 1.
A: The glass chip was not damaged.
○: There were 1 to 2 breakage of the glass chip.
X: There were three or more broken glass chips.

[Test Example 8] (Evaluation of adhesive residue)
About 5000 glass chips picked up by the method shown in Test Example 7, the presence or absence of the adhesive from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet for glass dicing was checked with an electron microscope (manufactured by KEYENCE, product name “VHZ-100”). , Magnification: 300 times). The number of glass chips to which an adhesive having a maximum width of 30 μm or more adhered was counted, and the adhesive residue was evaluated according to the following criteria.
(Double-circle): The number of the glass chips to which the adhesive adhered was less than 50 pieces.
(Circle): The number of the glass chips to which the adhesive adhered was 50 or more and less than 500 pieces.
X: The number of the glass chips to which the adhesive was attached was 500 or more.

  As can be seen from Table 1, according to the pressure-sensitive adhesive sheet of the example, chip scattering, chipping, die shift and generation of adhesive residue can be suppressed, and good pickup can be performed.

  The pressure-sensitive adhesive sheet for glass dicing according to the present invention is used in a glass dicing process, and particularly preferably used in a thin glass dicing process.

Claims (13)

A glass dicing pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material,
The substrate has a thickness of 30 μm or more and less than 130 μm,
A pressure-sensitive adhesive sheet for glass dicing, wherein the pressure-sensitive adhesive layer has a thickness of more than 9 μm and 40 μm or less.   The pressure-sensitive adhesive layer for glass dicing according to claim 1, wherein the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive.   The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive formed from a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced in the side chain. The pressure-sensitive adhesive sheet for glass dicing according to claim 2.   The amount of energy measured using a probe tack under the condition in which the peeling speed is changed to 1 mm / min in the method described in JIS Z0237: 1991 in the pressure-sensitive adhesive layer is 0.01 to 5 mJ / 5 mmφ. The pressure-sensitive adhesive sheet for glass dicing according to any one of claims 1 to 3.   The pressure-sensitive adhesive sheet for glass dicing according to any one of claims 1 to 4, wherein the storage elastic modulus of the pressure-sensitive adhesive layer at 23 ° C is 30 to 100 kPa.   The pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet for glass dicing after sticking the surface of the pressure-sensitive adhesive layer opposite to the base material on alkali-free glass and allowing it to stand for 20 minutes is 8000 to 25000 mN / It is 25 mm, The adhesive sheet for glass dicing as described in any one of Claims 1-5 characterized by the above-mentioned.   Adhesion of the pressure-sensitive adhesive sheet to the alkali-free glass after the surface of the pressure-sensitive adhesive layer opposite to the base material is attached to non-alkali glass and the pressure-sensitive adhesive layer is irradiated with energy rays. The pressure-sensitive adhesive sheet for glass dicing according to claim 2 or 3, wherein the force is 50 to 250 mN / 25 mm.   The pressure-sensitive adhesive sheet for glass dicing according to claim 2, 3 or 7, wherein the pressure-sensitive adhesive layer has a tensile elastic modulus at 23 ° C after irradiation with energy rays of 15 to 1500 MPa.   The pressure-sensitive adhesive sheet for glass dicing according to any one of claims 1 to 8, wherein the substrate has a storage elastic modulus at 23 ° C of 100 to 8000 MPa.   The said adhesive composition contains a crosslinking agent (C) further, The adhesive sheet for glass dicing of Claim 3 characterized by the above-mentioned. A glass plate, glass dicing according to any one of claims 1 to 10, characterized in that for dicing glass chip plane having an area of 1 × 10 ^-6 mm ² ~1mm ² Adhesive sheet. A method for producing the pressure-sensitive adhesive sheet for glass dicing according to claim 3,
An acrylic copolymer (AP) obtained by copolymerizing at least a (meth) acrylic acid alkyl ester monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group;
A functional group capable of reacting with the functional group of the functional group-containing monomer (A2) and an energy ray-curable group-containing compound (A3) having an energy ray-curable carbon-carbon double bond are reacted to form a side chain. The step of preparing the (meth) acrylic acid ester copolymer (A) into which the energy ray curable group is introduced, and the pressure-sensitive adhesive composition containing the (meth) acrylic acid ester copolymer (A) are used. And the manufacturing method of the adhesive sheet for glass dicing characterized by including the process of laminating | stacking an adhesive layer on the at least one surface of a base material.   The reaction between the acrylic copolymer (AP) and the energy ray-curable group-containing compound (A3) is selected from an organic compound containing zirconium, an organic compound containing titanium, and an organic compound containing tin. The method for producing a pressure-sensitive adhesive sheet for glass dicing according to claim 12, which is carried out in the presence of at least one organometallic catalyst (D).