JP2017179025A - 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 chipping and die shift even when a thin glass sheet is diced to small chips 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, the adhesive layer consists of an energy ray curable adhesive formed from an adhesive composition containing a (meth)acrylic acid ester copolymer (A) having a side chain to which an energy ray curable group is introduced.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.

  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 deformation can be reduced and occurrence of chipping can be suppressed (paragraph 0010 of Patent Document 1).

Japanese Patent No. 3838637

  The pressure-sensitive adhesive sheet disclosed in Patent Document 1 uses a relatively thick glass plate having a thickness of 1 mm as a target of dicing (paragraph 0059 of Patent Document 1). However, the adhesive sheet cannot sufficiently suppress chipping when dicing a thinner glass plate as required in recent years.

  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 the intended position, and a glass chip having a desired shape cannot be obtained.

  The present invention has been made in view of the above circumstances, and provides a glass dicing pressure-sensitive adhesive sheet that hardly causes chipping and die shift even when a thin glass plate is diced into small chips, and a method for manufacturing the same. With the goal.

  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, the pressure-sensitive adhesive The layer is made of an energy ray-curable 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. An adhesive sheet for glass dicing is provided (Invention 1).

  According to the above invention (Invention 1), since the pressure-sensitive adhesive layer exhibits a relatively high elastic modulus when the temperature of the pressure-sensitive adhesive layer becomes high, such as about 100 ° C., due to frictional heat during dicing, As a result, the movement of the glass plate on the pressure-sensitive adhesive sheet is suppressed, and as a result, even when a thin glass plate is diced into small chips, the occurrence of chipping and die shift can be suppressed.

  In the said invention (invention 1), it is preferable that the said adhesive composition further contains energy-beam curable compounds (B) other than the said (meth) acrylic acid ester copolymer (A) (invention 2).

  In the said invention (invention 1 and 2), it is preferable that the said adhesive composition contains a crosslinking agent (C) further (invention 3).

  In the said invention (invention 1-3), it is preferable that the storage elastic modulus in 100 degreeC before the energy ray irradiation of the said adhesive layer is 5-50 kPa (invention 4).

  In the said invention (invention 1-4), 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 energy ray irradiation of the said adhesive sheet for glass dicing It is preferable that the adhesive force with respect to the said non-alkali glass is 5000-25000 mN / 25mm (invention 5).

  In the said invention (invention 1-5), the surface of the said adhesive layer on the opposite side to the said base material is affixed on an alkali free glass, The said glass dicing after 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 6).

  In the said invention (invention 1-6), it is preferable that the storage elastic modulus in 23 degreeC of the said base material is 100-8000 MPa (invention 7).

  In the said invention (invention 1-7), it is preferable to use the glass of thickness 50-10000 micrometers as a workpiece | work (invention 8).

In the above invention (invention 8), a glass plate, it is preferable plane is for dicing glass tip having an area of ^{1 × 10 -6 mm 2 ~1mm 2} ( invention 9).

  Second, the present invention relates to 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, and the functional group. An energy ray-curable group-containing compound (A3) having a substituent capable of reacting with a functional group of the group-containing monomer (A2) and an energy ray-curable carbon-carbon double bond (A3) is reacted to form an energy ray on the side chain. Using the step of preparing the (meth) acrylic acid ester copolymer (A) having a curable group introduced therein, and the pressure-sensitive adhesive composition containing the (meth) acrylic acid ester copolymer (A), 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 is provided (invention 10).

  In the said invention (invention 10), 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 11).

  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, chipping and die shift hardly occur even when a thin glass plate is diced into small chips.

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. .

1. Base material In the adhesive sheet for glass dicing which concerns on this embodiment, it is preferable that the storage elastic modulus in 23 degreeC of a base material is 100-8000 MPa, It is especially preferable that it is 1500-7000 MPa, Furthermore, it is 2000-6000 MPa. Preferably there is. Since the storage elastic modulus at 23 ° C. of the substrate is 100 MPa or more, the occurrence of shaking of the pressure-sensitive adhesive sheet in the dicing process is further reduced, and the movement of the glass plate on the pressure-sensitive adhesive sheet is suppressed. Can be more effectively suppressed. Moreover, since the storage elastic modulus at 23 ° C. of the substrate is 8000 MPa or less, the pressure-sensitive adhesive sheet has an appropriate elastic modulus, and the glass chip after dicing can be picked up 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

  The base material of the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment is not particularly limited as long as it exhibits a desired function in the process of using the pressure-sensitive adhesive sheet. 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 the above films, a polyethylene terephthalate film is preferably used as the substrate. By using the polyethylene terephthalate film, the above-described storage elastic modulus at 23 ° C. can be easily achieved, occurrence of chipping during dicing can be more effectively suppressed, and good pickup can be performed. 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.

  Although the thickness of a base material is not limited as long as it can function appropriately in the process in which an adhesive sheet is used, it is usually preferred that it is 20-450 micrometers, especially it is preferred that it is 25-300 micrometers, and also 50-200 micrometers. It is preferable that When the thickness of the substrate is 20 μm or more, the occurrence of breakage when handling the pressure-sensitive adhesive sheet is suppressed, and good handling properties can be obtained. Furthermore, the occurrence of shaking of the pressure-sensitive adhesive sheet in the dicing process is further reduced, and the movement of the glass plate on the pressure-sensitive adhesive sheet is suppressed. As a result, the occurrence of chipping and die shift can be more effectively suppressed. On the other hand, a manufacturing cost can be suppressed because the thickness of a base material is 450 micrometers or less. Moreover, it becomes easy to wind up an adhesive sheet in roll shape, and it becomes easy to eliminate curl at the time of use. That is, good handling properties can be obtained during production and use. Furthermore, the base material can be easily deformed according to the operation of the pickup, and the pickup can be performed without requiring excessive force. Therefore, the pickup process can be performed efficiently.

  In addition, it is preferable that the thickness of a base material shall be less than 130 micrometers from a viewpoint of suppressing manufacturing cost further and obtaining the outstanding handling property. Specifically, it is preferably 50 μm or more and less than 130 μm, particularly preferably 70 μm or more and 120 μm or less, and more preferably 80 μm or more and 110 μm or less.

2. Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer provided in the pressure-sensitive adhesive sheet for glass dicing according to this embodiment comprises a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain. It consists of an energy ray-curable adhesive formed from a product.

  In general, the energy ray-curable 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 ester copolymer. What was formed from the pressure-sensitive adhesive composition containing no energy beam curable compound (B) other than the polymer (A) (hereinafter sometimes referred to as “X type” for convenience) and energy beam curability. What was formed from the pressure-sensitive adhesive composition containing the energy-based curable compound (B) other than the acrylic polymer (N) and the (meth) acrylic acid ester copolymer (A) described above (hereinafter, for convenience) And (meth) acrylic acid ester copolymer (A) in which an energy ray curable group is introduced into the side chain, and the (meth) acrylic acid ester copolymer (A ) Or later Of the 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 is made of the above-described X-type or Z-type pressure-sensitive adhesive.

  In the pressure-sensitive adhesive sheet for blade dicing, frictional heat is generated during dicing, and in particular, the portion of the pressure-sensitive adhesive layer that contacts the rotating dicing blade is at a high temperature of about 100 ° C. In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer is made of an X-type or Z-type pressure-sensitive adhesive, and these have a relatively high elastic modulus in the high-temperature state as described above. The reason is that the pressure-sensitive adhesive composition for forming the X-type or Z-type pressure-sensitive adhesive does not contain the low-molecular energy beam curable compound (B) or contains it in a relatively small amount. It is expected to be caused by Such a pressure-sensitive adhesive composition is higher in viscosity than a pressure-sensitive adhesive composition for a Y-type pressure-sensitive adhesive that contains a relatively large amount of the energy beam curable compound (B), and accordingly, It is expected that the modulus of elasticity of the resulting adhesive will be high.

  As described above, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer exhibits a relatively high elastic modulus in a high temperature state, and thus the glass plate attached on the pressure-sensitive adhesive sheet is less likely to shake during dicing. . Therefore, an unintended collision between the cut surface of the glass plate and the dicing blade is suppressed. As a result, the occurrence of chipping during dicing is suppressed. Moreover, the glass plate affixed on the adhesive sheet becomes difficult to move, and dicing into an intended shape with high accuracy becomes possible. That is, the occurrence of die shift is suppressed.

  Of the X-type and Z-type pressure-sensitive adhesives, the X-type pressure-sensitive adhesive exhibits a higher elastic modulus at a high temperature, so that the X-type pressure-sensitive adhesive is effectively suppressed from chipping and die shift. It is preferable to use an agent. On the other hand, when a Z-type pressure-sensitive adhesive is used, the elastic modulus of the pressure-sensitive adhesive layer after irradiation with energy rays becomes higher. Therefore, it is preferable to use a Z-type pressure-sensitive adhesive from the viewpoint of good pickup.

  The (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain may be contained as it is in the pressure-sensitive adhesive layer, or may undergo a crosslinking reaction with a crosslinking agent (C) described later. May be included as a cross-linked product.

(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.

(1-1) Acrylic copolymer (AP)
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 a crosslinking agent (C), 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. Further, when the functional group-containing monomer (A2) and the crosslinking agent (C) are reacted using the crosslinking agent (C), the degree of crosslinking by the crosslinking agent (C), that is, the gel fraction is preferable. 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.

(1-2) Energy ray-curable group-containing compound (A3)
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.

(1-3) Preparation of (meth) acrylic acid ester copolymer (A) in which energy ray curable group is introduced into side chain (meth) acrylic acid ester copolymer in which energy ray curable group is introduced into side chain In preparing the polymer (A), the preparation of the acrylic copolymer (AP) and the reaction between the acrylic copolymer (AP) and the energy ray-curable group-containing compound (A3) are carried out by conventional methods. It can be carried out. 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%.

(1-4) Physical properties of (meth) acrylic acid ester copolymer (A) in which energy ray curable group is introduced into side chain (meth) acrylic acid ester copolymer in which energy ray curable group is introduced into side chain The weight average molecular weight (Mw) of the polymer (A) is preferably 100,000 to 2,500,000, particularly preferably 150,000 to 2,000,000, and more 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) Energy ray curable compound (B)
When the pressure-sensitive adhesive layer in the present embodiment is composed of the above-described Z-type pressure-sensitive adhesive, the pressure-sensitive adhesive composition is a (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain described above. ) Other than the 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 (monofunctional or polyfunctional monomers and oligomers) having an energy ray polymerizable group, specifically, trimethylolpropane triacrylate, Tetramethylol methane 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 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 for forming the pressure-sensitive adhesive layer in the present embodiment is a cross-linking agent capable of cross-linking the (meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced in the side chain ( C) is preferably contained. In this case, the pressure-sensitive adhesive layer in this embodiment contains a cross-linked product obtained by a cross-linking reaction between the (meth) acrylic acid ester copolymer (A) and the cross-linking agent (C). 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.

  The content of the crosslinking agent (C) in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer is based on 100 parts by mass of the (meth) acrylic acid ester copolymer (A) in which the energy ray-curable group is introduced into the side chain. 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass.

(4) Organometallic catalyst (D)
In order to obtain the (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced in the side chain, the acrylic copolymer (AP) and the energy ray curable group-containing compound (A3) are reacted. In the case of making it, the reaction is preferably carried out in the presence of the 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. By reacting in the presence of such an organometallic catalyst (D), the pressure-sensitive adhesive composition containing the (meth) acrylic acid ester copolymer (A) has a high storage elastic modulus at 100 ° C. It becomes possible to form an adhesive layer having an appropriate tack. And when a pressure sensitive adhesive layer exhibits an appropriate tack, a glass plate is appropriately fixed on a pressure sensitive adhesive sheet and chip scattering by dicing is effectively controlled. 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, particularly 0.01 to 5 parts in terms of metal amount, relative to 100 parts by mass of the solid content of the (meth) acrylic acid ester copolymer (A). It is preferable that it is a mass part, and it is further preferable that it is 0.05-3 mass parts. 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 Anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like are exemplified. 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 As energy rays for curing the (meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced in the side chain, ionizing radiation, that is, ultraviolet rays, electron beams And X-rays. 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. The amount of light is appropriately selected according to the type of energy ray-curable group and the thickness of the pressure-sensitive adhesive layer of the (meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced into the side chain. Bayoku, is usually 50 to 500 mJ / cm ² or so, preferably from ^{100~450mJ / cm 2, 200~400mJ / 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 type of energy beam curable group possessed by the (meth) acrylic acid ester copolymer (A) in which the energy beam curable group is introduced into the side chain is used for the acceleration voltage. And the thickness of the pressure-sensitive adhesive layer may be appropriately selected, and it is usually preferably about 10 to 1000 kV. Moreover, what is necessary is just to set the irradiation dose to the range which the said (meth) acrylic acid ester copolymer (A) 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.

(7) Physical properties and shape of pressure-sensitive adhesive layer The storage elastic modulus of the pressure-sensitive adhesive layer at 100 ° C before irradiation with energy rays is preferably 5 to 50 kPa, particularly preferably 7 to 40 kPa, and more preferably 10 to 10 kPa. It is preferable that it is 30 kPa. When the storage elastic modulus is 5 kPa or more, the occurrence of shaking during dicing is further suppressed, and the movement of the glass plate on the adhesive sheet is suppressed. As a result, chipping and die shift are further 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 suppressed. it can. In addition, 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.

  The storage elastic modulus of the pressure-sensitive adhesive layer at 23 ° C. before irradiation with energy rays 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 good adhesive force. In addition, 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 tensile elastic modulus at 23 ° C. after the energy ray irradiation of the pressure-sensitive adhesive layer is preferably 20 to 100 MPa, particularly preferably 25 to 90 MPa, and more preferably 25 to 85 MPa. When the tensile elastic modulus is 20 MPa or more, the glass chip can be favorably picked up after irradiation with energy rays. Moreover, when the tensile elastic modulus is 100 MPa or less, the adhesive strength of the glass dicing pressure-sensitive adhesive sheet is prevented from excessively decreasing, and when the energy beam irradiation is performed before expanding, the chips are scattered during expansion. Can be effectively suppressed. 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 amount of energy (also referred to as “tack value” in the present specification) measured using the probe tack before energy beam irradiation in the pressure-sensitive adhesive layer is preferably 0.01 to 5 mJ / 5 mmφ. It is preferably 13 to 4 mJ / 5 mmφ, and more preferably 0.18 to 3.5 mJ / 5 mmφ. When the tack value is within the above range, occurrence of chip scattering can be effectively suppressed. In addition, in this specification, the tack value is measured under the condition 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 thickness of the pressure-sensitive adhesive layer is preferably 5 to 25 μm, more preferably 7 to 20 μm, particularly preferably 8 to 19 μm, further preferably 9 to 15 μm, and further Is preferably 10 to 12 μm. When the thickness of the pressure-sensitive adhesive layer is 5 μm or more, it is easy to control the adhesive force before energy beam irradiation, and the occurrence of chip scattering, die shift and chipping during dicing can be effectively suppressed. In particular, when the thickness of the pressure-sensitive adhesive layer is 9 μm or more, the occurrence of chip scattering during dicing can be more effectively suppressed. As described above, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer is made of an X-type or Z-type pressure-sensitive adhesive, so that the elastic modulus is higher than that of the Y-type pressure-sensitive adhesive layer. . Therefore, even if the thickness of the pressure-sensitive adhesive layer is 5 μm or more, shaking of the pressure-sensitive adhesive layer and the glass plate during dicing is suppressed well, and the movement of the glass plate on the pressure-sensitive adhesive sheet is suppressed well. In addition, since the thickness of the pressure-sensitive adhesive layer is 25 μm or less, the occurrence of shaking of the pressure-sensitive adhesive layer during dicing is further reduced, and the movement of the glass plate on the pressure-sensitive adhesive sheet is suppressed. Generation | occurrence | production can be suppressed more effectively.

  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.

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 Before applying energy rays to the pressure-sensitive adhesive sheet for glass dicing according to this embodiment, the surface of the pressure-sensitive adhesive layer opposite to the base material is pasted on an alkali-free glass and allowed to stand for 20 minutes. Is preferably 5,000 to 25000 mN / 25 mm, particularly preferably 9000 to 22000 mN / 25 mm, and more preferably 9500 to 18000 mN / 25 mm. It becomes possible to hold | maintain a glass chip and a glass plate favorably on an adhesive sheet in the case of dicing because the adhesive force before energy ray irradiation is 5000 mN / 25mm or more. As a result, the deviation of the glass chip and the glass plate on the adhesive sheet is suppressed, and the occurrence of chipping and die shift is effectively suppressed. Furthermore, since the glass chip is satisfactorily held on the adhesive sheet during dicing, the occurrence of chip scattering is also suppressed. On the other hand, when the adhesive strength before irradiation with energy rays is 25000 mN / 25 mm or less, the adhesive strength after irradiation with energy rays is easily lowered until the adhesive strength is easy to pick up.

  The surface of the pressure-sensitive adhesive layer opposite to the base material is affixed to non-alkali glass, and the pressure-sensitive adhesive layer is irradiated with energy rays. The adhesive force is preferably 50 to 250 mN / 25 mm, particularly preferably 60 to 160 mN / 25 mm, and further preferably 70 to 130 mN / 25 mm. Since the adhesive strength after irradiation with energy rays is 50 mN / 25 mm or more, the glass chip can be prevented from unintentionally peeling or shifting from the adhesive sheet before the glass chip is picked up from the adhesive sheet. . On the other hand, when the adhesive force after irradiation with energy rays is 250 mN / 25 mm or less, for example, when individually picking up glass chips after cutting, the glass chips can be favorably picked up without being damaged.

  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. Generally, during dicing, frictional heat is generated by contact between the pressure-sensitive adhesive layer and the dicing blade, and the pressure-sensitive adhesive layer is heated to a high temperature state of about 100 ° C. Here, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer contains a (meth) acrylic acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain. Since it is made of a pressure-sensitive adhesive formed from an object, the pressure-sensitive adhesive layer exhibits a relatively high elastic modulus at such a high temperature state. Therefore, at the time of dicing, the glass plate affixed on the adhesive sheet becomes difficult to shake, and unintended collision between the cut surface of the glass plate and the dicing blade and movement of the glass plate on the adhesive sheet are suppressed. For this reason, according to the adhesive sheet for glass dicing which concerns on this embodiment, it can dice, suppressing generation | occurrence | production of the chipping and die shift at the time of dicing.

  After completion of the dicing step, energy beam irradiation is performed from the glass chip side surface or the substrate side surface to the adhesive sheet to which the plurality of glass chips are attached. As a result, the polymerization reaction of the energy ray curable group of the (meth) acrylic acid ester copolymer (A) in which the energy ray curable group is introduced into the side chain proceeds to reduce the adhesiveness, and the subsequent pick-up step It becomes easy to do.

  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 addition, you may 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.

  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, since the pressure-sensitive adhesive layer is relatively hard as described above, even a thin glass with a thickness of 50 μm can be diced while suppressing the occurrence of chipping. .

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 adhesive sheet for glass dicing which concerns on this embodiment, even if it is a small glass chip which has an area of the said range, it can obtain, suppressing generation | occurrence | production of the chipping and die shift at the time of dicing.

  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 acid ester copolymer (A) in which an energy ray-curable group is introduced into the side chain 75 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of methyl methacrylate, and acrylic acid 2 -Acrylic copolymer (AP) was obtained by copolymerizing with 15 parts by mass of hydroxyethyl. 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 14]
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 Example 1]
(1) Preparation of pressure-sensitive 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) having no energy beam curability. When the molecular weight of the obtained polymer (N) was measured, the weight average molecular weight (Mw) was 600,000.

  100 parts by mass of the acrylic polymer (N) obtained as described above and having no energy beam curability and a trifunctional urethane acrylate oligomer (product name, manufactured by Dainichi Seika Kogyo Co., Ltd.) as the energy beam curable compound (B) 127 parts by mass of “EXL810TL”, Mw = 5000), 4 parts by mass of α-hydroxycyclohexyl phenyl ketone (manufactured by BASF, product name “Irgacure 184”) as a photopolymerization initiator, and trimethylolpropane modification as a crosslinking agent 11 parts by mass of tolylene diisocyanate (manufactured by Tosoh Corporation, product name “Coronate L”) was mixed in a solvent to obtain a coating solution of the pressure-sensitive adhesive composition. In addition, a Y type adhesive is obtained by using this adhesive composition.

(2) Production of pressure-sensitive adhesive sheet for glass dicing A pressure-sensitive adhesive sheet for glass dicing was produced in the same manner as in Example 1 except that the coating solution of the pressure-sensitive adhesive composition obtained in the above step (1) was used.

[Comparative Example 2]
(1) Preparation of pressure-sensitive adhesive composition An acrylic polymer having no energy ray curability by copolymerizing 50 parts by mass of 2-ethylhexyl acrylate, 40 parts by mass of methyl acrylate, and 10 parts by mass of acrylic acid. (N) was obtained. When the molecular weight of the obtained polymer (N) was measured, the weight average molecular weight (Mw) was 800,000.

  100 parts by mass of the acrylic polymer (N) obtained as described above and having no energy beam curability, and a 10-functional urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name “ UV-1700B ”, molecular weight: 1700) 40 parts by mass, 0.1 part by mass of α-hydroxycyclohexyl phenyl ketone (manufactured by BASF, product name“ Irgacure 184 ”) as a photopolymerization initiator, and tri 10 parts by mass of methylolpropane-modified tolylene diisocyanate (manufactured by Tosoh Corporation, product name “Coronate L”) was mixed in a solvent to obtain a coating solution of the pressure-sensitive adhesive composition. In addition, a Y type adhesive is obtained by using this adhesive composition.

(2) Production of pressure-sensitive adhesive sheet for glass dicing A pressure-sensitive adhesive sheet for glass dicing was produced in the same manner as in Example 1 except that the coating solution of the pressure-sensitive adhesive composition obtained in the above step (1) was used.

[Comparative Examples 3 and 4]
A glass dicing pressure-sensitive adhesive sheet was produced in the same manner as in Comparative Example 2 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 (product name “A-4100” manufactured by Toyobo Co., Ltd.)
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 (Toyochem, “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 , UV (UV) irradiation (illuminance: 230 mW / cm ² , light amount: 190 mJ / cm ² ) was performed using an ultraviolet 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 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 )

After completion of the dicing, the presence and absence of the chipping at the end and the shape of the glass chip located in the center of the pressure-sensitive adhesive sheet for glass dicing and in the vicinity thereof were observed. 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.

  As can be seen from Table 1, the pressure-sensitive adhesive sheet according to the example can suppress chipping and die shift.

  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 (11)

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 pressure-sensitive adhesive layer is made of an energy ray-curable 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. An adhesive sheet for glass dicing characterized by the above.   The pressure-sensitive adhesive composition for glass dicing according to claim 1, wherein the pressure-sensitive adhesive composition further contains an energy ray-curable compound (B) other than the (meth) acrylic acid ester copolymer (A). .   The pressure-sensitive adhesive composition for glass dicing according to claim 1 or 2, wherein the pressure-sensitive adhesive composition further contains a crosslinking agent (C).   The pressure-sensitive adhesive sheet for glass dicing according to any one of claims 1 to 3, wherein a storage elastic modulus at 100 ° C of the pressure-sensitive adhesive layer before irradiation with energy rays is 5 to 50 kPa.   The adhesive strength of the pressure-sensitive adhesive layer to the alkali-free glass before irradiation with energy rays of the pressure-sensitive adhesive sheet for glass dicing after sticking the surface of the pressure-sensitive adhesive layer opposite to the base material to alkali-free glass and allowing it to stand for 20 minutes is The glass dicing pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive sheet is 5000 to 25000 mN / 25 mm.   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. A pressure is 50-250mN / 25mm, The adhesive sheet for glass dicing as described in any one of Claims 1-5 characterized by the above-mentioned.   The pressure-sensitive adhesive sheet for glass dicing according to any one of claims 1 to 6, wherein the base material has a storage elastic modulus at 23 ° C of 100 to 8000 MPa.   The glass dicing pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein a glass having a thickness of 50 to 10000 µm is used as a workpiece. A glass plate, glass dicing according to any one of claims 1 to 8, characterized in that for dicing glass chip plane having an area of 1 × 10 ^-6 mm ² ~1mm ² Adhesive sheet. 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;
By reacting the functional group-containing monomer (A2) with a functional group capable of reacting with the functional group and an energy ray-curable group-containing compound (A3) having an energy ray-curable carbon-carbon double bond, 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 10, wherein the method is performed in the presence of at least one organometallic catalyst (D).