TWI811187B - Adhesive sheet for glass cutting and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide an adhesive plate for glass cutting that is less prone to chipping and crystal pushing even when a thin glass plate is cut into small wafers, and a manufacturing method thereof.

The solution of the present invention is an adhesive sheet for glass cutting, which is an adhesive sheet for glass cutting including a base material and an adhesive layer laminated on at least one surface of the base material, and the adhesive layer is It consists of an energy ray curable adhesive composed of an adhesive composition containing a (meth)acrylate copolymer (A) with an energy ray curable group introduced into the side chain.

Description

Adhesive plate for glass cutting and manufacturing method thereof

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

When manufacturing camera modules for mobile phones and smartphones, tiny pieces of glass are needed. Such a glass sheet is obtained by cutting a glass plate using a cutting plate. That is, after the glass plate is attached to the cutting plate, the glass is cut with a cutting blade to obtain individual pieces of glass (hereinafter sometimes referred to as "glass wafers"). In recent years, as smartphones and the like have become thinner and the camera modules mounted thereon have also been miniaturized, there has been a need to manufacture thinner microglass wafers (hereinafter sometimes referred to as "small wafers").

When cutting brittle materials such as glass, chipped corners are prone to occur. The so-called missing corner here means that the end or cutting surface of the glass wafer is defective during cutting. The thinner the thickness of the glass plate, the more markedly chipping occurs.

Patent Document 1 discloses an adhesive plate for cutting glass substrates in which an adhesive layer is provided on a base film. Patent Document 1 discloses that using a film with a thickness of 130 μm or more and a tensile elastic modulus of 1 GPa or more as the base film, and further making the thickness of the adhesive layer 9 μm or less can reduce the pressure on the adhesive plate due to the cutting blade. deformation, thereby suppressing chipping (paragraph 0010 of Patent Document 1).

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent No. 3838637

The adhesive plate disclosed in Patent Document 1 uses a relatively thick glass plate with a thickness of 1 mm as the cutting object (paragraph 0059 of Patent Document 1). However, when using this adhesive plate to cut thinner glass plates required in recent years, chipping cannot be sufficiently suppressed.

In addition, as glass wafers become smaller, a problem called die shift becomes more likely to occur. When manufacturing small wafers, the contact area between the glass wafer and the adhesive plate becomes smaller, making it easier for the glass plate or the glass wafer to shift on the adhesive plate due to cutting vibration. If crystal pushing occurs, cutting cannot be performed at the target position, and a glass wafer having a desired shape cannot be obtained.

The present invention was completed in view of the above-mentioned actual situation, and aims to provide an adhesive plate for glass cutting that is less likely to cause chipping and crystal pushing even when a thin glass plate is cut into small wafers, and a manufacturing method thereof.

In order to achieve the above object, first, the present invention provides an adhesive sheet for glass cutting, which is an adhesive sheet for glass cutting including: a base material; and an adhesive layer laminated on at least one surface of the base material, It is characterized in that the above-mentioned adhesive layer is composed of an energy ray curable adhesive composed of an adhesive composition containing a (meth)acrylate copolymer (A) with an energy ray curable group introduced into the side chain. Composition (Invention 1).

According to the above invention (Invention 1), when the temperature of the adhesive layer reaches a high temperature of about 100°C due to frictional heat during cutting, the adhesive layer exhibits a relatively high elastic modulus, so that shaking during cutting can be fully controlled. , as a result of suppressing the displacement of the glass plate on the adhesive plate, even when cutting a thin glass plate into small wafers, the occurrence of chipping and crystal pushing can be suppressed.

In the above invention (Invention 1), it is preferable that the above-mentioned adhesive composition further contains an energy ray curable compound (B) other than the above-mentioned (meth)acrylate copolymer (A) (Invention 2).

In the above inventions (Inventions 1 and 2), it is preferred that the adhesive composition further contains a bridging agent (C) (Invention 3).

In the above inventions (Inventions 1 to 3), the storage elastic modulus of the adhesive layer at 100°C before irradiation with energy rays is preferably 5 to 50 kPa (Invention 4).

In the above inventions (Inventions 1 to 4), the surface of the adhesive layer opposite to the base material is adhered to the alkali-free glass, and after leaving it to stand for 20 minutes, the adhesive plate for glass cutting is placed before irradiating energy rays. The adhesion force to the above-mentioned alkali-free glass is preferably 5000~25000mN/25mm (Invention 5).

In the above inventions (Inventions 1 to 5), the surface of the adhesive layer opposite to the base material is adhered to alkali-free glass, and the adhesive layer is irradiated with energy rays, and the adhesive plate for glass cutting is The adhesion force to the above-mentioned alkali-free glass is preferably 50~250mN/25mm (Invention 6).

In the above inventions (Inventions 1 to 6), the storage elastic modulus of the base material at 23°C is preferably 100 to 8000 MPa (Invention 7).

In the above-mentioned inventions (Inventions 1 to 7), glass with a thickness of 50 to 10,000 μm is used. Glass is preferred as the workpiece (Invention 8).

In the above-mentioned inventions (Inventions 1 to 8), it is preferable that the glass plate is cut into glass wafers having a flat surface area of 1×10 ^-6 mm ² to 1 mm ² (Invention 9).

Secondly, the present invention provides a method for manufacturing an adhesive plate for glass cutting, which is characterized by comprising: combining at least alkyl (meth)acrylate monomer (A1) and a functional group-containing material having a reactive functional group. An acrylic copolymer (AP) copolymerized with the monomer (A2), bonded with a carbon-carbon double bond having a substituent capable of reacting with the functional group of the above-mentioned functional group-containing monomer (A2) and energy ray curability The step of reacting a compound (A3) containing an energy ray curable group to prepare a (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain; and using the (meth)acrylate copolymer containing the The step of laminating an adhesive layer on at least one surface of the base material using the adhesive composition of object (A) (Invention 10).

In the above invention (Invention 10), the above acrylic copolymer (AP) and the above energy ray curable group-containing compound (A3) are reacted so as to react with a compound selected from the group consisting of an organic compound containing zirconium, an organic compound containing titanium, and an organic compound containing titanium. It is preferable to carry out in the presence of at least one organometallic catalyst (D) which is an organic compound of tin (Invention 11).

According to the adhesive sheet for glass cutting of the present invention and the adhesive sheet for glass cutting produced by the manufacturing method of the present invention, even when a thin glass plate is cut into small wafers, chipping and pushing are less likely to occur. crystal.

Hereinafter, embodiments of the present invention will be described.

The adhesive plate for glass cutting according to this embodiment (hereinafter, may only be referred to as an "adhesive plate") is composed of a base material and an adhesive layer laminated on one surface of the base material.

1.Substrate

Regarding the adhesive plate for glass cutting according to this embodiment, the storage elastic modulus of the base material at 23°C is preferably 100 to 8000 MPa, particularly preferably 1500 to 7000 MPa, and further preferably 2000 to 6000 MPa. By making the storage elastic modulus of the base material at 23°C above 100MPa, the shaking of the adhesive plate during the cutting step can be further reduced, and the displacement of the glass plate on the adhesive plate can be suppressed, which can more effectively suppress the occurrence of chipped corners and Push the crystal. In addition, by setting the storage elastic modulus of the base material at 23°C to 8000 MPa or less, the adhesive plate has a moderate elastic modulus and can pick up the cut glass wafers well. In addition, the storage elastic modulus of the base material at 23°C was measured under the following conditions using a dynamic elastic modulus measuring device (manufactured by TA INSTRUMENT, product name "DMAQ800").

Test starting temperature: 0℃

Test end temperature: 200℃

Heating rate: 3℃/min

Frequency: 11Hz

Amplitude: 20μm

Regarding the base material of the adhesive plate for glass cutting according to this embodiment, its constituent material is not particularly limited as long as it performs a desired function in the step of using the adhesive plate. The base material may be a film (resin film) containing a resin-based material as a main material. It is preferable that the base material consists only of a resin film. Specific examples of the resin film include ethylene-vinyl acetate copolymer film, ethylene-(meth)acrylic acid Ethylene-based copolymer films such as copolymer films and ethylene-(meth)acrylate copolymer films; polyethylene films, polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, ethylene films -Polyolefin-based films such as norbornene copolymer films and norbornene resin films; polyvinyl chloride-based films such as polyvinyl chloride films and vinyl chloride copolymer films; polyethylene terephthalate films, polyethylene terephthalate films, etc. Polyester films such as butylene terephthalate film; polyurethane film; polyimide film; polystyrene film; polycarbonate film; fluororesin film, etc. Examples of polyethylene films include low-density polyethylene (LDPE) films, linear low-density polyethylene (LLDPE) films, high-density polyethylene (HDPE) films, and the like. In addition, modified films such as these bridge films and ionic polymer films can also be used. The base material may be a film composed of one of these, or a film in which two or more of these are combined and laminated. As the base material, among the above-mentioned films, a polybutylene terephthalate film is preferably used. By using polybutylene terephthalate film, it is easy to achieve the above-mentioned storage elastic modulus at 23°C, which can more effectively suppress chipping during cutting and enable good pick-up. In addition, "(meth)acrylic acid" in this specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.

The base material and the film may contain various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, smoothing agents, and fillers. Examples of pigments include titanium dioxide, carbon black, and the like. Examples of the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. Although the content of these additives is not particularly limited, it is preferably within a range in which the desired function for the base material can be exerted without loss of smoothness and softness.

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

In order to improve the adhesion with the adhesive layer, surface treatments such as primer treatment, corona treatment, plasma treatment, and roughening treatment (matte processing) can be applied to the surface of the base material on the adhesive layer side. Examples of the roughening treatment include embossing, sandblasting, and the like. In addition, various coating films may be provided on the surface opposite to the base material and the adhesive layer.

The thickness of the substrate is not limited as long as it can be used appropriately during the step of using the adhesive plate. Generally, 20 to 450 μm is preferred, 25 to 300 μm is particularly preferred, and 50 to 200 μm is further preferred. By setting the thickness of the base material to 20 μm or more, breakage during handling of the adhesive plate can be suppressed and good workability can be achieved. Furthermore, it can further reduce the shaking of the adhesive plate during the cutting step, suppress the displacement of the glass plate on the adhesive plate, and more effectively suppress the occurrence of chipping and crystal pushing. On the other hand, by setting the thickness of the base material to 450 μm or less, manufacturing costs can be suppressed. In addition, the adhesive sheet can be easily rolled into a roll and can be easily uncurled during use. That is, good operability can be obtained during production and use. Furthermore, the substrate becomes easily deformed in accordance with the picking action and can be picked up without undue force. Therefore, the picking step can be performed efficiently.

Furthermore, from the viewpoint of further suppressing manufacturing costs and obtaining better workability, the thickness of the base material is preferably less than 130 μm. Specifically, it is preferably from 50 μm to less than 130 μm, particularly preferably from 70 μm to 120 μm, and further preferably from 80 μm to 110 μm.

2. Adhesive layer

The adhesive layer of the adhesive plate for glass cutting according to this embodiment is composed of an energy-containing adhesive composition containing a (meth)acrylate copolymer (A) with an energy-beam-curing group introduced into the side chain. Made of linear hardening adhesive.

Generally speaking, energy ray curable adhesives include: (meth)acrylate copolymer (A) containing side chains with energy ray curable groups introduced therein, excluding the (meth)acrylate copolymer (A) ) is formed of an adhesive composition of an energy ray curable compound (B) other than the energy ray curable compound (B) (hereinafter, sometimes conveniently referred to as "X type".); composed of an acrylic polymer (N) that does not have energy ray curable properties. ) and an adhesive composition of an energy ray curable compound (B) other than the above-mentioned (meth)acrylate copolymer (A) (hereinafter, sometimes conveniently referred to as "Y type"); and Adhesive composition containing a (meth)acrylate copolymer (A) with an energy ray curable group introduced into the side chain and an energy ray curable compound (B) other than the (meth)acrylate copolymer (A) What is formed (hereinafter, sometimes conveniently referred to as "Z-shaped".). In the adhesive plate for glass cutting according to this embodiment, the adhesive layer is composed of the above-mentioned X-type or Z-type adhesive.

Adhesive plates used for blade cutting will generate frictional heat during cutting. Especially in the adhesive layer, the part in contact with the rotating cutting blade will become a high temperature state of about 100°C. In the adhesive plate for glass cutting according to this embodiment, the adhesive layer is composed of the above-mentioned X-type or Z-type adhesive. In the above-mentioned high-temperature state, the adhesive layer shows a relatively high elastic modulus. . The reason for this is presumably because the adhesive composition used to form the X-type or Z-type adhesive does not contain the low-molecular energy ray curable compound (B) or contains a relatively small amount. It can be speculated that such adhesive compositions are used for applications containing relatively large amounts of energy. Compared with the Y-type adhesive composition of the linear curable compound (B), the viscosity is high, and with this, the elastic modulus of the resulting adhesive becomes high in a high-temperature state.

As described above, in the adhesive plate for glass cutting according to this embodiment, since the adhesive layer exhibits a high elastic modulus at a high temperature, the glass plate adhered to the adhesive plate is less likely to shake during cutting. Therefore, unintentional collision between the cutting surface of the glass plate and the cutting blade can be suppressed. As a result, chipping during cutting can be suppressed. In addition, the glass plate attached to the adhesive plate becomes less likely to move, so it can be cut into the desired shape with high precision. This can inhibit the occurrence of crystal pushing.

Furthermore, among the X-type and Z-type adhesives, since the X-type adhesive shows a higher elastic modulus at high temperatures, the X-type adhesive is used from the perspective of effectively suppressing chipping and crystal pushing. Better. On the other hand, when using a Z-type adhesive, the elastic modulus of the adhesive layer after irradiation with energy rays will become higher. Therefore, from the viewpoint of good pickup, it is better to use a Z-type adhesive.

The (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain can be directly contained in the adhesive layer, or it can be contained in a bridged product through a bridge reaction with a bridge agent (C) described below.

(1) (Meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain

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

(1-1) Acrylic copolymer (AP)

Acrylic copolymer (AP) copolymerized with at least alkyl (meth)acrylate monomer (A1) and functional group-containing monomer (A2) having a reactive functional group Better.

The alkyl (meth)acrylate monomer (A1) preferably has an alkyl group having 1 to 18 carbon atoms, and particularly preferably one having a carbon number of 1 to 4. Specific examples of the (meth)acrylic acid alkyl ester monomer (A1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, ( Lauryl methacrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, etc. These can be used individually or in combination of 2 or more types.

The mass ratio of the structural part derived from the alkyl (meth)acrylate monomer (A1) to the total mass of the acrylic copolymer (AP) is preferably 50 to 98 mass %, particularly 60 to 95 mass %. The best is 70~90% by mass.

The functional group-containing monomer (A2) has a reactive functional group that can react with the functional group of the energy ray curable group-containing compound (A3). The functional group of the functional group-containing monomer (A2) includes, for example, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, an epoxy group, and the like. Among them, a hydroxyl group and a carboxyl group are preferred, and a hydroxyl group is particularly preferred. Furthermore, when a bridging agent (C) is used, the reactive functional group of the functional group-containing monomer (A2) can also react with the bridging agent (C).

When a monomer having a hydroxyl group (containing hydroxyl monomer) is used as the functional group-containing monomer (A2), an example thereof is hydroxyalkyl (meth)acrylate, and a specific example thereof is (meth)acrylic acid. 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. It deserves Among them, 2-hydroxyethyl (meth)acrylate is preferred due to its reactivity and copolymerizability of hydroxyl groups. These can be used individually or in combination of 2 or more types.

When a monomer having a carboxyl group (carboxyl group-containing monomer) is used as the functional group-containing monomer (A2), examples thereof include ethylenically unsaturated carboxylic acid, and specific examples thereof include acrylic acid, methacrylic acid, and crotonic acid. , maleic acid, itaconic acid, citraconic acid, etc. Among these, acrylic acid is preferred due to its reactivity and copolymerizability of the carboxyl group. These can be used individually or in combination of 2 or more types.

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

The mass ratio of the structural part derived from the functional group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is preferably 5 to 40 mass %, particularly preferably 7 to 35 mass %, and further preferably 10 mass %. ~30% by mass is preferred. By setting the mass ratio of the structural moiety derived from the functional group-containing monomer (A2) within the above range, the (methyl) group of the energy ray curable group can be introduced into the side chain of the energy ray curable group-containing compound (A3). The introduction amount of the acrylate copolymer (A) is within a favorable range. In addition, when the bridging agent (C) is used to react the functional group-containing monomer (A2) with the bridging agent (C), the bridging degree of the bridging agent (C), that is, the gel fraction can be within a good range. Physical properties such as the cohesion of the adhesive layer can be controlled.

The acrylic copolymer (AP) consists of the monomers plus the above-mentioned (meth)acrylic acid alkyl ester monomer (A1) and the functional group-containing monomer (A2), and may also contain other monomers.

Examples of the other monomer include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and (meth)acrylate. (Meth)acrylate containing alkoxyalkyl groups such as ethoxyethyl acrylate; (meth)acrylate having an aliphatic ring such as cyclohexyl (meth)acrylate; (Meth) (meth)acrylates with aromatic rings such as phenyl acrylate; non-bridging acrylamide such as acrylamide and methacrylamide; (meth)acrylic acid N,N-dimethylamino group (meth)acrylates with non-bridging tertiary amine groups such as ethyl ester and N,N-dimethylaminopropyl (meth)acrylate; vinyl acetate; styrene, etc. These can be used individually or in combination of 2 or more types.

The polymerization state of acrylic copolymer (AP) can be a random copolymer or a block copolymer. In addition, the polymerization method is not particularly limited, and a general polymerization method can be used.

(1-2) Compound (A3) containing an energy ray curable group

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

Examples of functional groups that react with the functional group of the functional group-containing monomer (A2) include an isocyanate group, an epoxy group, and the like. Among them, an isocyanate group having high reactivity with a hydroxyl group is preferred.

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

Examples of the compound (A3) containing an energy ray curable group include 2-methacryloxyethyl isocyanate, o-isopropenyl-α,α-dimethylbenzyl isocyanate, methacrylyl isocyanate, Allyl isocyanate, 1,1-(bispropene Acryloxymethyl)ethyl isocyanate; diisocyanate compound or polyisocyanate compound, acrylyl monoisocyanate compound obtained by reacting with hydroxyethyl (meth)acrylate; diisocyanate compound or polyisocyanate compound, and polyol compound , and acrylyl monoisocyanate compounds obtained by the reaction of hydroxyethyl (meth)acrylate, etc. Among these, 2-methacryloyloxyethyl isocyanate is particularly preferred. In addition, the energy ray curable group-containing compound (A3) may be used alone or in combination of two or more types.

(1-3) Preparation of (meth)acrylate copolymer (A) in which energy ray curable groups are introduced into the side chain

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

In the (meth)acrylate copolymer (A) having an energy ray curable group introduced into the side chain, the amount of the energy ray curable group-containing compound (A3) relative to the reactivity of the functional group-containing monomer (A2) The amount of functional groups 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)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain

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

(2) Energy ray curable compound (B)

When the adhesive layer of this embodiment is composed of the above-mentioned Z-type adhesive, the adhesive composition contains an energy-beam-curable material other than the (meth)acrylate copolymer (A) in which energy-ray-curable groups are introduced into the side chain. Sexual compound (B).

The energy ray curable compound (B) is a compound that polymerizes and hardens 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 can be used. , tetramethylolmethane tetraacrylate, neopentylerythritol triacrylate, dineopenterythritol monohydroxypentacrylate, dineopenterythritol hexaacrylate, 1,4-butanediol diacrylate, 1 , Acrylates such as 6-hexanediol diacrylate, acrylates containing a cyclic aliphatic skeleton such as dicyclopentadiene dimethoxy diacrylate, isobornyl acrylate, etc., polyethylene glycol diacrylate Acrylate compounds such as ester, oligoester acrylate, urethane acrylate oligomer, epoxy modified acrylate, polyether acrylate, and itaconic acid oligomer. Such compounds have energy line-hardening double bonds within the molecule, and usually have a molecular weight of 100 to 30,000. The best value is around 300~10,000.

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

(3)Bridging agent (C)

The adhesive composition formed in the adhesive layer of this embodiment preferably contains a bridging agent (C) capable of bridging the (meth)acrylate copolymer (A) having an energy ray curable group introduced into the side chain. At this time, the adhesive agent of this embodiment contains a bridge|crosslinking material obtained by the bridge|crossing reaction of this (meth)acrylate copolymer (A) and the bridge|crossing agent (C). By using this bridging agent (C), the gel fraction of the adhesive forming the adhesive layer can be easily adjusted to a good range, and physical properties suitable for cutting can be obtained.

Examples of the bridging agent (C) include polyimine compounds such as epoxy compounds, polyisocyanate compounds, metal chelate compounds, and ethylenimine compounds, melamine resins, and urea resins. , dialdehydes, hydroxymethyl polymers, metal alkoxy compounds, metal salts, etc. Among these, it is preferable to use an epoxy compound or a polyisocyanate compound for the reason that it is easy to control a cross-linking reaction, and it is particularly preferable to use a polyisocyanate compound.

Epoxy compounds include, for example, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl m-xylylene Amine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine, etc.

The polyisocyanate compound is a compound having two or more isocyanate groups per molecule. Specific examples include aromatic polyisocyanates such as tonylene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate, and Hydroxylyl diisocyanate and other alicyclic polyisocyanates. Further examples include these biurets, isocyanurates, adducts, and the like. Examples of the adduct include reaction products with compounds containing low-molecular active hydrogen such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.

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

The content of the bridging agent (C) in the adhesive composition forming the adhesive layer is 0.01 to 15 parts by mass relative to 100 parts by mass of the (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain. Preferably, 0.05 to 10 parts by mass is particularly preferred, and 0.1 to 2 parts by mass is more preferred.

(4)Organometallic catalyst (D)

In order to obtain a (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain, when the acrylic copolymer (AP) and the compound (A3) containing an energy ray curable group are reacted, the reaction is: It is better to carry out in the presence of organometallic catalyst (D). The organic metal catalyst (D) is preferably at least one selected from the group consisting of zirconium-containing organic compounds, titanium-containing organic compounds, and tin-containing organic compounds. By reacting in the presence of such an organic metal catalyst (D), an adhesive composition containing the (meth)acrylate copolymer (A) is obtained, which can form a high storage elastic modulus at 100°C and perform appropriately. sticky adhesive layer. Then, the glass plate is properly fixed to the adhesive plate through the adhesive layer exerting appropriate viscosity. to effectively prevent wafers from flying due to cutting. As the organometallic catalyst (D), among the above three types of organic compounds, at least one of an organic compound containing zirconium and an organic compound containing titanium is preferred, and an organic compound containing zirconium is particularly preferred.

Examples of the form of the organic compound include an alkoxy compound, a chelate compound, a chelate compound, and the like, and among these, a chelate compound is preferred.

Specific examples of the organic metal catalyst (D) include zirconium alkoxy compounds, zirconium chelate compounds, titanium alkoxy compounds, titanium chelate compounds, tin alkoxy compounds, tin chelate compounds, and the like. Among these, zirconium chelate is preferred. The organometallic catalyst (D) may be composed of one type of these compounds, or may be composed of two or more types of these compounds.

The amount of the organic metal catalyst (D) used in the reaction to obtain the (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain is not limited. The usage amount is preferably 0.001 to 10 parts by mass in terms of metal content relative to 100 parts by mass of the solid content of the (meth)acrylate copolymer (A), particularly preferably 0.01 to 5 parts by mass, and further preferably 0.05 to 0.05 parts by mass. 3 parts by mass is optimal. In addition, in the present invention, the metal amount conversion refers to the blending amount or blending ratio calculated from only the mass of the metal in the organic metal catalyst (D), excluding the mass corresponding to the molecular weight of the structure constituting the organic substance.

(5)Other ingredients

The adhesive composition formed in the adhesive layer of this embodiment may contain, in addition to the above-mentioned components, a photopolymerization initiator, a bridge accelerator, coloring materials such as dyes or pigments, a flame retardant, a filler, and an antistatic agent. and various additives.

Photopolymerization initiator, such as benzoin compounds and acetophenone compounds Photoinitiators such as compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, etc., photosensitizers such as amines or quinones, etc. Specific examples include α-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethylthiuram sulfide, azobisisobutyronitrile, and Benzyl, diacetyl, β-chloroanthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. When using ultraviolet rays as energy rays, the irradiation time and amount can be reduced by formulating a photopolymerization initiator.

When the adhesive composition formed in the adhesive layer of this embodiment contains a bridge agent (C), an appropriate bridge accelerator may be included according to the type of the bridge agent (C).

(6)Irradiation of energy rays

Examples of energy rays used for hardening the (meth)acrylate copolymer (A) in which an energy ray curable group has been introduced into the side chain include ionizing radiation, that is, ultraviolet rays, electron beams, and X-rays. Among them, ultraviolet rays that are relatively easy to be introduced by irradiation equipment are preferred.

When using ultraviolet rays as ionizing radiation, it is preferable to use near ultraviolet rays including ultraviolet rays with a wavelength of approximately 200 to 380 nm due to ease of operation. The amount of light can be appropriately selected according to the type of energy ray curable group of the (meth)acrylate copolymer (A) having an energy ray curable group introduced into the side chain or the thickness of the adhesive layer. It is usually 50 to 500 mJ. /cm ² , preferably 100~450mJ/ ^cm2 , and 200~400mJ/ ^cm2 even better. In addition, the ultraviolet illumination is usually about 50~500mW/ ^cm2 , with 100~450mW/ ^cm2 being preferred, and 200~400mW/ ^cm2 being more preferred. The ultraviolet source is not particularly limited. For example, high-pressure mercury lamps, metal halide lamps, UV-LEDs, etc. can be used.

When using electron beams as ionizing radiation, regarding its accelerating electric The voltage can be appropriately selected according to the type of energy ray curable group of the (meth)acrylate copolymer (A) having an energy ray curable group introduced into the side chain or the thickness of the adhesive layer. Generally, the acceleration voltage is 10~1000kV. In addition, the irradiation dose should be set in a range in which the (meth)acrylate copolymer (A) can be appropriately cured, and is usually selected in the range of 10 to 1000 krad. The electron beam source is not particularly limited and may be Cockcroft-Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, or linear type. , Dynamitron type, high frequency type, etc. various electron beam accelerators.

(7) Physical properties and shape of the adhesive layer

The storage elastic modulus of the adhesive layer at 100°C before irradiation with energy rays is preferably 5 to 50 kPa, particularly preferably 7 to 40 kPa, and further preferably 10 to 30 kPa. By setting the storage elastic modulus to 5 kPa or more, shaking during cutting can be further suppressed, and the resultant displacement of the glass plate on the adhesive plate can be suppressed, making chipping and crystal pushing less likely to occur. In addition, by setting the storage elastic modulus to 50 kPa or less, the elastic modulus of the adhesive layer does not become extremely high, and good adhesion can be obtained. As a result, wafer scattering during dicing can be suppressed. In addition, the method for measuring the storage elastic modulus of the adhesive layer at 100°C before irradiation with energy rays is as shown in the test example described below.

The storage elastic modulus of the 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. By setting the elastic modulus within the above range, the adhesive sheet for glass cutting can exhibit good adhesive force. Furthermore, the method for measuring the storage elastic modulus of the adhesive layer at 23°C before irradiation with energy rays is as follows: Example shown.

After the adhesive layer is irradiated with energy rays, the tensile elastic modulus at 23°C is preferably 20~100MPa, particularly preferably 25~90MPa, and further preferably 25~85MPa. By setting the tensile elastic modulus to 20 MPa or more, the glass wafers irradiated with energy rays can be favorably picked up. In addition, by setting the tensile elastic modulus to 100 MPa or less, the adhesive force of the adhesive plate for glass cutting can be suppressed from excessively decreasing, and when energy rays are irradiated before expansion, the occurrence of errors during expansion of the wafer can be effectively suppressed. In addition, the method of measuring the tensile elastic modulus at 23°C of the adhesive layer before irradiation with energy rays is as shown in the test example described below.

為佳，以0.13~4mJ/5mm

特別佳，進一步以0.18~3.5mJ/5mm

為佳。藉由使黏性值在上述範圍，可有效地抑制發生晶片飛散。再者，在本說明書，黏性值係以JIS Z0237：2009所記載的方法，將剝離速度變更為1mm/分的條件測定，詳細情況係如後述的試驗例所示。 On the adhesive layer, use a probe tack to measure the energy before irradiating the energy ray (referred to as "viscosity value" in this manual.), with a value of 0.01~5mJ/5mm.

It is better to use 0.13~4mJ/5mm

Especially good, further with 0.18~3.5mJ/5mm

Better. By setting the viscosity value within the above range, the occurrence of chip scattering can be effectively suppressed. In addition, in this specification, the viscosity value is measured according to the method described in JIS Z0237:2009, with the peeling speed changed to 1 mm/min. Details are shown in the test examples described below.

The thickness of the 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 preferably 10 to 12 μm. By making the thickness of the adhesive layer 5 μm or more, it is easy to control the adhesion force before irradiating energy rays, which can effectively suppress the scattering, pushing and chipping of the wafer during cutting. In particular, when the thickness of the adhesive layer is 9 μm or more, scattering of the wafer during dicing can be more effectively suppressed. In addition, as mentioned above, in the adhesive plate for glass cutting according to this embodiment, since the adhesive layer is composed of X-type or Z-type adhesive, the elastic modulus is changed compared to the Y-type adhesive layer. high. Therefore, even if the thickness of the adhesive layer becomes 5 μm or more, the shaking of the adhesive layer and the glass plate during cutting can be well suppressed, and the displacement of the glass plate on the adhesive plate can be well restrained. In addition, by keeping the thickness of the adhesive layer below 25 μm, the vibration of the adhesive layer during cutting is further reduced, and the displacement of the glass plate on the adhesive plate is suppressed, which can more effectively suppress chipping and crystal pushing.

The gel fraction of the adhesive constituting the adhesive layer is preferably 12.5 to 100%, particularly preferably 37.5 to 100%, and further preferably 50 to 95%. When the gel fraction of the adhesive is within the above range, it is easy to satisfy the physical properties of the adhesive layer. In addition, by setting the gel fraction of the adhesive to 12.5% or more, the adhesive can have good cohesion and maintain the durability of the adhesive layer.

3. Peel off the film

Regarding the adhesive sheet for glass cutting according to this embodiment, a release film may be laminated on the side of the adhesive layer opposite to the base material for a period of time before the adherend is adhered. The composition of the release film is arbitrary, and an example thereof is a plastic film that has been subjected to release treatment with a release agent or the like. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polypropylene or polyethylene films. Polyolefin film. As the release agent, silicone release agents, fluorine release agents, long-chain alkyl release agents, etc. can be used. Among these, a silicone-based release agent that can provide low-cost and stable performance is preferred. The thickness of the peelable film is not particularly limited, but is usually about 20 to 250 μm.

4. Physical properties of adhesive plates for glass cutting

The surface of the adhesive layer opposite to the base material is adhered to the alkali-free glass and left to stand for 20 minutes. Regarding the adhesive plate for glass cutting according to this embodiment, before irradiating the energy ray, the alkali-free glass is Adhesion strength is preferably 5000~25000mN/25mm. 9000~22000mN/25mm is particularly good, and 9500~18000mN/25mm is even better. By setting the adhesive force before irradiating energy rays to 5000mN/25mm or more, the glass wafer and glass plate can be well held on the adhesive plate during cutting. As a result, the glass wafer and glass plate can be effectively prevented from being offset, chipped and pushed on the adhesive plate. Furthermore, since the glass wafer can be well held on the adhesive plate during cutting, the occurrence of wafer scattering can be suppressed. On the other hand, by setting the adhesive force before energy ray irradiation to 25000mN/25mm or less, the adhesive force after energy ray irradiation can be easily reduced to an adhesive force that is easy to pick up.

The surface of the adhesive layer opposite to the base material is adhered to alkali-free glass, and after the adhesive layer is irradiated with energy rays, the adhesive force of the adhesive plate for glass cutting according to this embodiment to the alkali-free glass is measured at 50 ~250mN/25mm is preferred, 60~160mN/25mm is particularly preferred, and 70~130mN/25mm is further preferred. By setting the adhesive force after energy ray irradiation to 50mN/25mm or more, it is possible to prevent the glass wafer from being unintentionally peeled off from the adhesive plate in the stage before picking up the glass wafer from the adhesive plate. On the other hand, by setting the adhesive force after irradiation with energy rays to 250 mN/25 mm or less, for example, when picking up individual glass wafers after cutting, the glass wafers can be picked up satisfactorily without being damaged.

In addition, the adhesive force in this manual is the adhesive force (mN/25mm) measured by the 180° peel and tear method using alkali-free glass as the adherend in accordance with JIS Z0237:2009. The details of the measurement method are as follows. is shown in the test example.

5. Manufacturing method of adhesive plate for glass cutting

The manufacturing method of the adhesive plate for glass cutting is not particularly limited as long as the adhesive layer formed of the above-mentioned adhesive composition can be laminated on one side of the base material.

An example of a method of manufacturing an adhesive plate for glass cutting involves first preparing a coating composition containing the adhesive composition and, if desired, a solvent or a dispersant. Next, the coating composition is applied to one surface of the base material using a die coater, shower coater, spray coater, slit coater, knife coater, etc. to form a coating film. . Furthermore, by drying the coating film, an adhesive layer can be formed. The properties of the coating composition are not particularly limited as long as it can be coated. The component for forming the adhesive layer may be contained in the coating composition as a solute, or may be contained as a dispersion.

When the coating composition contains a bridging agent (C), in order to form a bridging structure at a desired density, the drying conditions (temperature, time, etc.) may be changed, or a heat treatment may be additionally provided. In order to fully carry out the bridging reaction, after laminating the adhesive layer on the substrate by the above method, the obtained adhesive plate for glass cutting can be left to stand for 1 week to 2 in an environment of 23°C and 50% relative humidity. It takes about a week to mature.

In another example of the method of manufacturing an adhesive plate for glass cutting, first, a coating composition is applied to the release-treated surface of the release film as described above to form a coating film. Next, the coating film is dried to form a laminate composed of an adhesive layer and a release film. Furthermore, the surface of the laminate opposite to the release film of the adhesive layer is bonded to the base material. Through the above method, a laminate of an adhesive plate and a release film for glass cutting can be obtained. The release film on the laminate can be peeled off as an engineering material, or it can protect the adhesive layer until a period of time before it is attached to the adherend.

6. About the use of adhesive plates for glass cutting

The adhesive plate for glass cutting according to this embodiment can be used for cutting glass plates. Cut. In addition, the adhesive plate for glass cutting according to this embodiment can also be used for a series of steps including cutting of a glass plate and subsequent picking up.

When used in a series of steps including cutting and subsequent picking up, first, the surface of the adhesive layer of the glass cutting adhesive plate of this embodiment opposite to the base material (hereinafter sometimes referred to as "adhesive" surface".) is pasted on the glass plate. When a release film is laminated on the adhesive surface, peel off the release film and stick the glass plate to the exposed adhesive surface. On the other hand, a ring-shaped jig called a ring frame for conveying or fixing the device is attached to the peripheral portion of the adhesive surface. Furthermore, it is better to let it sit for 10 to 120 minutes from pasting the glass plate to the subsequent cutting steps, especially 15 to 60 minutes, and a further 20 to 40 minutes. By letting it stand for such a period, the adhesion between the glass plate and the adhesive plate can be fully achieved.

Next, the cutting step is performed. That is, the glass plate adhered to the adhesive plate for glass cutting is cut with a cutting blade. Thereby, a plurality of glass wafers adhered to the adhesive plate for glass cutting are obtained. Generally, when cutting, frictional heat is generated due to the contact between the adhesive layer and the cutting blade, and the adhesive layer is heated to a high temperature of about 100°C. Here, in the adhesive plate for glass cutting according to this embodiment, the adhesive layer is formed of an adhesive composition containing a (meth)acrylate copolymer (A) with an energy ray curable group introduced into the side chain. It is composed of adhesive, so in such a high temperature state, the adhesive layer shows a higher elastic modulus. Therefore, when cutting, the glass plate adhered to the adhesive plate is not easy to shake, which can prevent unintentional collision between the cutting surface of the glass plate and the cutting blade, or the displacement of the glass plate on the adhesive plate. Therefore, with the adhesive plate for glass cutting according to this embodiment, cutting can be performed while suppressing the occurrence of chipping and crystal pushing during cutting.

After the cutting step is completed, the adhesive plate to which the plurality of glass wafers are bonded is irradiated with energy rays from the surface on the glass wafer side or the surface on the base material side. Thereby, the energy ray curable group of the (meth)acrylate copolymer (A) in which the energy ray curable group is introduced into the side chain is polymerized to reduce the adhesiveness, making it easier to perform the subsequent pickup step.

The picking step can be performed by common means such as a vacuum chuck. At this time, in order to facilitate picking up, it is preferable to push the target glass wafer from the surface opposite to the adhesive layer on the base material side with a push pin or a needle.

Furthermore, the expansion step can also be performed before the picking step. At this time, the adhesive plate for glass cutting is extended in the plane direction. This widens the distance between the glass wafers, making them easier to pick up. The degree of elongation can be appropriately set taking into account the optimal spacing, the tensile strength of the base material, etc. Furthermore, the expansion step can also be performed before irradiating energy rays.

When cutting a glass plate using the adhesive plate for glass cutting according to this embodiment, the thickness of the glass plate as the workpiece is preferably 50 to 10000 μm, particularly preferably 100 to 5000 μm, and further preferably 300 to 800 μm. In addition, in this specification, the term "workpiece" refers to a workpiece adhered to the adhesive plate for glass cutting according to this embodiment, or a workpiece processed using the adhesive plate. According to the adhesive plate for glass cutting according to this embodiment, since the adhesive layer is relatively hard as described above, even a thin glass plate with a thickness of 50 μm can be cut while suppressing chipping.

In addition, when the glass plate is cut using the adhesive plate for glass cutting according to this embodiment, the plane area of the resulting glass wafer is preferably 1×10 ^-6 mm ² ~1mm ² and preferably 1×10 ^-4 mm ² ~ 0.25mm ² is more preferred, 2.5×10 ^-3 mm ² ~0.09mm ² is particularly preferred, and 0.01mm ² ~0.03mm ² is further preferred. The adhesive plate for glass cutting according to this embodiment can be obtained while suppressing chipping and crystal pushing during cutting even if it is a small glass wafer having an area within the above range.

The embodiments described above are described to facilitate understanding of the present invention and are not described to limit the present invention. Therefore, each element disclosed in the above-mentioned embodiment is intended to include all design changes or equivalents falling within the technical scope of the present invention.

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

[Example]

Hereinafter, the present invention will be described in more detail using examples and the like, but the present invention is not limited to these examples. In addition, the following descriptions of parts by mass are expressed in terms of solid parts conversion values.

[Example 1]

(1) Preparation of (meth)acrylate copolymer (A) in which energy ray curable groups are introduced into the side chain

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 to obtain an acrylic copolymer (AP). 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 this example is the weight average molecular weight converted to standard polystyrene using gel permeation chromatography (GPC) measurement (GPC measurement).

Next, the obtained acrylic copolymer (AP) and 2-methacryloxyethyl isocyanate as the energy ray curable group-containing compound (A3) are The ester (MOI) is reacted in the presence of a zirconium chelate catalyst (manufactured by Matsumoto Fine Chemical Co., Ltd., product name "ZC-700") as the organometallic catalyst (D). Thereby, a (meth)acrylate copolymer (A) in which an energy ray curable group (methacrylyl group) is introduced into the side chain is obtained. At this time, the MOI of the 2-hydroxyethyl acrylate unit of the acrylic copolymer (AP) was 100 molar equivalents, and the two were reacted to 60 moles (60 mol%). In addition, the compounding amount of the organic metal catalyst (D) was 0.1 parts by mass relative to 100 parts by mass of the acrylic copolymer (AP).

(2) Preparation of adhesive composition

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

(3) Production of adhesive plates for glass cutting

The coating solution of the adhesive composition obtained in the above step (2) is coated on a release film of a polyethylene terephthalate film that has been peeled off by a silicone-based release agent on one side using a die coater (LINTEC Co., Ltd. manufactured, product name "SP-PET381031", thickness: 38μm) peeling surface. Next, it was treated at 100° C. for 1 minute to dry the coating film and simultaneously perform a bridging reaction. Thereby, a laminate consisting of a release film and an adhesive layer having a thickness of 10 μm was obtained. Furthermore, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "A-4100", thickness: 100 μm) was adhered to the adhesive layer side surface of the laminate. ). Through this, get support An adhesive plate for glass cutting that sequentially stacks a base material, an adhesive layer and a release film.

[Examples 2~14]

The material of the base material, the thickness of the base material, the amount of 2-methacryloxyethyl isocyanate (MOI) used to form the adhesive layer, and the type of organic metal catalyst (D) used to form the adhesive layer , and the thickness of the adhesive layer was changed to those shown in Table 1, and an adhesive plate for glass cutting was manufactured in the same manner as in Example 1.

[Comparative example 1]

(1) Preparation of adhesive composition

90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid were copolymerized to obtain an acrylic polymer (N) having no energy ray curability. The molecular weight of the obtained polymer (N) was measured and the weight average molecular weight (Mw) was 600,000.

100 parts by mass of the acrylic polymer (N) without energy ray curability obtained as above and 127 parts by mass of trifunctional urethane acrylate oligomer (Dainichi Seika Industrial Co., Ltd.) as the energy ray curable compound (B) (manufactured by BASF, product name "EXL810TL", Mw=5000), 4 parts by mass of α-hydroxycyclohexylbenzophenone (manufactured by BASF, product name "IRGACURE184") as a photopolymerization initiator, and 11 parts by mass of triacetin as a bridging agent. Methylolpropane-denatured toluene diisocyanate (manufactured by TOSO, product name "CORONATE L") was mixed with a solvent to obtain a coating solution of an adhesive composition. Furthermore, by using this adhesive composition, a Y-shaped adhesive is obtained.

(2) Production of adhesive plates for glass cutting

An adhesive plate for glass cutting was produced in the same manner as in Example 1, except that the coating solution of the adhesive composition obtained in the above step (1) was used.

(Comparative example 2)

(1) Preparation of adhesive composition

50 parts by mass of 2-ethylhexyl acrylate, 40 parts by mass of methyl acrylate, and 10 parts by mass of acrylic acid were copolymerized to obtain an acrylic polymer (N) without energy ray curability. The molecular weight of the obtained polymer (N) was measured and the weight average molecular weight (Mw) was 800,000.

100 parts by mass of the acrylic polymer (N) without energy ray curability obtained as above and 40 parts by mass of 10-functional urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as the energy ray curable compound (B) name "UV-1700B", molecular weight: 1700), 0.1 parts by mass of α-hydroxycyclohexylphenone (manufactured by BASF, product name "IRGACURE184") as a photopolymerization initiator, and 10 parts by mass of trihydroxyl as a bridging agent Methylpropane-denatured toluene diisocyanate (manufactured by TOSO, product name "CORONATE L") was mixed with a solvent to obtain a coating solution of an adhesive composition. Furthermore, by using this adhesive composition, a Y-shaped adhesive is obtained.

(2) Production of adhesive plates for glass cutting

An adhesive plate for glass cutting was produced in the same manner as in Example 1, except that the coating solution of the adhesive composition obtained in the above step (1) was used.

[Comparative Examples 3 and 4]

The thickness of the adhesive layer was changed to other than those shown in Table 1, and an adhesive sheet for glass cutting was produced in the same manner as in Comparative Example 2.

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

[Material of base material]

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

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

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

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

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

PI: Polyimide film (manufactured by MPRTECH, product name "MordoharPIF100")

[Organometallic Catalyst]

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

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

[Test Example 1] (Measurement of storage elastic modulus of base material)

Regarding the base materials used in the examples and comparative examples, the storage elastic modulus at 23° C. was measured using the following equipment and conditions. The results are shown in Table 1.

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

Test starting temperature: 0℃

Test end temperature: 200℃

Heating rate: 3℃/min

Frequency: 11Hz

Amplitude: 20μm

[Test Example 2] (Storage bomb of adhesive layer before irradiation with ultraviolet rays) Determination of sexual modulus)

The coating solution of the adhesive composition used in Examples and Comparative Examples was applied to the release-treated surface of a first release film (manufactured by LINTEC, product name "SP-PET381031") with a thickness of 38 μm. The obtained coating film was kept at 100° C. for 1 minute to dry the coating film. Thereby, an adhesive layer having a thickness of 40 μm was formed on the first release film. Furthermore, the surface of the adhesive layer opposite to the first release film was adhered to the release-treated surface of the second release film (manufactured by LINTEC, product name "SP-PET381031") with a thickness of 38 μm, to obtain the sequential A laminate including a first release film, an adhesive layer with a thickness of 40 μm, and a second release film. The adhesive layer obtained through the above process was laminated in multiple layers to obtain a thickness of 800 μm. A circular shape with a diameter of 10 mm was punched out from the 800 μm-thick laminate to serve as a sample for measurement. Using a viscoelastic measuring device (manufactured by TA Instrument, product name "ARES"), the sample was deformed at a frequency of 1 Hz, and the storage elastic modulus at -50~150°C was measured to obtain the storage elastic modulus at 23°C and 100°C. Number value. The results are shown in Table 1. In addition, when laminating a plurality of adhesive layers, after forming the adhesive layer, the above-mentioned laminate is used as the above-mentioned laminate that is left in an environment with a temperature of 23° C. and a humidity of 50% for 1 week.

[Test Example 3] (Measurement of tensile elastic modulus of the adhesive layer after ultraviolet irradiation)

In the same procedure as Test Example 2, a plurality of adhesive layers were laminated to a thickness of 200 μm.

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

The peeling film was peeled off from the obtained test piece, and the tensile elastic modulus of the hardened adhesive layer at 23°C was measured in accordance with JIS K7161:1994 and JIS K7127:1999. Specifically, a tensile testing machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS500N") was used, and after setting the clamp distance to 100 mm, a tensile test was performed at a speed of 200 mm/min, and the tensile elastic modulus ( Pa). The results are shown in Table 1.

[Test Example 4] (Measurement of viscosity value)

)的探頭，以探頭黏性試驗機(Rhesca公司製，產品名「RPT-100」)測定黏性值。測定方法，係以JIS Z0237：2009所記載的方法，將剝離速度變更為1mm/分，另一方面荷重為100gf/cm²，接觸時間為1秒鐘，係如上述JIS的規定所記載。求測定的能量(波峰積算值)，將此作為黏性值(單位：mJ/5mm

)。將結果示於表1。再者，在上述測定，使用在形成黏著劑層之後，在溫度23℃，濕度50%的環境放置1週的黏著板片。 Regarding the surface on the adhesive layer side of the adhesive sheets produced in Examples and Comparative Examples, a diameter of 5 mm (5 mm

) probe, measure the viscosity value with a probe viscosity testing machine (manufactured by Rhesca, product name "RPT-100"). The measurement method is the method described in JIS Z0237:2009, except that the peeling speed is changed to 1 mm/min, the load is 100 gf/cm ² , and the contact time is 1 second, as described in the above-mentioned JIS regulations. Calculate the measured energy (integrated peak value) and use this as the viscosity value (unit: mJ/5mm

). The results are shown in Table 1. Furthermore, in the above measurement, an adhesive plate was used that was placed in an environment with a temperature of 23°C and a humidity of 50% for 1 week after the adhesive layer was formed.

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

At room temperature, the adhesive plate for glass cutting manufactured by the Examples and Comparative Examples was placed in an environment with a temperature of 23° C. and a humidity of 50% for one week, and the release film was peeled off. The surface exposed to the adhesive layer was laminated on one surface of a 6-inch alkali-free glass plate, and bonded by applying a load back and forth once with a 2kg roller, and left for 20 minutes. After that, use the 180° peeling and tearing method in compliance with JIS Z0237:2009 to cut the peeled glass from the alkali-free glass plate at a peeling speed of 300mm/min and a peeling angle of 180°. Use an adhesive plate to measure the adhesion force (mN/25mm). This measured value was used as the adhesive force before ultraviolet irradiation. The results are shown in Table 1.

In addition, in the same manner as above, the adhesive sheets for glass cutting produced in Examples and Comparative Examples were bonded to a 6-inch alkali-free glass plate and left for 20 minutes. Then, ultraviolet rays were applied from the base material side of the adhesive sheets for glass cutting. An irradiation device (manufactured by LINTEC, product name "RAD-2000") irradiates ultraviolet (UV) light (illuminance: 230mW/cm ² , light intensity: 190mJ/cm ² ) to harden the adhesive layer. Thereafter, the adhesive force (mN/25mm) was measured in the same manner as above. The measured value was regarded as the adhesive force after ultraviolet irradiation. The results are shown in Table 1.

[Test Example 6] (Evaluation of chipping and crystal pushing)

The adhesive plate for glass cutting produced in Examples and Comparative Examples was left for one week in an environment with a temperature of 23°C and a humidity of 50%. The release film was peeled off and a tape applicator (manufactured by LINTEC, product name "Adwill RAD2500m/ 12"), stick a 6-inch alkali-free glass plate with a thickness of 550μm and a ring frame for cutting on the exposed surface of the adhesive layer. Next, the adhesive plate for glass cutting is cut to match the outer diameter of the ring frame. Furthermore, a cutting device (manufactured by DISCO, product name "DFD-651") was used to cut from the glass plate side under the following cutting conditions to obtain a 0.6 mm square glass wafer.

<Cutting conditions>

‧Cutting device: DISCO DFD-651

‧Blade: DISCO NBC-2H 2050 27HECC

‧Blade width: 0.025~0.030mm

‧Infeed amount: 0.640~0.760mm

‧Blade rotation speed: 30000rpm

‧Cutting speed: 80mm/sec

‧Substrate cutting depth: 20μm

‧Cutting water volume: 1.0L/min

‧Cutting water temperature: 20℃

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

After cutting is completed, place the glass wafer located at the center of the glass cutting adhesive plate and its vicinity to observe whether there are any defects and shapes at the ends. Specifically, an electron microscope (manufactured by KEYENCE, product name "VHZ-100, magnification: 300 times)" was used to observe the sides of 50 wafers in the flow direction (MD direction) during the production of the base material and the edges orthogonal to the MD direction. direction (CD direction). Then, defects with a width or depth of 20 μm or more are determined as missing corners, and their number is counted. Based on the results, the missing corners are evaluated based on the following standards. The evaluation results are shown in Table 1.

◎: The number of chipped wafers is less than 5.

○: The number of wafers with chipped corners is 5 or more and less than 50.

×: The number of wafers with chipped corners is 50 or more.

In addition, for all glass wafers obtained by the above-mentioned cutting, the length of the four sides in plan view is measured, and the difference between the maximum value and the minimum value is counted. The maximum value is 10% or more of the wafers (hereinafter sometimes referred to as "NG wafers"). .) number. Based on this result, the crystal push was evaluated based on the following criteria. The evaluation results are shown in Table 1.

◎: The number of NG wafers is less than 50.

○: The number of NG wafers is 50 or more and less than 500.

×: The number of NG wafers is 500 or more.

As can be seen from Table 1, according to the adhesive plate of the embodiment, chipping and crystal pushing can be suppressed.

[Industrial profitability]

The adhesive sheet for glass cutting of the present invention can be used in the cutting process of glass, especially in the cutting process of thin glass.

Claims (10)

A method for manufacturing an adhesive plate for glass cutting, which is characterized by comprising: making at least alkyl (meth)acrylate monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group. A polymerized acrylic copolymer (AP) containing energy ray curable properties bonded with a carbon-carbon double bond having a substituent capable of reacting with the functional group of the functional group-containing monomer (A2) and energy ray curable properties The step of preparing a (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain by reacting the compound (A3) with the group; and using an adhesive containing the (meth)acrylate copolymer (A). The agent composition is a step of laminating an adhesive layer on at least one surface of the base material, wherein the acrylic copolymer (AP) and the energy ray curable group-containing compound (A3) are reacted to form a zirconium-containing compound. It is carried out in the presence of an organic metal catalyst (D) of an organic compound, and the thickness of the above-mentioned adhesive layer is 5 μm or more and 19 μm or less. The method for manufacturing an adhesive plate for glass cutting as described in item 1 of the patent application, wherein the adhesive composition further contains an energy ray curable compound (B) other than the (meth)acrylate copolymer (A). ). The method for manufacturing an adhesive plate for glass cutting as described in item 1 of the patent application, wherein the adhesive composition further contains a bridging agent (C). For example, in the manufacturing method of an adhesive plate for glass cutting as described in item 1 of the patent application, the storage elastic modulus of the adhesive layer at 100°C before irradiation with energy rays is 5~50kPa. Manufacturing of adhesive plates for glass cutting as described in Item 1 of the patent application Method, wherein in the above-mentioned adhesive plate for glass cutting, the surface of the above-mentioned adhesive layer opposite to the above-mentioned base material is adhered to the alkali-free glass, and after leaving it standing for 20 minutes, the above-mentioned adhesive plate for glass cutting is irradiated with energy The adhesion force to the above-mentioned alkali-free glass before threading is 5000~25000mN/25mm. The manufacturing method of an adhesive plate for glass cutting as described in Item 1 of the patent application, wherein the adhesive plate for glass cutting adheres the surface of the adhesive layer opposite to the base material to the alkali-free glass, After the adhesive layer is irradiated with energy rays, the adhesive force of the above-mentioned glass cutting adhesive plate to the above-mentioned alkali-free glass is 50~250mN/25mm. For example, in the manufacturing method of adhesive plates for glass cutting described in item 1 of the patent application, the storage elastic modulus of the above-mentioned base material at 23°C is 100~8000MPa. For example, in the manufacturing method of an adhesive plate for glass cutting described in the first item of the patent application, the adhesive plate for glass cutting uses glass with a thickness of 50 to 10,000 μm as a workpiece. For example, in the manufacturing method of an adhesive plate for glass cutting described in the first item of the patent application, the above-mentioned adhesive plate for glass cutting is used to cut the glass plate into a flat surface with an area of 1×10 ^-6 mm ² ~1mm ² glass wafer. An adhesive sheet for glass cutting, which is an adhesive sheet for glass cutting that includes a base material and an adhesive layer laminated on at least one surface of the base material, wherein the adhesive layer is made of It consists of an energy ray curable adhesive composed of an adhesive composition of a (meth)acrylate copolymer (A) with an energy ray curable group introduced into the side chain. The thickness of the above-mentioned adhesive layer is 5 μm or more and 19 μm or less. The above-mentioned adhesive plate for glass cutting is manufactured by a manufacturing method including the following steps: at least alkyl (meth)acrylate monomer (A1) and a An acrylic copolymer (AP) in which a reactive functional group-containing monomer (A2) is copolymerized, has a substituent that can react with the functional group of the functional group-containing monomer (A2), and is cured by energy rays The step of preparing a (meth)acrylate copolymer (A) in which an energy ray curable group is introduced into the side chain by reacting a compound (A3) containing an energy ray curable group bonded with a permanent carbon-carbon double bond; and using An adhesive composition containing the (meth)acrylate copolymer (A), a step of laminating an adhesive layer on at least one surface of the base material, wherein the acrylic copolymer (AP) and the energy ray-containing The reaction of the curable group compound (A3) is carried out in the presence of an organic metal catalyst (D) containing an organic compound containing zirconium.