KR102638359B1 - Glass dicing adhesive sheet and method of manufacturing the same - Google Patents

Abstract

(Problem) To provide a pressure-sensitive adhesive sheet for glass dicing that suppresses chipping and can efficiently dice a glass plate, and a method for manufacturing the same.
(Solution) A pressure-sensitive adhesive sheet for glass dicing comprising a base material and an adhesive layer laminated on at least one side of the base material, wherein the thickness of the base material is 30 μm or more and less than 130 μm, and the pressure-sensitive adhesive layer has a temperature of 100° C. An adhesive sheet for glass dicing having a storage modulus of 6 to 50 kPa.
(Selectivity) None

Description

Adhesive sheet for glass dicing and method of manufacturing the same {GLASS DICING ADHESIVE SHEET AND METHOD OF MANUFACTURING THE SAME}

The present invention relates to an adhesive sheet for glass dicing, which is used to obtain glass chips by dicing a glass plate, and a method for producing the same.

In manufacturing camera modules mounted on mobile phones and smart phones, fine pieces of glass are required. Such glass pieces can be obtained by dicing one glass plate using a dicing sheet. That is, after attaching a glass plate to a dicing sheet, the glass plate is cut with a dicing blade to obtain individual pieces of glass (hereinafter sometimes referred to as "glass chips"). In recent years, smartphones and the like have become thinner, and the camera modules mounted on them have also become smaller. As a result, there is a need to manufacture thinner and finer glass chips (hereinafter sometimes referred to as “small chips”).

When dicing brittle materials such as glass, chipping is prone to occur. Here, chipping means that the end or cut surface of the glass chip is damaged during dicing. The occurrence of chipping becomes more noticeable as the thickness of the glass plate becomes thinner.

Patent Document 1 discloses an adhesive sheet for glass substrate dicing in which an adhesive layer is formed on a base film. In this patent document 1, by using a film with a thickness of 130 ㎛ or more and a tensile elastic modulus of 1 GPa or more as a base film, and by setting the thickness of the adhesive layer to 9 ㎛ or less, deformation of the adhesive sheet due to the pressure of the dicing blade can be reduced. It is disclosed that chipping and chip scattering can be suppressed (paragraph 0010 of Patent Document 1).

Japanese Patent Publication No. 3838637

Recently, camera modules have been miniaturized, and the size of the glass chip required is also becoming very small. In the adhesive sheet disclosed in Patent Document 1, such chipping of small chips cannot be sufficiently suppressed.

The present invention has been made in consideration of the above-described actual situation, and its purpose is to provide a pressure-sensitive adhesive sheet for glass dicing that can suppress chipping and efficiently dice a glass plate, and a method for manufacturing the same.

In order to achieve the above object, firstly, the present invention is an adhesive sheet for glass dicing comprising a base material and an adhesive layer laminated on at least one side of the base material, wherein the thickness of the base material is 30 μm or more and less than 130 μm. A pressure-sensitive adhesive sheet for glass dicing is provided, wherein the pressure-sensitive adhesive layer has a storage modulus of 6 to 50 kPa at 100°C (invention 1).

In the above invention (invention 1), when the base material has the above-mentioned thickness, handling properties as an adhesive sheet for glass dicing become good. In addition, because the pressure-sensitive adhesive layer exhibits the above-mentioned storage modulus at 100°C, when the temperature of the pressure-sensitive adhesive layer becomes high, such as about 100°C, due to frictional heat during dicing, shaking occurs during dicing. As a result of this being sufficiently suppressed, the occurrence of chipping can be suppressed even when dicing a thin glass plate into small chips. By controlling the thickness of the base material and the elastic modulus of the adhesive layer as described above, it becomes possible to efficiently obtain small chips from a thin glass plate.

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

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

In the above inventions (inventions 1 to 3), the side of the adhesive layer opposite to the substrate is affixed to alkali-free glass and left to stand for 20 minutes, and then applied to the alkali-free glass of the adhesive sheet for glass dicing. The adhesive force is preferably 8000 to 25000 mN/25 mm (invention 4).

In the above inventions (inventions 1 to 4), the amount of energy measured using a probe tack in the adhesive layer under the condition that the peeling speed was changed to 1 mm/min in the method described in JIS Z0237:1991 is , it is preferably 0.01 to 5 mJ/5 mmϕ (Invention 5).

In the above inventions (inventions 1 to 5), the adhesive layer is preferably made of an energy ray-curable adhesive (invention 6).

In the above invention (invention 6), the adhesive layer is preferably composed of an adhesive formed from an adhesive composition containing a (meth)acrylic acid ester copolymer (A) into which an energy ray curable group is introduced into the side chain (invention 7). .

In the above invention (invention 7), the pressure-sensitive adhesive composition preferably further contains an energy ray-curable compound (B) other than the (meth)acrylic acid ester copolymer (A) (invention 8).

In the above inventions (inventions 7 and 8), the pressure-sensitive adhesive composition preferably further contains a crosslinking agent (C) (invention 9).

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

Secondly, the present invention is a method for producing the above-described adhesive sheet for glass dicing (invention 7), which comprises an acrylic copolymer copolymerized with at least an alkyl (meth)acrylate monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group. The polymer (AP) is reacted with a compound (A3) containing an energy ray-curable group having 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, thereby forming an energy ray-curable side chain. A step of preparing a (meth)acrylic acid ester copolymer (A) into which a group is introduced, and laminating an adhesive layer on at least one side of a substrate using an adhesive composition containing the (meth)acrylic acid ester copolymer (A). A method for manufacturing an adhesive sheet for glass dicing is provided, which includes the following steps (invention 11).

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

According to the adhesive sheet for glass dicing according to the present invention and the adhesive sheet for glass dicing manufactured by the manufacturing method according to the present invention, chipping can be suppressed and a glass plate can be diced efficiently.

Hereinafter, embodiments of the present invention will be described.

The adhesive sheet for glass dicing (hereinafter sometimes simply referred to as “adhesive sheet”) according to the present embodiment is comprised of a base material and an adhesive layer laminated on one side of the base material.

In the adhesive sheet for glass dicing according to the present embodiment, the thickness of the base material is 30 μm or more and less than 130 μm. Moreover, the storage elastic modulus of the adhesive layer at 100°C is 6 to 50 kPa.

In the adhesive sheet for glass dicing according to the present embodiment, when the base material has the above-mentioned thickness, the handling property regarding glass dicing becomes good. In addition, when the storage modulus of the adhesive layer at 100°C is within the above range, shaking of the adhesive sheet is suppressed even when the adhesive layer is brought to a high temperature due to frictional heat generated during dicing. Accordingly, collision between glass chips or unintentional collision between the glass plate or the cutting surface of the glass chip and the dicing blade is suppressed, and the occurrence of chipping is suppressed. As a result, it becomes possible to efficiently obtain small chips from thin glass plates.

1. Description

In the adhesive sheet for glass dicing according to the present embodiment, the thickness of the base material is preferably 30 μm or more and less than 130 μm, 50 μm or more and 120 μm or less, and especially preferably 70 μm or more and 110 μm or less. If the thickness of the base material is less than 30 ㎛, the adhesive sheet is likely to shake during the dicing process, and as a result, the glass plate becomes easy to move on the adhesive sheet, resulting in chipping and further die shift. It becomes easier to do. In addition, die shift means that the glass plate is shifted from its original position on the adhesive sheet during dicing. If dicing is further progressed with die shift occurring, the glass plate cannot be cut at the intended position, and as a result, glass chips having the desired shape cannot be obtained. Additionally, if the thickness of the base material is less than 30 μm, it becomes easy to break when handling the adhesive sheet or during the expand process. On the other hand, if the thickness of the base material is 130 μm or more, the flexibility of the entire adhesive sheet decreases, and the adhesive sheet is likely to fall off from the ring frame or jig when affixing it to a ring frame or a dicing jig or when dicing a glass plate. Lose.

In the adhesive sheet for glass dicing according to the present embodiment, the storage modulus of the substrate at 23°C is preferably 100 to 8000 MPa, particularly preferably 1500 to 7000 MPa, and more preferably 2000 to 6000 MPa. do. When the storage modulus of the substrate at 23°C is 100 MPa or more, the occurrence of shaking of the adhesive sheet during the dicing process is reduced, and movement of the glass plate on the adhesive sheet is suppressed, resulting in effective suppression of chipping. In addition to this, die shift can also be suppressed. In addition, when the storage modulus of the base material at 23°C is 8000 MPa or less, the flexibility of the base material is ensured and the stretchability (expandability) of the base material becomes more excellent. Accordingly, during the expand process, the adhesive sheet exhibits superior expandability, and glass chips after dicing can be picked up satisfactorily. In addition, the storage elastic modulus of the substrate at 23°C was measured under the following conditions using a dynamic elastic modulus measuring device (manufactured by TA Instruments, product name “DMA Q800”).

Test start temperature: 0 ℃

Test end temperature: 200℃

Temperature increase rate: 3℃/min

Frequency: 11 ㎐

Amplitude: 20 ㎛

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

In the base material, various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, slip agents, and fillers may be contained in the above films. Pigments include, for example, titanium dioxide and carbon black. Additionally, examples of the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metallic materials such as nickel particles. The content of these additives is not particularly limited, but is preferably set within a range that allows the base material to perform the desired function and does not lose smoothness or flexibility.

When using ultraviolet rays as an energy ray irradiated to cure the adhesive layer, it is preferable that the base material has transparency to ultraviolet rays. In addition, when using an electron beam as the energy beam, it is preferable that the substrate has transparency to the electron beam.

The surface of the base material on the adhesive layer side may be subjected to surface treatment such as primer treatment, corona treatment, plasma treatment, or roughening treatment (mat processing) in order to increase adhesion to the adhesive layer. Examples of the roughening treatment include embossing, sandblasting, etc. Additionally, various coating films may be formed on the surface of the substrate opposite to the adhesive layer.

2. Adhesive layer

(1) Thickness and physical properties of adhesive layer

The storage elastic modulus of the adhesive layer at 100°C is 6 to 50 kPa, preferably 7 to 40 kPa, and especially preferably 10 to 30. Generally, in the adhesive sheet for glass dicing, frictional heat is generated during dicing, and the adhesive layer becomes at a high temperature such as about 100°C. In such a high temperature state, if the adhesive layer exhibits a low storage modulus of less than 6 kPa, the adhesive sheet will be shaken during dicing, and the glass plate or glass chip will easily move on the adhesive sheet, resulting in chipping. It becomes In addition, when the storage elastic modulus is higher than 50 kPa, the storage elastic modulus at 23 ° C. (when the adhesive layer is made of an energy ray curable adhesive described later, the storage elastic modulus at 23 ° C before energy ray irradiation). It tends to increase and it becomes difficult to obtain good adhesion. As a result, it becomes difficult to properly hold the glass plate and glass chips on the adhesive sheet, and chipping during dicing cannot be sufficiently suppressed. In addition, in this specification, when the pressure-sensitive adhesive layer is made of an energy-ray curable pressure-sensitive adhesive described later, the storage elastic modulus is taken as the value measured before energy-ray irradiation. In addition, the method of measuring the storage elastic modulus at 100°C before energy ray irradiation of the adhesive layer is as shown in the test example described later.

The storage modulus of the adhesive layer at 23°C is preferably 30 to 100 kPa, particularly preferably 40 to 90 kPa, and more preferably 50 to 80 kPa. When the storage elastic modulus is within the above range, the adhesive sheet for glass dicing can exhibit good adhesive force, and as a result, the glass chips are well held in the adhesive sheet, and chipping during dicing can be effectively suppressed. Together, die shift and chip scattering can also be suppressed. In addition, in this specification, when the pressure-sensitive adhesive layer is made of an energy-ray curable pressure-sensitive adhesive described later, the storage elastic modulus is taken as the value measured before energy-ray irradiation. In addition, the method of measuring the storage elastic modulus at 23°C before energy ray irradiation of the adhesive layer is as shown in the test example described later.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, 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, and further preferably 9 to 9 μm. It is preferable that it is -15 ㎛, and furthermore, it is preferable that it is 10-12 ㎛. When the thickness of the adhesive layer is 5 μm or more, control of the adhesive force becomes easy and chipping can be effectively suppressed, as well as die shift and chip scattering. In addition, when the thickness of the adhesive layer is 25 ㎛ or less, the occurrence of shaking of the adhesive layer during dicing is further reduced, and the movement of the glass plate on the adhesive sheet is effectively suppressed, resulting in effective suppression of chipping. In addition, die shift can also be suppressed.

The energy amount (also referred to as "tack value" in this specification) measured using a probe tack in the adhesive layer is preferably 0.01 to 5 mJ/5 mmϕ, especially 0.13 to 4 mJ/5 mm. It is preferable that it is ϕ, and moreover, it is preferably 0.18 to 3.5 mJ/5 mmϕ. When the tack value is within the above range, the glass chips are well maintained on the adhesive sheet for glass dicing, and the occurrence of chip scattering during dicing can be suppressed. In addition, in this specification, when the adhesive layer is made of an energy ray-curable adhesive described later, the tack value is the value measured before energy ray irradiation. In addition, in this specification, the tack value is measured in the method described in JIS Z0237:2009 under conditions where the peeling speed is changed to 1 mm/min, and the details are as shown in the test examples described later.

When the adhesive layer is made of an energy ray-curable adhesive described later, the tensile modulus of elasticity of the adhesive layer at 23°C after energy ray irradiation is preferably 15 to 70 MPa, and particularly preferably 50 to 60 MPa, and further. It is preferably 23 to 50 MPa. When the tensile elastic modulus is 15 MPa or more, the glass chip after energy ray irradiation can be picked up satisfactorily. Moreover, when the tensile elastic modulus is 70 MPa or less, the expandability of the adhesive sheet for glass dicing becomes more excellent, and pickup can be performed satisfactorily. In addition, the method of measuring the tensile modulus of elasticity at 23°C before energy ray irradiation of the adhesive layer is as shown in the test example described later.

The gel fraction of the adhesive constituting the adhesive layer is preferably 12.5 to 100%, particularly preferably 37.5 to 100%, and more preferably 50 to 95%. If the gel fraction of the adhesive is within the above range, it becomes easy to satisfy the physical properties of the adhesive layer described above. Moreover, when the gel fraction of the adhesive is 12.5% or more, the cohesive force of the adhesive is good and the durability of the adhesive layer is maintained.

(2) Adhesive that makes up the adhesive layer

The adhesive constituting the adhesive layer may be a non-curable adhesive or a curable adhesive. Moreover, the curable adhesive may be in a state before curing or in a state after curing. When the adhesive layer consists of multiple layers, a combination of a non-curable adhesive and a curable adhesive may be used. Non-curable adhesives include, for example, acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, polyester adhesives, and polyvinyl ether adhesives. Examples of the curable adhesive include an energy ray curable adhesive and a thermosetting adhesive.

In the adhesive sheet for glass dicing according to the present embodiment, the adhesive layer is preferably made of an energy ray-curable adhesive, and is particularly preferably made of an energy ray-curable acrylic adhesive. Since the adhesive layer is made of an energy ray-curable adhesive, it becomes possible to cure the adhesive by irradiating an energy ray to the adhesive layer before the pickup process. As a result, the adhesive strength of the adhesive sheet to the glass chip is moderately reduced, making it possible to perform satisfactory pickup.

In general, energy ray curable acrylic adhesives contain (meth)acrylic acid ester copolymer (A) into which an energy ray curable group is introduced into the side chain, and energy ray curable adhesives other than the (meth)acrylic acid ester copolymer (A) A product formed from an adhesive composition not containing a curable compound (B) (hereinafter sometimes referred to as “X type” for convenience), an acrylic polymer (N) without energy ray curability, and the above-mentioned (meth)acrylic acid ester. Those formed from an adhesive composition containing an energy ray curable compound (B) other than the copolymer (A) (hereinafter sometimes referred to as “Y type” for convenience), and those formed with an energy ray curable group introduced into the side chain ( Formed from an adhesive composition containing a meth)acrylic acid ester copolymer (A) and an energy ray curable compound (B) other than the (meth)acrylic acid ester copolymer (A) (hereinafter referred to as “Z type” for convenience) There is.) exists.

In the adhesive sheet for glass dicing according to the present embodiment, the adhesive layer may be made of any of these types of adhesive. In particular, since the X-type adhesive exhibits a higher elastic modulus at high temperatures, it is better to use the desirable. In addition, since the Y-type adhesive is easy to obtain excellent tack, it is preferable to use the Y-type adhesive, especially from the viewpoint of suppressing chip scattering during dicing. Additionally, when a Z-type adhesive is used, the elastic modulus of the adhesive layer after energy ray irradiation becomes higher, and therefore, from the viewpoint of performing good pickup, it is preferable to use a Z-type adhesive.

The above-mentioned (meth)acrylic acid ester copolymer (A) into which an energy ray curable group is introduced into the side chain and the acrylic polymer (N) without energy ray curability may be contained as is in the adhesive layer, and a crosslinking agent (C) described later. It may be contained as a cross-linked product by performing a cross-linking reaction.

(2-1) (meth)acrylic acid ester copolymer with energy ray curable group introduced into the side chain (A)

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

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

As the (meth)acrylic acid alkyl ester monomer (A1), the alkyl group preferably has 1 to 18 carbon atoms, and especially preferably has 1 to 4 carbon atoms. Specific examples of alkyl (meth)acrylate monomer (A1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isooctyl, (meth)acrylic acid n-decyl, (meth)acrylic acid lauryl, (meth)acrylic acid myristyl, (meth)acrylic acid Palmityl, (meth)acrylic acid stearyl, etc. are mentioned. These may be used individually or in combination of two or more types.

The mass ratio of the structural moiety derived from the above-mentioned (meth)acrylic acid alkyl ester monomer (A1) to the total mass of the acrylic copolymer (AP) is preferably 50 to 98 mass%, and especially 60 to 95 mass%. It is preferable, and it is more preferable that it is 70-90 mass %.

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

When using a monomer having a hydroxyl group (hydroxyl group-containing monomer) as the functional group-containing monomer (A2), examples thereof include (meth)acrylic acid hydroxyalkyl ester, and a specific example thereof is (meth)acrylic acid 2-hyde. Roxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hyde Roxybutyl, etc. can be mentioned. Among these, 2-hydroxyethyl (meth)acrylate is preferable from the viewpoint of hydroxyl group reactivity and copolymerizability. These may be used individually or in combination of two or more types.

When using a monomer having a carboxyl group (carboxyl group-containing monomer) as the functional group-containing monomer (A2), examples thereof include ethylenically unsaturated carboxylic acids, and specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, Maleic acid, itaconic acid, citraconic acid, etc. can be mentioned. Among these, acrylic acid is preferable from the viewpoint of the reactivity of the carboxyl group and copolymerizability. These may be used individually or in combination of two or more types.

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

The mass ratio of the structural portion derived from the functional group-containing monomer (A2) to the total mass of the acrylic copolymer (AP) is preferably 5 to 40 mass%, especially preferably 7 to 35 mass%, and further. It is preferably 10 to 30 mass%. When the mass ratio of the structural portion derived from the functional group-containing monomer (A2) is within the above range, the energy-ray-curable group-containing compound (A3) is converted to the (meth)acrylic acid ester copolymer (A) into which the energy-ray-curable group is introduced into the side chain. The amount of introduction can be within an appropriate range. In addition, when reacting the functional group-containing monomer (A2) with the crosslinking agent (C) using the crosslinking agent (C) described later, the degree of crosslinking by the crosslinking agent (C), that is, the gel fraction, can be kept in an appropriate range. , it becomes possible to control physical properties such as cohesion of the adhesive layer.

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

Other monomers include (meth)acrylic acid containing an alkoxyalkyl group such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. Acrylic acid ester; (meth)acrylic acid ester having an aliphatic ring such as cyclohexyl (meth)acrylate; (meth)acrylic acid ester having an aromatic ring such as phenyl (meth)acrylate; non-crosslinkable acrylic such as acrylamide, methacrylamide, etc. Amide; (meth)acrylic acid ester having a non-crosslinkable tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate; vinyl acetate; styrene, etc. . These may be used individually or in combination of two or more types.

The polymerization mode of the acrylic copolymer (AP) may be a random copolymer or a block copolymer. Moreover, there is no particular limitation regarding the polymerization method, and polymerization can be performed by a general polymerization method.

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

Examples of the functional group capable of reacting with the functional group of the functional group-containing monomer (A2) include an isocyanate group and an epoxy group, and among these, an isocyanate group with high reactivity with a hydroxyl group is preferable.

The curable group (energy ray curable group) having an energy ray curable carbon-carbon double bond is preferably a (meth)acryloyl group. Moreover, it is preferable that 1 to 5 energy ray curable carbon-carbon double bonds exist in 1 molecule of the energy ray curable group-containing compound (A3), and it is especially preferable that 1 to 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 a diisocyanate compound or polyisocyanate compound and hydroxyethyl (meth)acrylate; a diisocyanate compound or polyisocyanate compound, An acryloyl monoisocyanate compound obtained by reaction between a polyol compound and hydroxyethyl (meth)acrylate, etc. can be mentioned. Among these, 2-methacryloyloxyethyl isocyanate is particularly preferable. In addition, the energy ray-curable group-containing compound (A3) may be used individually, or may be used in combination of 2 or more types.

In preparing a (meth)acrylic acid ester copolymer (A) into which an energy radiation curable group is introduced into the side chain, preparation of an acrylic copolymer (AP), and acrylic copolymer (AP) and a compound containing an energy radiation curable group (A3) ) The reaction 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). In this way, a (meth)acrylic acid ester copolymer (A) in which an energy beam 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 organometallic catalyst (D).

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

The weight average molecular weight (Mw) of the (meth)acrylic acid ester copolymer (A) into which an energy radiation curable group is introduced into the side chain is preferably 100,000 to 2.5 million, especially preferably 150,000 to 2 million, and furthermore 300,000. It is preferable that it is between 10,000 and 1.5 million. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured by gel permeation chromatography (GPC) method. When the weight average molecular weight (Mw) of the (meth)acrylic acid ester copolymer (A) into which an energy radiation curable group is introduced into the side chain is within the above range, the coatability of the adhesive composition is ensured and the cohesiveness of the adhesive layer is good. Therefore, physical properties suitable for dicing can be obtained.

(2-2) Acrylic polymer without energy ray curing property (N)

As the acrylic polymer (N) which does not have energy ray curing property, a conventionally known acrylic polymer can be used as long as it does not have energy ray curing property. The acrylic polymer may be a homopolymer formed from one type of acrylic monomer, a copolymer formed from multiple types of acrylic monomers, or a copolymer formed from one type or multiple types of acrylic monomer and a monomer other than the acrylic monomer.

The specific type of the compound that becomes the acrylic monomer is not particularly limited, and specific examples include (meth)acrylic acid, (meth)acrylic acid ester, and its derivatives (acrylonitrile, itaconic acid, etc.). More specific examples include the above-mentioned alkyl (meth)acrylate monomer (A1) and functional group-containing monomer (A2), and in addition, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ( (meth)acrylic acid esters containing alkoxyalkyl groups such as ethoxymethyl (meth)acrylate and ethoxyethyl (meth)acrylate; (meth)acrylic acid esters with aliphatic rings such as cyclohexyl (meth)acrylate; phenyl (meth)acrylate, etc. (meth)acrylic acid esters having an aromatic ring; non-crosslinkable acrylamides such as acrylamide and methacrylamide; polyesters such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate (meth)acrylic acid ester having a cross-linked tertiary amino group; vinyl acetate; styrene, etc.

When the non-energy ray-curable acrylic adhesive (N) has a reactive functional group derived from the functional group-containing monomer (A2), from the viewpoint of keeping the degree of crosslinking within a good range, the functional group-containing monomer (A2) accounts for the entire mass of the acrylic polymer. ) It is preferable that the mass ratio of the derived structural portion is about 1 to 20 mass%, and it is more preferable that it is 2 to 10 mass%.

The weight average molecular weight (Mw) of the acrylic polymer (N) without energy ray curability is preferably 100,000 to 2.5 million, particularly preferably 150,000 to 2 million, and more preferably 200,000 to 1.5 million. When the weight average molecular weight (Mw) of the acrylic polymer (N) without energy ray curability is within the above range, the coatability of the adhesive composition is ensured and the cohesiveness of the adhesive layer is good, making it suitable for dicing. physical properties can be obtained.

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

An energy ray curable compound (B) is a compound that polymerizes and hardens when irradiated with energy rays such as ultraviolet rays or electron beams. Examples of the energy ray curable compound (B) include low molecular weight compounds (monofunctional or polyfunctional monomers and oligomers) having an energy ray polymerizable group, and specifically, trimethylolpropane triacrylate and tetramethyl Allmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate Acrylates such as acrylates, acrylates containing a cyclic aliphatic skeleton such as dicyclopentadiene dimethoxy diacrylate and isobornyl acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, and epoxy-modified acrylic. Acrylate-based compounds such as acrylate, polyether acrylate, and itaconic acid oligomer are used. Such compounds have an energy-ray curable double bond in the molecule, and usually have 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 made of the Y-type pressure-sensitive adhesive described above, the content of the energy-beam curable compound (B) in the pressure-sensitive adhesive composition is based on 100 parts by mass of the acrylic polymer (N) without energy-beam curability. , it is preferably 20 to 200 parts by mass, especially preferably 40 to 160 parts by mass, and further preferably 40 to 150 parts by mass.

When the adhesive layer in the present embodiment is made of the above-described Z type adhesive, the content of the energy ray curable compound (B) in the adhesive composition is a (meth)acrylic acid ester copolymer into which an energy ray curable group is introduced into the side chain. (A) Relative to 100 parts by mass, it is preferably 3 to 60 parts by mass, especially preferably 5 to 50 parts by mass, and further preferably 10 to 40 parts by mass.

(3) Cross-linking agent (C)

The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment is crosslinked with a (meth)acrylic acid ester copolymer (A) having an energy-ray-curable group introduced into the side chain or an acrylic polymer (N) without energy-ray-curability. It is desirable to contain a possible crosslinking agent (C). In this case, the adhesive layer in this embodiment contains a crosslinked product obtained by a crosslinking reaction between the (meth)acrylic acid ester copolymer (A) or the acrylic polymer (N) and the crosslinking agent (C). By using such a crosslinking agent (C), it becomes easy to adjust the gel fraction of the adhesive forming the adhesive layer to an appropriate range, and physical properties suitable for dicing can be obtained.

Types of the crosslinking agent (C) include, for example, epoxy-based compounds, polyisocyanate-based compounds, metal chelate-based compounds, polyimine-based compounds such as aziridine-based compounds, melamine resins, urea resins, dialdehydes, and methylol polymers. , metal alkoxides, metal salts, etc. Among these, it is preferable to use an epoxy-based compound or a polyisocyanate-based compound for reasons such as easy control of the crosslinking reaction, and it is especially preferable to use a polyisocyanate-based compound.

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

A polyisocyanate-based compound is a compound having two or more isocyanate groups per molecule. Specifically, 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. Polyisocyanate, etc. can be mentioned. Furthermore, these burette bodies, isocyanurate bodies, adduct bodies, etc. can be mentioned. Examples of the adduct include reactants with low-molecular-weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.

The crosslinking agent (C) may be used individually or in combination of two or more types.

When the adhesive is of type , it is preferably 0.01 to 15 parts by mass, especially preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass. Moreover, when the adhesive is Y type, the content of the crosslinking agent (C) in the adhesive composition forming the adhesive layer is preferably 3 to 20 parts by mass, especially 5 parts by mass, relative to the acrylic polymer (N) that does not have energy ray curability. It is preferably from 17 to 17 parts by mass, and more preferably from 7 to 14 parts by mass.

(4) Organometallic catalyst (D)

In order to obtain a (meth)acrylic acid ester copolymer (A) having an energy ray curable group introduced into the side chain, when reacting an acrylic copolymer (AP) with a compound (A3) containing an energy ray curable group, the reaction is carried out using an organometallic catalyst. (D) is preferably carried out in the presence of. As the organometallic catalyst (D), it is particularly preferable to use at least one selected from the group consisting of zirconium-containing organic compounds, titanium-containing organic compounds, and tin-containing organic compounds. By reacting in the presence of such an organometallic catalyst (D), the pressure-sensitive adhesive composition containing the obtained (meth)acrylic acid ester copolymer (A) becomes possible to form a pressure-sensitive adhesive layer with better tack and effectively prevents chip scattering. It becomes possible to suppress Among the above three types of organic compounds, the organometallic catalyst (D) is preferably at least one of a zirconium-containing organic compound and a titanium-containing organic compound, and is particularly preferably a zirconium-containing organic compound.

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

Specific examples of the organometallic catalyst (D) include zirconium alkoxide, zirconium chelate, titanium alkoxide, titanium chelate, tin alkoxide, and tin chelate. Among these, zirconium chelate is preferable. 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 organometallic catalyst (D) used in the reaction for obtaining the (meth)acrylic acid ester copolymer (A) into which an energy beam curable group is introduced into the side chain is not limited. The amount used is preferably 0.001 to 10 parts by mass, particularly preferably 0.01 to 5 parts by mass, in terms of the amount of metal, based on 100 parts by mass of solid content of the (meth)acrylic acid ester copolymer (A). It is preferably 3 parts by mass. In addition, in the present invention, the metal amount conversion refers to a blending amount or blending ratio calculated based on the mass of the metal alone, excluding the mass corresponding to the molecular weight of the structure composed of organic matter, in the organometallic catalyst (D).

(5) Other ingredients

In addition to the above components, the adhesive composition forming the adhesive layer in this embodiment may contain various additives such as photopolymerization initiators, crosslinking accelerators, coloring materials such as dyes and pigments, flame retardants, fillers, and antistatic agents.

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-hydroxycyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrate. Examples include ronitrile, dibenzyl, diacetyl, β-chloranthraquinone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. When using ultraviolet rays as energy rays, the irradiation time and irradiation amount can be reduced by mixing a photopolymerization initiator.

When the adhesive composition forming the adhesive layer in this embodiment contains a crosslinking agent (C), it may contain an appropriate crosslinking accelerator depending on the type of the crosslinking agent (C), etc.

(6) Irradiation of energy lines

In the adhesive sheet for glass dicing according to the present embodiment, when the adhesive layer is made of an energy ray-curable adhesive, the energy rays for curing the adhesive include ionizing radiation, that is, ultraviolet rays, electron beams, X-rays, etc. You can. Among these, ultraviolet rays are preferable because they are relatively easy to introduce into irradiation equipment.

When using ultraviolet rays as ionizing radiation, it is preferable to use near-ultraviolet rays containing ultraviolet rays with a wavelength of about 200 to 380 nm for ease of handling. The amount of light may be appropriately selected depending on the type of energy ray-curable component contained in the adhesive composition or the thickness of the adhesive layer, and is usually about 50 to 500 mJ/cm2, with 100 to 450 mJ/cm2 being preferred, and 200 to 200 mJ/cm2. 400 mJ/cm2 is more preferable. Moreover, the ultraviolet irradiance is usually about 50 to 500 mW/cm2, preferably 100 to 450 mW/cm2, and more preferably 200 to 400 mW/cm2. There are no particular restrictions on the ultraviolet ray source, and for example, high-pressure mercury lamps, metal halide lamps, UV-LEDs, etc. are used.

When using an electron beam as an ionizing radiation, the acceleration voltage can be appropriately selected depending on the type of energy beam curable component contained in the adhesive composition or the thickness of the adhesive layer, and the acceleration voltage is usually about 10 to 1000 kV. desirable. Additionally, the irradiation dose can be set within a range that allows the adhesive to properly harden, and is usually selected in the range of 10 to 1000 krad. The electron beam source is not particularly limited, and for example, various electron beam accelerators such as Cockcroft-Walton type, Vandergraaff type, resonant transformer type, insulating core transformer type, or linear type, dynamitron type, or high-frequency type can be used. .

3. Release film

In the adhesive sheet for glass dicing according to the present embodiment, a release film may be laminated on the side of the adhesive layer opposite to the base material while the adherend is attached, for the purpose of protecting the side. The structure of the release film is arbitrary, and an example is a plastic film subjected to a release treatment with a release agent or the like. Specific examples of plastic films 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-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, etc. can be used. Among these, silicone-based release agents are preferred because they are inexpensive and provide stable performance. The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.

4. Physical properties of adhesive sheet for glass dicing

The adhesive force of the adhesive sheet for glass dicing according to this embodiment to the alkali-free glass after attaching the surface of the adhesive layer opposite to the base material to alkali-free glass and leaving it still for 20 minutes is 8000 to 25000 mN/ It is preferably 25 mm, especially preferably 9000 to 22000 mN/25 mm, and more preferably 10000 to 19000 mN/25 mm. When the adhesive force is within the above range, the glass chip is well maintained on the adhesive sheet during dicing. Accordingly, collisions between glass chips resulting from misalignment of glass chips on the adhesive sheet and unintentional collisions between the cutting surfaces of the glass plate or glass chips and the dicing blade are effectively suppressed, and chipping is effectively suppressed. In addition, as a result of making it possible to maintain the glass plate well on the adhesive sheet during dicing, the occurrence of chip scattering and die shift is also suppressed. In addition, in this specification, when the adhesive layer is made of the above-mentioned energy ray curable adhesive, the adhesive force is taken as the value measured before energy ray irradiation.

When the pressure-sensitive adhesive layer is made of the energy-beam curable pressure-sensitive adhesive described above, the surface of the pressure-sensitive adhesive layer opposite to the base material is affixed to alkali-free glass, and the pressure-sensitive adhesive layer is irradiated with energy rays. The adhesive force of the adhesive sheet for glass dicing to alkali-free glass is preferably 50 to 250 mN/25 mm, particularly preferably 60 to 160 mN/25 mm, and more preferably 70 to 130 mN/25 mm. do. When the adhesive force after energy ray irradiation is 50 mN/25 mm or more, it is possible to prevent the glass chip from unintentionally peeling off or shifting from the adhesive sheet in the step before picking up the glass chip from the adhesive sheet, Pickup can be performed more satisfactorily. On the other hand, since the adhesive force after energy ray irradiation is 250 mN/25 mm or less, for example, when picking up glass chips individually, the glass chips can be picked up satisfactorily without being damaged, and adhesive residue can be removed. The occurrence of can be suppressed.

In addition, the adhesive force in this specification is the adhesive force (mN/25 mm) measured by the 180° peeling method according to JIS Z0237:2009 using alkali-free glass as the adherend, and details of the measuring method are described later. It is 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 is not particularly limited as long as the adhesive layer formed from the above-described adhesive composition can be laminated on one side of the substrate.

As an example of a method for producing an adhesive sheet for glass dicing, first, a coating composition containing the above-described adhesive composition and a solvent or dispersion medium as desired is prepared. Next, this coating composition is applied to one side of the substrate using a die coater, curtain coater, spray coater, slit coater, knife coater, etc. to form a coating film. Additionally, an adhesive layer can be formed by drying the coating film. The properties of the coating composition are not particularly limited as long as it can be applied. The component for forming the adhesive layer may be contained as a solute or a dispersoid in the coating composition.

When the coating composition contains a crosslinking agent (C), the above drying conditions (temperature, time, etc.) may be changed or heat treatment may be provided separately in order to form a crosslinked structure at a desired density. In order to sufficiently advance the crosslinking reaction, after laminating the adhesive layer on the substrate by the above method, etc., the obtained adhesive sheet for glass dicing is left to stand in an environment of, for example, 23°C and 50% relative humidity for about 1 to 2 weeks. You can also carry out curing.

In another example of the method for producing an adhesive sheet for glass dicing, first, a coating composition is applied onto the peeling treated surface of the peeling film as described above to form a coating film. Next, the coating film is dried to form a laminate consisting of an adhesive layer and a release film. Additionally, the side of the adhesive layer of this laminate opposite to the release film is attached to the base material. By the above, a laminate of the adhesive sheet for glass dicing and the release film can be obtained. The release film in this laminate may be peeled off as a process material, and may protect the adhesive layer until it is affixed to the adherend.

6. How to use adhesive sheet for glass dicing

The 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 also be used for a series of processes including dicing of a glass plate and the pickup following it.

When used in a series of processes including dicing and subsequent pickup, first, the surface opposite to the base material in the adhesive layer of the adhesive sheet for glass dicing according to this embodiment (hereinafter referred to as “adhesive surface”) (There are cases) is attached to the glass plate. When a release film is laminated on the adhesive surface, the release film is peeled off and a glass plate is attached to the exposed adhesive surface. Meanwhile, the peripheral edge of the adhesive surface is attached to an annular jig called a ring frame for transportation or fixation to the device. In addition, after attaching the glass plate, it is preferable to leave it for 10 to 120 minutes, and especially preferably for 15 to 60 minutes, and further for 20 to 40 minutes. It is desirable to engage in politics. By allowing it to stand for such a period of time, the adhesion between the glass plate and the adhesive sheet can be ensured to be sufficient.

Next, a dicing process is performed. That is, the glass plate affixed on the adhesive sheet for glass dicing is cut using a dicing blade. Accordingly, a plurality of glass chips affixed on the adhesive sheet for glass dicing are obtained. In the adhesive sheet for glass dicing according to the present embodiment, when the base material has the thickness described above, handling properties as an adhesive sheet become good. In addition, because the storage modulus of the adhesive layer at 100°C is within the above-mentioned range, when the temperature of the adhesive layer becomes high, such as about 100°C, due to frictional heat during dicing, shaking occurs during dicing. As a result of this being sufficiently suppressed, the occurrence of chipping can be suppressed even when dicing a thin glass plate into small chips. As a result, it becomes possible to efficiently obtain small chips from thin glass plates.

When the adhesive layer is made of the energy ray-curable adhesive described above, after the dicing process is completed, the adhesive sheet on which a plurality of glass chips are attached is irradiated with energy rays from the surface on the glass chip side or the surface on the substrate side. As a result, the polymerization reaction of the energy ray curable group of the (meth)acrylic acid ester copolymer (A) progresses, the adhesiveness decreases, and the subsequent pickup process becomes easier to perform.

The pickup process can be performed by general-purpose means such as a suction collet. At this time, in order to make it easier to pick up, it is preferable to push up the target glass chip with a pin or needle, etc. from the side of the base material opposite to the adhesive layer. In the adhesive sheet for glass dicing according to the present embodiment, when the thickness of the base material is within the range described above, the adhesive sheet has good flexibility. Accordingly, good pickup can be performed.

Additionally, it is preferable to perform an expand process before the pick-up process. In this case, the adhesive sheet for glass dicing is stretched in the plane direction. Accordingly, the gap between glass chips widens, making it easier to pick them up. The degree of elongation may be set appropriately in consideration of the desired spacing, the tensile strength of the base material, etc. Additionally, the expand process may be performed before energy ray irradiation.

In addition, when dicing a glass plate using the adhesive sheet for glass dicing according to the present embodiment, the area of the plane of the glass chip obtained is preferably 1 × 10 ^-6 mm2 to 1 mm2, and 1 × 10 ^-4 It is more preferable that it is 0.25 mm2 to 0.25 mm2, and especially preferably 2.5 x 10 ^-3 mm2 to 0.09 mm2, and more preferably 0.01 mm2 to 0.03 mm2. According to the adhesive sheet for glass dicing according to the present embodiment, the storage elastic modulus at 100°C of the adhesive layer is within the above-described range, so that shaking of the adhesive sheet during dicing is suppressed, so the area within the above range is Even small glass chips can be obtained while suppressing the occurrence of chipping.

When dicing a glass plate using the adhesive sheet for glass dicing according to the present embodiment, the thickness of the glass plate used as the workpiece is preferably 50 to 10000 μm, especially preferably 100 to 5000 μm, and furthermore 300 μm. It is preferably ~800 ㎛. In addition, in this specification, “work” refers to an adherend to which the adhesive sheet for glass dicing according to the present embodiment is affixed, or a workpiece to be processed using the adhesive sheet. According to the adhesive sheet for glass dicing according to the present embodiment, the storage elastic modulus at 100°C of the adhesive layer is within the above-described range, so that shaking of the adhesive sheet during dicing is suppressed, and thus the adhesive sheet has a thickness of 50 μm. Even thin glass plates can be diced while suppressing chipping.

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 embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

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

Example

Hereinafter, the present invention will be described in more detail through examples, etc., but the scope of the present invention is not limited to these examples. In addition, the description of the mass part below is described as a solid content conversion value.

[Example 1]

(1) Preparation of (meth)acrylic acid ester copolymer (A)

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

Next, the obtained acrylic copolymer (AP) and 2-methacryloyloxyethyl isocyanate (MOI) as the energy ray-curable group-containing compound (A3) were used as a zirconium chelate catalyst (Matsumoto Fine Chemical Co., Ltd.) as the organometallic catalyst (D). The reaction was carried out in the presence of (manufactured by, product name “ZC-700”). Accordingly, a (meth)acrylic acid ester copolymer (A) in which an energy ray-curable group (methacryloyl group) was introduced into the side chain was obtained. At this time, the two were reacted so that the MOI was 60 mol (60 mol%) per 100 mol of 2-hydroxyethyl acrylate units of the acrylic copolymer (AP). In addition, the compounding amount of the organometallic catalyst (D) was 0.1 part by mass with respect to 100 parts by mass of the acrylic copolymer (AP).

(2) Preparation of adhesive composition

100 parts by mass of the (meth)acrylic acid ester copolymer (A) obtained in the above step (1), and 3.0 parts by mass of α-hydroxycyclohexylphenyl ketone (manufactured by BASF, product name “Irgacure 184”) as a photopolymerization initiator. and 0.2 parts by mass of trimethylolpropane-modified tolylene diisocyanate (manufactured by Tosoh Corporation, product name "Colonate L") as a crosslinking agent (C) were mixed in a solvent to obtain a coating solution of the adhesive composition. Additionally, by using this adhesive composition, an X-type adhesive is obtained.

(3) Manufacturing of adhesive sheets for glass dicing

The coating solution of the adhesive composition obtained in the above step (2) was applied to the peeled surface of a release film (manufactured by Lintec, product name "SP-PET381031", thickness: 38 ㎛) obtained by peeling one side of a polyethylene terephthalate film with a silicone-based release agent. It was applied with a die coater. Next, treatment was performed at 100°C for 1 minute to dry the coating film and to advance the crosslinking reaction. Accordingly, a laminate consisting of a release film and an adhesive layer with a thickness of 10 μm was obtained. Additionally, a polyethylene terephthalate (PET) film (manufactured by Toyobo Corporation, product name “A-4100”, thickness: 100 μm) as a substrate was bonded to the side of the laminate on the adhesive layer side. Accordingly, an adhesive sheet for glass dicing was obtained in which the base material, the adhesive layer, and the release film were laminated in that order.

[Examples 2 to 12]

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

[Comparative Example 1]

A pressure-sensitive adhesive sheet for glass dicing was manufactured in the same manner as in Example 1, except that the thickness of the base material was changed as shown in Table 1.

[Comparative Example 2]

(1) Preparation of adhesive composition

90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid were copolymerized to obtain an acrylic polymer (N) without energy ray curability. As a result of measuring the molecular weight of the obtained polymer (N), the weight average molecular weight (Mw) was 600,000.

100 parts by mass of an acrylic polymer (N) without energy ray curability obtained as described above, and a trifunctional urethane acrylate oligomer as an energy ray curable compound (B) (manufactured by Dainichi Seika Industries, Ltd., product name "EXL810TL", Mw = 5000) 127 parts by mass, 4 parts by mass of α-hydroxycyclohexylphenyl ketone (manufactured by BASF, product name “Irgacure 184”) as a photopolymerization initiator, and trimethylolpropane-modified tolylene diisocyanate (manufactured by Tosoh Corporation, product name) as a crosslinking agent. 11 parts by mass of “Colonate L”) were mixed in a solvent to obtain a coating solution of the adhesive composition. Additionally, by using this adhesive composition, a Y type adhesive is obtained.

(2) Manufacturing of adhesive sheets for glass dicing

A pressure-sensitive adhesive sheet for glass dicing was manufactured 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 3]

(1) Preparation of adhesive composition

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

100 parts by mass of an acrylic polymer (N) without energy ray curability obtained as described above, and 10-functional urethane acrylate as an energy ray curable compound (B) (manufactured by Nippon Chemical Industry Co., Ltd., product name "UV-1700B", molecular weight: 1700) ) 40 parts by mass, 0.1 parts by mass of α-hydroxycyclohexylphenyl ketone (manufactured by BASF, product name “Irgacure 184”) as a photopolymerization initiator, and trimethylolpropane-modified tolylene diisocyanate (manufactured by Tosoh Corporation, product name) as a crosslinking agent. 10 parts by mass of product name "Colonate L") were mixed in a solvent to obtain a coating solution of the adhesive composition. Additionally, by using this adhesive composition, a Y type adhesive is obtained.

(2) Manufacturing of adhesive sheets for glass dicing

A pressure-sensitive adhesive sheet for glass dicing was manufactured 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 4 and 5]

A pressure-sensitive adhesive sheet for glass dicing was manufactured in the same manner as in Comparative Example 3, except that the thickness of the pressure-sensitive adhesive layer was changed as shown in Table 1.

Details of the abbreviations and other symbols listed in Table 1 are as follows.

[Material of base material]

PET (thickness 100 ㎛): Polyethylene terephthalate film (manufactured by Toyobo Corporation, product name “A-4100”)

PET (thickness 50 ㎛): Polyethylene terephthalate film (manufactured by Toyobo Corporation, product name “A-4100”)

PET (thickness 188 ㎛): Polyethylene terephthalate film (manufactured by Toyobo Corporation, product name “A-4100”)

PO: Polyolefin film (manufactured by Ricken Technos, product name “ADN09-100T-M8”)

PP: Polypropylene film (manufactured by Diaplus Film, product name “PL109”)

PI: Polyimide film (manufactured by MPRTECH, product name “Mordohar PIF100”)

[Organometallic catalyst]

Zr: Zirconium chelate catalyst (manufactured by Matsumoto Fine Chemicals, product name “ZC-700”)

Sn: Dibutyltin laurylate catalyst (manufactured by Toyochem, “BXX-3778”)

[Test Example 1] (Measurement of storage modulus of substrate)

For the substrates used in the examples and comparative examples, the storage 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 Instruments, product name “DMA Q800”

Test start temperature: 0 ℃

Test end temperature: 200℃

Temperature increase rate: 3℃/min

Frequency: 11 ㎐

Amplitude: 20 ㎛

[Test Example 2] (Measurement of storage modulus of adhesive layer before ultraviolet irradiation)

The coating solution of the adhesive composition used in the Examples and Comparative Examples was applied onto the peeling-treated surface of a 38-μm-thick first peeling film (manufactured by Lintec, product name "SP-PET381031"). The obtained coating film was dried by holding it at 100°C for 1 minute. Accordingly, an adhesive layer with a thickness of 40 μm was formed on the first release film. Additionally, the peeling-treated surface of a 38-μm-thick second peeling film (manufactured by Lintec, product name “SP-PET381031”) is bonded to the side of the adhesive layer opposite to the first peeling film, and the first peeling is carried out. A laminate was obtained by laminating a film, a 40-μm-thick adhesive layer, and a second peeling film in this order. The adhesive layer obtained through the above procedure was laminated in multiple layers so as to have a thickness of 800 μm. A circular shape with a diameter of 10 mm was punched out from this 800 μm thick laminate to serve as a sample for measurement. Using a viscoelasticity measuring device (manufactured by TA Instruments, product name "ARES"), a strain at a frequency of 1 Hz was applied to the sample, the storage elastic modulus was measured at -50 to 150°C, and the storage elastic modulus at 23°C and 100°C was measured. The value of was obtained. The results are shown in Table 1. In addition, when laminating multiple adhesive layers, the laminate that was left for one week in an environment with a temperature of 23°C and a humidity of 50% after forming the adhesive layer was used.

[Test Example 3] (Measurement of tensile modulus of elasticity of adhesive layer after irradiation with ultraviolet rays)

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

Subsequently, the adhesive layer was cured by applying ultraviolet (UV) irradiation (illuminance: 230 mJ/cm2, light quantity: 190 mJ/cm2) using an ultraviolet irradiation device (manufactured by Lintec, product name "RAD-2000"). . Additionally, it was cut into 15 mm x 140 mm to obtain a test piece.

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

[Test Example 4] (Measurement of tag value)

The surface on the adhesive layer side of the adhesive sheets manufactured in the examples and comparative examples was tested using a probe with a diameter of 5 mm (5 mmϕ) using a probe tack tester (manufactured by Resca, product name "RPT-100"). The tack value was measured. The measurement method was as described in JIS Z0237:2009, with the peeling speed changed to 1 mm/min, the load being 100 gf/cm2, and the contact time being 1 second, as described in the above JIS regulations. The measured energy amount (peak integrated value) was determined, and this was used as the selected value (unit: mJ/5 mmϕ). The results are shown in Table 1. In addition, for the above measurement, an adhesive sheet that was left for one week in an environment with a temperature of 23°C and a humidity of 50% after forming the adhesive layer was used.

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

The release film was peeled from the adhesive sheet for glass dicing prepared in the examples and comparative examples at room temperature and left for one week in an environment with a temperature of 23°C and a humidity of 50%. The surface where the adhesive layer was exposed was overlapped on one side of a 6-inch alkali-free glass plate, a load was applied and bonded by reciprocating a 2 kg roller once, and the plates were left for 20 minutes. Afterwards, the adhesive sheet for glass dicing was peeled from the alkali-free glass plate using a 180° peeling method in accordance with JIS Z0237:2009 at a peeling speed of 300 mm/min and a peeling angle of 180°, and the adhesive force (mN/25 mm) was measured. Measured. This measured value was taken as the adhesive force before ultraviolet irradiation. The results are shown in Table 1.

Also, in the same manner as above, the adhesive sheet for glass dicing manufactured in Examples and Comparative Examples and the 6-inch alkali-free glass plate were bonded together, left to stand for 20 minutes, and then irradiated with an ultraviolet irradiation device (Lin) from the substrate side of the adhesive sheet for glass dicing. Ultraviolet ray (UV) irradiation (illuminance: 200 mJ/cm2, light quantity: 180 mJ/cm2) was performed using Tecsa, product name "RAD-2000", and the adhesive layer was cured. After that, the adhesive force (mN/25 mm) was measured in the same manner as above. This measured value was taken as the adhesive force after ultraviolet irradiation. The results are shown in Table 1.

[Test Example 6] (Chipping Evaluation)

The release film was peeled from the adhesive sheet for glass dicing prepared in the examples and comparative examples and left for 1 week in an environment of 23° C. and 50% humidity, and placed on a tape mounter (manufactured by Lintec, product name “Adwill RAD2500m/12”). ), a 6-inch alkali-free glass plate with a thickness of 550 μm and a ring frame for dicing were attached to the surface where the adhesive layer was exposed. Subsequently, the adhesive sheet for glass dicing was cut to match the outer diameter of the ring frame. Furthermore, using a dicing device (product name "DFD-651" manufactured by Disco Corporation), dicing was performed to cut from the glass plate side under the following dicing conditions to obtain glass chips measuring 0.6 mm in width and height.

＜Dicing conditions＞

· Dicing device: DFD-651 manufactured by Disco.

Blade: NBC-2H 2050 27HECC manufactured by Disco

·Blade width: 0.025 ~ 0.030 mm

·Blade tip protrusion: 0.640 ~ 0.760 ㎜

·Blade rotation speed: 30000 rpm

·Cutting speed: 80 mm/sec

·Substrate penetration depth: 20 ㎛

·Amount of cutting water: 1.0 ℓ/min

·Cutting water temperature: 20℃

· Dicing size: 0.6 ㎜ width and height (flat area is 0.36 ㎟)

After dicing was completed, the presence or absence of defects at the ends and the shape of the glass chips located in and near the center of the adhesive sheet for glass dicing were observed. Specifically, using an electron microscope (manufactured by KEYENCE, product name "VHZ-100", magnification: 300x), 50 chip deviations in the flow direction (MD direction) during manufacture of the substrate and orthogonal to the MD direction were measured. 50 chip variations were observed in the direction (CD direction). Then, defects with a width or depth of 20 ㎛ or more were determined to be chipping, and their number was counted. Based on these results, chipping was evaluated based on the following criteria. The evaluation results are shown in Table 1.

◎: The number of chips where chipping occurred is less than 5.

○: The number of chips where chipping occurred is 5 or more but less than 50.

×: The number of chips in which chipping occurred is 50 or more.

[Test Example 7] (Evaluation of handling properties)

The release film was peeled from the adhesive sheet for glass dicing prepared in the Examples and Comparative Examples and left for 1 week in an environment of 23° C. and 50% humidity, and placed on a dicing tape mounter (manufactured by Lintec, product name “RAD-2500F”) /8"), it was attached to a 6-inch alkali-free glass plate with a thickness of 550 μm and a ring frame on the exposed side of the adhesive layer. This operation was repeated 50 times, and the handling properties of the adhesive sheet were evaluated based on the following.

○: It was possible to apply the product 50 times in succession without any special problems occurring.

×: An error occurred along the way and the work was stopped, making it impossible to apply the paste 50 times in succession.

As can be seen from Table 1, according to the adhesive sheet according to the example, the occurrence of chipping can be suppressed. Additionally, it can be seen that the adhesive sheets according to the examples have excellent handling properties.

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

Claims (13)

An adhesive sheet for glass dicing comprising a base material and an adhesive layer laminated on at least one side of the base material,
The thickness of the substrate is 30 ㎛ or more and less than 130 ㎛,
The storage modulus of the adhesive layer at 100°C is 6 to 50 kPa,
The adhesive layer does not contain phthalic acid esters.
An adhesive sheet for glass dicing, characterized in that: According to claim 1,
An adhesive sheet for glass dicing, characterized in that the thickness of the adhesive layer is 5 to 25 ㎛. According to claim 1,
An adhesive sheet for glass dicing, wherein the adhesive layer has a storage modulus of 30 to 100 kPa at 23°C. According to claim 1,
The adhesive force of the adhesive sheet for glass dicing to the alkali-free glass after attaching the surface of the adhesive layer opposite to the substrate to alkali-free glass and leaving it to stand for 20 minutes is 8000 to 25000 mN. /25 mm Adhesive sheet for glass dicing. According to claim 1,
The amount of energy in the adhesive layer measured using a probe tack in the method described in JIS Z0237:1991 under the condition that the peeling speed was changed to 1 mm/min was 0.01 to 5 mJ/5 mmϕ. Features an adhesive sheet for glass dicing. According to claim 1,
An adhesive sheet for glass dicing, wherein the adhesive layer is made of an energy-ray curable adhesive. According to claim 6,
An adhesive sheet for glass dicing, characterized in that the adhesive layer is made of an adhesive formed from an adhesive composition containing a (meth)acrylic acid ester copolymer (A) into which an energy ray curable group is introduced into the side chain. According to claim 7,
An adhesive sheet for glass dicing, characterized in that the adhesive composition further contains an energy ray curable compound (B) other than the (meth)acrylic acid ester copolymer (A). According to claim 7,
An adhesive sheet for glass dicing, characterized in that the adhesive composition further contains a crosslinking agent (C). According to claim 1,
An adhesive sheet for glass dicing, characterized in that the storage modulus of the base material at 23°C is 100 to 8000 MPa. A method for producing the adhesive sheet for glass dicing according to claim 7, comprising:
An acrylic copolymer (AP) obtained by copolymerizing at least an (meth)acrylic acid alkyl ester monomer (A1) and a functional group-containing monomer (A2) having a reactive functional group,
Compound (A3) containing an energy ray-curable group having 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.
A step of reacting to prepare a (meth)acrylic acid ester copolymer (A) into which an energy beam curable group is introduced into the side chain, and
A process of laminating an adhesive layer on at least one side of a substrate using an adhesive composition containing the (meth)acrylic acid ester copolymer (A).
A method of manufacturing an adhesive sheet for glass dicing, comprising: According to claim 11,
The reaction between the acrylic copolymer (AP) and the energy ray-curable group-containing compound (A3) is carried out with at least one organic compound selected from the group consisting of an organic compound containing zirconium, an organic compound containing titanium, and an organic compound containing tin. A method for producing an adhesive sheet for glass dicing, characterized in that it is carried out in the presence of a metal catalyst (D). According to claim 1,
An adhesive sheet for glass dicing, characterized in that it is for dicing a glass plate into glass chips having a plane area of 1 × 10 ^-6 mm2 to 1 mm2.