KR20170113059A - Glass dicing adhesive sheet and method of manufacturing the same - Google Patents

Abstract

A pressure-sensitive adhesive sheet for glass dicing, in which chip scattering does not occur at the time of dicing, occurrence of chipping and die shift is suppressed, good pick-up is possible, And a manufacturing method thereof.
A pressure-sensitive adhesive sheet for glass dicing comprising a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material, wherein the thickness of the base material is 30 占 퐉 or more and less than 130 占 퐉 and the thickness of the pressure- And more preferably 40 占 퐉 or less.
(Selectivity) None

Description

Technical Field [0001] The present invention relates to a pressure-sensitive adhesive sheet for glass dicing,

The present invention relates to a pressure-sensitive adhesive sheet for glass dicing, which is used for dicing a glass plate to obtain a glass chip, and a manufacturing method thereof.

In manufacturing a camera module mounted on a cellular phone or a smart phone, a minute glass piece is required. Such glass pieces can be obtained by dicing a single glass plate using a dicing sheet. That is, after the glass plate is stuck to the dicing sheet, the glass plate is cut by the dicing blade to obtain a glass piece (hereinafter, also referred to as "glass chip"). 2. Description of the Related Art In recent years, the thinning of smart phones and the like has progressed, and a camera module to be mounted is also downsized. As a result, there is a need to manufacture thinner and finer glass chips (hereinafter referred to as " small chips ").

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

It is required that the dicing sheet described above does not cause a phenomenon (hereinafter also referred to as " chip scattering ") in which the formed glass chips are scattered and scattered from the sheet when dicing is performed.

Patent Document 1 discloses a pressure-sensitive adhesive sheet for glass substrate dicing, in which a pressure-sensitive adhesive layer is formed on a base film. Patent Document 1 discloses a technique in which a film having a thickness of 130 占 퐉 or more and a tensile modulus of 1 占 ㎬ or more is used as the base film and the thickness of the pressure-sensitive adhesive layer is 9 占 퐉 or less so that the deformation of the pressure- And can suppress the occurrence of chipping and chip scattering (paragraph 0010 of patent document 1).

Japanese Patent Publication No. 3838637

In recent years, the miniaturization of the camera module has progressed, and the size of the glass chip, which is required, has become very small. In the adhesive sheet disclosed in Patent Document 1, chip scattering of such a small chip can not be sufficiently suppressed.

In addition, with the miniaturization of the glass chip, a problem called a die shift tends to occur. This is because, when a small chip is manufactured, the contact area between the glass chip and the pressure sensitive adhesive sheet becomes small, and the displacement of the glass plate or the glass chip on the pressure sensitive adhesive sheet tends to occur due to vibration of the dicing. When a die shift occurs, dicing at an intended position can not be performed, and a glass chip having a desired shape can not be obtained. For this reason, it is required that die shift does not occur in the manufacture of a small chip.

Incidentally, in the production of a glass chip, a pickup process may be carried out in the state that the glass chip is attached to the dicing sheet after the above-described dicing process. In this process, it is required that the glass chip is picked up improperly without damaging the glass chip when the glass chip is picked up incorrectly or picked up. Further, it is required that the picked-up glass chip is not attached with a pressure-sensitive adhesive derived from the dicing sheet (hereinafter sometimes referred to as " pressure-sensitive adhesive residue ").

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances, and it is an object of the present invention to provide a chip package that does not cause chip scattering during dicing, suppresses occurrence of chipping and die shift, enables satisfactory pickup, And an adhesive sheet for glass dicing that does not cause adhesion, and a method for producing the same.

In order to attain the above object, firstly, the present invention provides a pressure-sensitive adhesive sheet for glass dicing comprising a substrate and a pressure-sensitive adhesive layer laminated on at least one surface of the substrate, wherein the thickness of the substrate is 30 탆 or more and less than 130 탆 , And the thickness of the pressure-sensitive adhesive layer is more than 9 占 퐉 and not more than 40 占 퐉 (Invention 1).

In the above invention (Invention 1), handling properties of the pressure-sensitive adhesive sheet for glass dicing are improved by having the base material having the thickness described above. In addition, when the pressure-sensitive adhesive layer has the above-mentioned thickness, the pressure-sensitive adhesive layer exhibits excellent tack and the glass chip is favorably held in the pressure-sensitive adhesive sheet for glass dicing, so that chip scattering is suppressed at the time of dicing. Further, when the pressure-sensitive adhesive layer and the base material each have the thickness described above, occurrence of chipping and die shift is suppressed, satisfactory pickup becomes possible, and adhesive residue is less likely to remain. Particularly, when the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer is an X-type pressure-sensitive adhesive described below, the effects on chipping, die shift, pick-up and adhesive remnant become remarkable.

In the above invention (Invention 1), it is preferable that the pressure-sensitive adhesive layer is made of an energy radiation curable pressure-sensitive adhesive (invention 2).

In the invention (Invention 2), the pressure-sensitive adhesive layer preferably comprises a pressure-sensitive adhesive formed from a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer (A) having an energy radiation curable group introduced into its side chain. .

In the above invention (Invention 1 to 3), the amount of energy measured by the probe test using the pressure-sensitive adhesive layer under the condition of changing the peeling speed to 1 mm / min in the method described in JIS Z0237: 1991 , And 0.01 to 5 mJ / 5 mmφ (invention 4).

In the above inventions (inventions 1 to 4), it is preferable that the pressure-sensitive adhesive layer has a storage elastic modulus at 23 캜 of 30 to 100 ((invention 5).

In the above inventions (Invention 1 to 5), the surface of the pressure-sensitive adhesive layer opposite to the substrate was attached to an alkali-free glass, and after standing for 20 minutes, It is preferable that the adhesive force is 8000 to 25000 mN / 25 mm (invention 6).

In the above invention (Invention 2 or 3), after the surface of the pressure-sensitive adhesive layer opposite to the substrate is attached to alkali-free glass and the energy ray is irradiated to the pressure-sensitive adhesive layer, The adhesive force to the alkali-free glass is preferably 50 to 250 mN / 25 mm (invention 7).

In the invention (Inventions 2, 3 and 7), the tensile modulus of elasticity of the pressure-sensitive adhesive layer at 23 캜 after irradiation with energy rays is preferably 15 to 1500 MPa (Inventive 8).

In the above inventions (Invention 1 to 8), the storage modulus of the base material at 23 캜 is preferably 100 to 8000 MPa (Invention 9).

In the above invention (Invention 3), it is preferable that the pressure-sensitive adhesive composition further contains a crosslinking agent (C) (Invention 10).

In the above inventions (Invention 1 to 10), it is preferable that the glass plate is for dicing into a glass chip whose plane has an area of 1 x 10 ^-6 mm 2 to 1 mm 2 (invention 11).

Secondly, the present invention relates to a process for producing the pressure-sensitive adhesive sheet for glass dicing (invention 3), which comprises the steps of: (1) preparing an acrylic-based copolymer (A3) having a functional group capable of reacting with a functional group of the functional group-containing monomer (A2) and an energy ray-curable group having an energy ray-curable carbon-carbon double bond is reacted with an energy radiation curable (Meth) acrylate ester copolymer (A) having a group-introduced (meth) acrylate ester copolymer (A) and a pressure-sensitive adhesive composition containing the The present invention also provides a method for producing a pressure-sensitive adhesive sheet for glass dicing, comprising the steps of:

In the above invention (invention 12), the reaction between the acrylic copolymer (AP) and the energy ray-curable group-containing compound (A3) is carried out by reacting an organic compound containing zirconium, an organic compound containing titanium, In the presence of at least one organometallic catalyst (D) selected from the compounds (invention 13).

According to the adhesive sheet for glass dicing according to the present invention and the adhesive sheet for glass dicing produced by the manufacturing method according to the present invention, chip scattering does not occur at the time of dicing, and occurrence of chipping and die shift It is possible to perform a satisfactory pickup, and further, the adhesive residue is not generated well.

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 comprises a base material and a pressure-sensitive adhesive layer laminated on one surface of the base material.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the substrate is 30 占 퐉 or more and less than 130 占 퐉. The thickness of the pressure-sensitive adhesive layer is more than 9 占 퐉 and not more than 40 占 퐉.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, handling property with respect to glass dicing is improved by having the substrate having the above thickness.

Further, in the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer has the above thickness, so that the pressure-sensitive adhesive layer exhibits excellent tackiness. As a result, the glass chips formed by the dicing are favorably held on the adhesive sheet. As a result, even when the glass chip is impacted at the time of dicing, the glass chip is prevented from falling off the adhesive sheet. That is, chip scattering is prevented.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, as described above, the pressure-sensitive adhesive sheet exhibits excellent tack, so that the glass chip is favorably retained on the pressure-sensitive adhesive sheet during dicing. As a result, collision between the glass chips due to the deviation of the glass chips on the pressure-sensitive adhesive sheet, and unintentional collision of the cut surface of the glass plate or the glass chip and the dicing blade are suppressed. In addition, when the thickness of the base material is in the above-described range, the occurrence of chipping can be suppressed even when a thin glass plate is diced into small chips.

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

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the pressure-sensitive adhesive layer is in the range described above, so that the pressure-sensitive adhesive sheet has adhesive force capable of easily picking up the glass chip. In addition, when the thickness of the base material is in the above-mentioned range, the pressure-sensitive adhesive sheet has good flexibility, and as a result, the pickup can be satisfactorily performed.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer and the substrate each have the thickness described above, so that the pressure-sensitive adhesive derived from the pressure-sensitive adhesive layer is hardly left on the glass chip picked up. In particular, when the pressure-sensitive adhesive layer is made of an X-type pressure-sensitive adhesive described below, the X-type pressure-sensitive adhesive does not contain a low molecular weight compound such as an energy ray curable compound (B) none. Further, when an X-type pressure-sensitive adhesive is formed from a pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition is likely to undergo uniform crosslinking, and the resulting pressure-sensitive adhesive is uniformly crosslinked as a whole. As described above, the occurrence of residual adhesive can be effectively suppressed.

1. Equipment

In the adhesive sheet for glass dicing according to the present embodiment, the thickness of the base material is preferably 30 占 퐉 or more, less than 130 占 퐉, preferably 50 占 퐉 or more and 120 占 퐉 or less, particularly preferably 70 占 퐉 or more and 110 占 퐉 or less. If the thickness of the substrate is less than 30 占 퐉, the pressure sensitive adhesive sheet tends to be shaken during the dicing step, and the glass plate easily moves on the pressure sensitive adhesive sheet, resulting in easy chipping and die shift. Further, the pressure-sensitive adhesive sheet tends to be broken when handling the pressure-sensitive adhesive sheet or during the expanding process. On the other hand, when the thickness of the base material is 130 占 퐉 or more, the flexibility of the entire pressure sensitive adhesive sheet deteriorates and the pressure sensitive adhesive sheet tends to fall off from the ring frame or the jig when sticking to a ring frame or a dicing jig, Loses.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the storage modulus of the base material at 23 캜 is preferably 100 to 8000 MPa, more preferably 1500 to 7000 MPa, further preferably 2000 to 6000 MPa Do. Since the storage elastic modulus of the substrate at 23 deg. C is 100 MPa or more, the occurrence of shaking of the adhesive sheet in the dicing step is reduced and the movement of the glass sheet on the adhesive sheet is suppressed. As a result, It is possible to effectively suppress the occurrence of such a phenomenon. Further, when the base material has a storage modulus at 23 캜 of 8000 MPa or less, flexibility of the base material is ensured and the stretchability (expandability) of the base material is more excellent. As a result, at the time of the expanding process, the pressure-sensitive adhesive sheet exhibits excellent expandability and the glass chips after dicing can be picked up more satisfactorily. The storage elastic modulus of the base material at 23 캜 was measured under the following conditions using a dynamic elastic modulus measuring device (product name: DMA Q800, manufactured by TA Instruments Co., Ltd.).

Test start temperature: 0 ° C

Test end temperature: 200 ° C

Heating rate: 3 ° C / min

Frequency: 11 Hz

Amplitude: 20 탆

The base material of the adhesive sheet for glass dicing according to the present embodiment is not particularly limited as long as it has the above-described thickness. The base material may include a film (resin film) based on a resin-based material. Preferably, the substrate is made of only a resin film. Specific examples of the resin film include an ethylene copolymer film such as an ethylene-vinyl acetate copolymer film, an ethylene- (meth) acrylic acid copolymer film and an ethylene- (meth) acrylic acid ester copolymer film; a polyethylene film, Polyolefin films such as polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film and norbornene resin film, polyvinyl chloride films such as polyvinyl chloride film and vinyl chloride copolymer film ; A polyester film such as a polyethylene terephthalate film and a polybutylene terephthalate film; a polyurethane film; a polyimide film; a polystyrene film; a polycarbonate film; and a fluororesin film. Examples of the polyethylene film include a low-density polyethylene (LDPE) film, a linear low-density polyethylene (LLDPE) film, and a high-density polyethylene (HDPE) film. Also, a modified film such as a crosslinked film or an ionomer film may be used. The base material may be a film made of one of these, or a laminated film in which two or more kinds of these are combined. Among them, it is preferable to use a polyethylene terephthalate film from the viewpoint of easily achieving the above-mentioned storage elastic modulus. In the present specification, "(meth) acrylic acid" means both of acrylic acid and methacrylic acid. The same is true for other similar terms.

In the substrate, various additives such as a pigment, a dye, a flame retardant, a plasticizer, an antistatic agent, a slip agent, and a filler may be contained in the film. Examples of the pigment 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. The content of these additives is not particularly limited, but it is preferable that the range is such that the substrate exhibits a desired function and does not lose smoothness or flexibility.

When ultraviolet rays are used as the energy ray to be irradiated for curing the pressure-sensitive adhesive layer, it is preferable that the substrate has transparency to ultraviolet rays. When an electron beam is used as the energy beam, it is preferable that the base material has transparency to the electron beam.

The surface of the substrate on the side of the pressure-sensitive adhesive layer may be subjected to surface treatment such as primer treatment, corona treatment, plasma treatment, roughening treatment (matte working) or the like in order to improve adhesion with the pressure-sensitive adhesive layer. Examples of the roughening treatment include an embossing method and a sandblasting method. In addition, various coating films may be formed on the surface of the substrate opposite to the pressure-sensitive adhesive layer.

2. Adhesive layer

(1) Thickness and physical properties of the pressure-sensitive adhesive layer

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the pressure-sensitive adhesive layer is preferably more than 9 占 퐉 and not more than 40 占 퐉, more preferably not less than 9 占 퐉 and not more than 30 占 퐉, particularly preferably not less than 9 占 퐉 and not more than 20 占 퐉 . If the thickness of the pressure-sensitive adhesive layer is 9 占 퐉 or less, the tackiness of the pressure-sensitive adhesive layer is insufficient, and the glass chip can not be sufficiently retained in the pressure-sensitive adhesive sheet during dicing. As a result, chip scattering can not be prevented. When the thickness of the pressure-sensitive adhesive layer exceeds 40 占 퐉, the adhesive force becomes too strong and the glass chips can not be picked up satisfactorily. Further, during the dicing, the pressure-sensitive adhesive layer is liable to be shaken, and as a result, chipping and die shift tend to occur.

The energy amount (also referred to as " tack value " in this specification) measured by using the probe tack in the pressure-sensitive adhesive layer is preferably 0.01 to 5 mJ / 5 mmφ, more preferably 0.13 to 4 mJ / φ, and more preferably 0.18 to 3.5 mJ / 5 mmφ. When the tack value is within the above range, the occurrence of chip scattering during dicing can be effectively suppressed. In the present specification, in the case where the pressure-sensitive adhesive layer is made of a pressure-sensitive adhesive having an energy ray curable property to be described later, the tacky value is a value measured before the energy ray irradiation. In the present specification, the tack value is measured by the method described in JIS Z0237: 2009 under the condition that the peeling speed is changed to 1 mm / min. The details are as shown in the following test examples.

The storage elastic modulus of the pressure-sensitive adhesive layer at 23 캜 is preferably 30 to 100 ㎪, more preferably 40 to 90,, further preferably 50 to 80 ㎪. When the storage elastic modulus is in the above range, the adhesive sheet for glass dicing can exert a better adhesive force, whereby the glass chips can be well retained by the adhesive sheet and chip scattering can be effectively suppressed. In the present specification, in the case where the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive which will be described later, the storage elastic modulus is a value measured before energy ray irradiation. The method of measuring the storage elastic modulus at 23 占 폚 of the pressure-sensitive adhesive layer before the energy ray irradiation is as shown in the following test examples.

The pressure-sensitive adhesive layer preferably has a storage elastic modulus at 100 캜 of 3 to 50 ㎪, more preferably 3 to 30,, further preferably 10 to 30.. Generally, in the pressure-sensitive adhesive sheet for glass dicing, frictional heat is generated at the time of dicing, and the pressure-sensitive adhesive layer is in a high temperature state such as about 100 캜. Even in such a high-temperature state, the pressure-sensitive adhesive layer exhibits a storage elastic modulus of 3 or more, thereby suppressing the occurrence of shaking at the time of dicing and further suppressing the movement of the glass plate on the pressure-sensitive adhesive sheet. As a result, It becomes more difficult to occur. In addition, when the storage modulus is 50 ㎪ or less, the modulus of elasticity of the pressure-sensitive adhesive layer is not extremely increased, and good stickiness can be obtained. As a result, chip scattering during dicing can be effectively suppressed. In the present specification, in the case where the pressure-sensitive adhesive layer is made of an energy ray-curable pressure-sensitive adhesive which will be described later, the storage elastic modulus is a value measured before energy ray irradiation. The method of measuring the storage elastic modulus at 100 占 폚 of the pressure-sensitive adhesive layer before irradiation with energy rays is as shown in the following test examples.

When the pressure-sensitive adhesive layer is made of an energy ray curable pressure-sensitive adhesive described later, the pressure-sensitive adhesive layer preferably has a tensile elastic modulus at 23 ° C after irradiation with energy rays of preferably 15 to 1500 MPa, more preferably 20 to 1000 MPa, It is preferably 20 to 500 MPa. Since the tensile modulus of elasticity is 15 MPa or more, it is possible to perform the pick-up of the glass chip after irradiation with the energy ray more satisfactorily. In addition, when the tensile modulus is 1500 MPa or less, the extensibility of the adhesive sheet for glass dicing is more excellent, and the pickup can be performed more satisfactorily. The method for measuring the tensile modulus at 23 占 폚 of the pressure-sensitive adhesive layer before the energy ray irradiation is as shown in the test examples described later.

The gel fraction of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably 12.5 to 100%, more preferably 37.5 to 100%, further preferably 50 to 95%. When the gel fraction of the pressure sensitive adhesive is within the above range, the physical properties of the above-mentioned pressure sensitive adhesive layer can be easily satisfied. Further, when the gel fraction of the pressure sensitive adhesive is 12.5% or more, the cohesive force of the pressure sensitive adhesive becomes good, and the durability of the pressure sensitive adhesive layer is maintained.

(2) Adhesive constituting the pressure-sensitive adhesive layer

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may be a non-curable pressure-sensitive adhesive or a curable pressure-sensitive adhesive. The curable pressure sensitive adhesive may be in a state before curing or after curing. When the pressure-sensitive adhesive layer is composed of multiple layers, a combination of a non-curable pressure-sensitive adhesive and a curable pressure-sensitive adhesive may be used. Examples of the non-curable pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyester pressure-sensitive adhesives and polyvinyl ether pressure-sensitive adhesives. Examples of the curable pressure-sensitive adhesive include energy ray-curable pressure-sensitive adhesives, thermosetting pressure-sensitive adhesives, and the like.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer is preferably composed of an energy radiation curable pressure-sensitive adhesive, and more preferably an energy ray curable acrylic pressure-sensitive adhesive. Since the pressure-sensitive adhesive layer is made of an energy ray curable pressure-sensitive adhesive, it is possible to cure the pressure-sensitive adhesive by irradiating the pressure-sensitive adhesive layer with energy rays before the pickup process. As a result, the adhesive force of the adhesive sheet to the glass chip is appropriately lowered, and the pickup can be performed well.

Generally, the energy ray curable acrylic pressure sensitive adhesive contains a (meth) acrylic acid ester copolymer (A) having an energy ray curable group introduced into its side chain and an energy ray other than the (meth) acrylic acid ester copolymer (A) (Hereinafter sometimes simply referred to as " X type "), an acrylic polymer (N) having no energy ray curability, and a (meth) acrylic acid ester (Hereinafter sometimes referred to as " Y type " for convenience) formed from a pressure-sensitive adhesive composition containing an energy ray-curable compound (B) other than the copolymer (A) (B) other than the (meth) acrylic ester copolymer (A) and the (meth) acrylic acid ester copolymer (A) Be formed from a hydrous product (hereinafter, may be for convenience be referred to as a "Z-type") is present.

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the pressure-sensitive adhesive layer may be composed of any of these types of pressure-sensitive adhesives. Particularly, since the X-type pressure-sensitive adhesive exhibits a higher elastic modulus at a high temperature, it is possible to effectively suppress chipping and die shift during dicing. Further, since the X-type pressure-sensitive adhesive does not contain a low-molecular compound such as the energy ray curable compound (B), the compound does not remain on the glass chip, and when a cross- Is uniformly crosslinked. Therefore, the occurrence of residual adhesive can be effectively suppressed. Further, in the X type pressure-sensitive adhesive, since only one component of the (meth) acrylic acid ester copolymer (A) is involved in the component for curing by irradiation with energy rays, the imbalance of the component ratio Hardly occurs, and curing can be satisfactorily performed. As a result, since the adhesive force is easily lowered by energy ray irradiation, a better pickup can be achieved. From the above, it is preferable to use an X-type pressure-sensitive adhesive.

The (meth) acrylic ester copolymer (A) having an energy ray-curable group introduced into the aforementioned side chain and the acrylic polymer (N) having no energy radiation curing property may be contained in the pressure sensitive adhesive layer as they are, And may be contained as a crosslinked product.

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

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

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

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

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

As the functional group-containing monomer (A2), those having a reactive functional group capable of reacting with the functional group of the energy ray-curable group-containing compound (A3) are used. Examples of the functional group of the functional group-containing monomer (A2) include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group and an epoxy group. Among them, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is particularly preferable. When a crosslinking agent (C) described later is used, the reactive functional group contained in the functional group-containing monomer (A2) may be reacted with the crosslinking agent (C).

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

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 acids. Specific examples thereof include acrylic acid, methacrylic acid, Maleic acid, itaconic acid, citraconic acid and the like. Of these, acrylic acid is preferable in view of the reactivity and the copolymerization of the carboxyl group. These may be used alone or in combination of two or more.

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

The proportion of the mass of the structural part derived from the functional group-containing monomer (A2) in the total mass of the acrylic copolymer (AP) is preferably 5 to 40 mass%, more preferably 7 to 35 mass% And preferably 10 to 30% by mass. (A3) into the (meth) acrylic acid ester copolymer (A) to which the energy ray-curable group is introduced in the side chain because the ratio of the mass of the structural part derived from the functional group-containing monomer (A2) Can be set within a suitable range. When the functional group-containing monomer (A2) is reacted with the crosslinking agent (C) using a crosslinking agent (C) to be described later, the degree of crosslinking by the crosslinking agent (C), that is, the gel fraction, , And the cohesive force of the pressure-sensitive adhesive layer can be controlled.

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

Examples of other monomers include (meth) acrylic acid esters such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate and ethoxyethyl (Meth) acrylic esters having an aliphatic ring such as (meth) acrylate and cyclohexyl (meth) acrylate; (meth) acrylic acid esters having aromatic rings such as phenyl (meth) acrylate; acrylates such as acrylamide and methacrylamide Amide, (meth) acrylic acid ester, (meth) acrylic acid ester having a non-cross-linkable tertiary amino group such as N, N-dimethylaminoethyl and (meth) acrylic acid N, N-dimethylaminopropyl, vinyl acetate and styrene . These may be used alone or in combination of two or more.

The polymerization of the acrylic copolymer (AP) may be a random copolymer or a block copolymer. The polymerization method is not particularly limited, and polymerization can be carried out by a general polymerization method.

The energy ray-curable 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. Of these, an isocyanate group having high reactivity with a hydroxyl group is preferable.

As the curable group (energy ray curable group) having an energy ray-curable carbon-carbon double bond, a (meth) acryloyl group and the like are preferable. The energy ray-curable carbon-carbon double bond is preferably present in an amount of 1 to 5, particularly 1 to 3, in a molecule of the energy ray-curable group-containing compound (A3).

Examples of the energy ray-curable compound (A3) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl- alpha, alpha -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, Acryloyl mono isocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate, a diisocyanate compound or a polyisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) Acryloyl monoisocyanate compounds obtained by reacting a polyol compound with hydroxyethyl (meth) acrylate, and the like. Of these, 2-methacryloyloxyethyl isocyanate is particularly preferable. The energy ray-curable group-containing compound (A3) may be used alone, or two or more kinds thereof may be used in combination.

(AP) and an acrylic copolymer (AP) and an energy ray-curable group-containing compound (A3) in the preparation of a (meth) acrylic acid ester copolymer (A) having an energy ray- ) Can be carried out by a conventional method. In this reaction step, a reactive functional group derived from the functional group-containing monomer (A2) in the acrylic copolymer (AP) reacts with a functional group in the energy ray-curable group-containing compound (A3). Thus, a (meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced into the side chain is obtained. Further, as 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 the organometallic catalyst (D).

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) in the (meth) acrylate copolymer (A) having the energy ray- To 100 mol%, particularly preferably 40 to 95 mol%, and more preferably 50 to 90 mol%.

The weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) to which the energy ray-curable group is introduced in the side chain is preferably 100,000 to 2,500,000, particularly preferably 150,000 to 2,000,000, more preferably 30 To 1.5 million. The weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC). When the weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) having the energy ray curable group introduced into the side chain is in the above range, the coating property of the pressure sensitive adhesive composition is ensured and the cohesiveness of the pressure sensitive adhesive layer It is possible to obtain physical properties suitable for dicing.

(2-2) Acrylic Polymer Having No Energy Line Curability (N)

As the acrylic polymer (N) having no energy ray curability, conventionally known acrylic polymers may be used as long as they do not have energy ray curability. The acrylic polymer may be a homopolymer formed from one kind of acrylic monomer, a copolymer formed from a plurality of kinds of acrylic monomers, or a copolymer formed from one kind or plural kinds of acrylic monomers and monomers other than acrylic monomers.

The specific kind of the compound to be an acrylic monomer is not particularly limited and specific examples include (meth) acrylic acid, (meth) acrylic acid ester and derivatives thereof (acrylonitrile, itaconic acid, etc.). More specific examples include the above-mentioned (meth) acrylic acid alkyl ester monomer (A1) and the functional group containing monomer (A2). In addition, methoxymethyl (meth) acrylate, methoxyethyl (meth) (Meth) acrylic acid esters having an aliphatic ring such as (meth) acrylic acid esters such as ethoxymethyl and ethoxyethyl (meth) acrylate; (meth) acrylic esters having aliphatic rings such as (Meth) acrylic acid esters having aromatic rings, non-crosslinkable acrylamides such as acrylamide and methacrylamide, and the like, such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (Meth) acrylic acid esters having a tertiary amino group in a condensed state, vinyl acetate, and styrene.

When the non-energy ray ray-curable acrylic pressure-sensitive adhesive (N) has a reactive functional group derived from the functional group-containing monomer (A2), from the viewpoint of setting the degree of crosslinking to a favorable range, the functional group- ) Is preferably about 1 to 20% by mass, and more preferably 2 to 10% by mass.

The weight average molecular weight (Mw) of the acrylic polymer (N) having no energy ray curability is preferably 100,000 to 2,500,000, particularly preferably 150,000 to 2,000,000, and more preferably 200,000 to 1,500,000. When the weight average molecular weight (Mw) of the acrylic polymer (N) having no energy ray curability is within the above range, the coating property of the pressure sensitive adhesive composition is ensured and the cohesiveness of the pressure sensitive adhesive layer is good. Physical properties can be obtained.

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

The energy ray curable compound (B) is a compound that undergoes polymerization curing upon irradiation with an energy ray such as ultraviolet ray or electron ray. Examples of the energy ray curable compound (B) include low molecular weight compounds having an energy ray polymerizable group (monofunctional or polyfunctional monomers and oligomers), and specific examples thereof include trimethylolpropane triacrylate, tetramethyl Hexanediol diacrylate, 1,6-hexanediol diacrylate, dipentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, Acrylate and the like, cyclic aliphatic skeleton-containing acrylates such as dicyclopentadiene dimethoxydiacrylate and isobornyl acrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acryl Acrylate such as polyether acrylate, itaconic acid oligomer and the like This teugye compound is used. Such a compound has an energy ray-curable double bond in the molecule, and usually has a molecular weight of about 100 to 30000, preferably about 300 to 10000.

When the pressure-sensitive adhesive layer in the present embodiment is composed of the above-described Y-type pressure-sensitive adhesive, the content of the energy ray-curable compound (B) in the pressure-sensitive adhesive composition is preferably in the range of 100 parts by mass to 100 parts by mass of the acrylic polymer , Preferably 20 to 200 parts by mass, particularly preferably 40 to 160 parts by mass, and more preferably 40 to 150 parts by mass.

When the pressure-sensitive adhesive layer in the present embodiment is composed of the Z-type pressure-sensitive adhesive described above, the content of the energy ray-curable compound (B) in the pressure-sensitive adhesive composition is preferably such that the content of the (meth) acrylic acid ester copolymer Is preferably 3 to 60 parts by mass, particularly preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin (A).

(3) Crosslinking agent (C)

The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer in the present embodiment is obtained by crosslinking (meth) acrylic ester copolymer (A) having an energy ray-curable group introduced into its side chain or acrylic polymer (N) It is preferable to contain a crosslinking agent (C) as much as possible. In this case, the pressure-sensitive adhesive layer in the present embodiment contains a crosslinked product obtained by cross-linking the (meth) acrylic acid ester copolymer (A) or the acrylic polymer (N) and the crosslinking agent (C). By using such a cross-linking agent (C), it is easy to adjust the gel fraction of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer to a suitable range, and physical properties suitable for dicing can be obtained.

Examples of the crosslinking agent (C) include polyimine compounds such as epoxy compounds, polyisocyanate compounds, metal chelate compounds and aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers , Metal alkoxides, metal salts, and the like. Among them, it is preferable to use an epoxy compound or a polyisocyanate compound, particularly a polyisocyanate compound, because of easy control of the crosslinking reaction and the like.

Examples of the epoxy compound include 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m- Diamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol propane diglycidyl ether, diglycidyl aniline, diglycidyl amine, and the like.

The polyisocyanate compound is a compound having two or more isocyanate groups per molecule. Specific examples thereof include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; Polyisocyanate and the like. Further, examples thereof include buret resins, isocyanurates, and adducts. As the adduct, there can be mentioned a reaction product with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylol propane, castor oil and the like.

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

When the pressure-sensitive adhesive is of X type or Z type, the content of the crosslinking agent (C) in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer is preferably such that the amount of the crosslinking agent (C) relative to 100 parts by mass of the (meth) acrylic acid ester copolymer , Preferably 0.01 to 15 parts by mass, particularly preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass. When the pressure-sensitive adhesive is Y-type, the content of the crosslinking agent (C) in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is preferably 3 to 20 parts by mass, more preferably 5 to 20 parts by mass based on the acrylic polymer (N) To 17 parts by mass, and more preferably 7 to 14 parts by mass.

(4) Organometallic catalyst (D)

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

Examples of the form of the organic compound include an alkoxide compound, a chelate compound, and an acylate compound, among which a chelate compound is preferable.

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

The amount of the organometallic catalyst (D) used in the reaction for obtaining the (meth) acrylic acid ester copolymer (A) to which the energy ray-curable group is introduced in the side chain is not limited. The amount to be used is preferably 0.001 to 10 parts by mass, particularly preferably 0.01 to 5 parts by mass, more preferably 0.05 to 5 parts by mass, in terms of the metal amount, based on 100 parts by mass of the solid content of the (meth) acrylic acid ester copolymer (A) 3 parts by mass. In the present invention, the metal amount conversion means a compounding amount or compounding ratio calculated as the mass of the metal except for the mass corresponding to the molecular weight of the structure composed of the organic material in the organometallic catalyst (D).

(5) Other components

The pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer in the present embodiment may contain various additives such as a photopolymerization initiator, a crosslinking accelerator, a coloring material such as a dye and a pigment, a flame retardant, a filler and an antistatic agent in addition to the above components.

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. Specific examples thereof include a -hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide, azobisisobutyl Rhenitrile, dibenzyl, diacetyl,? -Chlorantraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. When ultraviolet rays are used as an energy ray, irradiation time and amount of irradiation can be reduced by blending a photopolymerization initiator.

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

(6) Investigation of energy wire

When the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment is made of an energy ray curable pressure-sensitive adhesive, ionizing radiation such as ultraviolet rays, electron beams, X rays or the like may be used as the energy ray for curing the pressure- . Of these, ultraviolet rays which are relatively easy to introduce irradiation equipment are preferable.

When ultraviolet rays are used as the ionizing radiation, near-ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm are preferably used for ease of handling. The amount of light is appropriately selected according to the type of the energy ray curable component contained in the pressure-sensitive adhesive composition and the thickness of the pressure-sensitive adhesive layer, and is usually about 50 to 500 mJ / cm 2, preferably 100 to 450 mJ / And more preferably 400 mJ / cm 2. The ultraviolet illuminance is usually about 50 to 500 mW / cm 2, preferably 100 to 450 mW / cm 2, and more preferably 200 to 400 mW / cm 2. The ultraviolet source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.

When an electron beam is used as the ionizing radiation, the acceleration voltage may be suitably selected according to the type of the energy ray curable component contained in the pressure-sensitive adhesive composition and the thickness of the pressure-sensitive adhesive layer, and is usually about 10 to 1000 kV desirable. The irradiation dose may be set in a range in which the pressure-sensitive adhesive is properly cured, and is usually selected in the range of 10 to 1000 krad. The electron beam source is not particularly limited and various electron beam accelerators such as a Cockloft Walton type, a Vandegraph type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamictron type and a high frequency type can be used .

3. Release film

In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, a release film may be laminated on the surface in order to protect the surface of the pressure-sensitive adhesive layer on the side opposite to the substrate, until the adherend is pasted. The constitution of the peeling film is arbitrary, and the peeling treatment of the plastic film with a peeling agent or the like is exemplified. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the releasing agent, a silicone releasing agent, a fluorine releasing agent, a long-chain alkyl releasing agent and the like can be used. Among them, a silicone-based stripper is preferable which can achieve an inexpensive and stable performance. Although the thickness of the release film is not particularly limited, it is usually about 20 to 250 占 퐉.

4. Properties of adhesive sheet for glass dicing

The adhesive force of the adhesive sheet for glass dicing according to the present embodiment to the alkali-free glass after the surface opposite to the substrate of the pressure-sensitive adhesive layer is attached to the alkali-free glass and left standing for 20 minutes is 8000 to 25000 mN / 25 mm, and more preferably 9000 to 22000 mN / 25 mm, further preferably 10000 to 19000 mN / 25 mm. When the adhesive force is in the above-mentioned range, it is possible to maintain the glass plate and the glass chip on the adhesive sheet better at the time of dicing. As a result, chip scattering is effectively suppressed. In addition, since the glass plate and the glass chip are kept better on the adhesive sheet, the deviation of the glass plate and the glass chip on the adhesive sheet is suppressed, and the die shift and chipping are difficult to occur. In the present specification, when the pressure-sensitive adhesive layer is composed of the above-mentioned energy ray curable pressure-sensitive adhesive, the pressure-sensitive adhesive force is a value measured before the energy ray irradiation.

In the case where the pressure-sensitive adhesive layer is made of the above-mentioned energy ray curable pressure-sensitive adhesive, the surface of the pressure-sensitive adhesive layer opposite to the substrate is attached to the alkali-free glass, and the pressure- The adhesive force of the adhesive sheet for glass dicing to the alkali-free glass is preferably 50 to 250 mN / 25 mm, more preferably 60 to 160 mN / 25 mm, further preferably 70 to 130 mN / 25 mm Do. The adhesive force after the energy beam irradiation is 50 mN / 25 mm or more, it is possible to prevent the glass chip from being inadvertently peeled or shifted from the adhesive sheet in the step before picking up the glass chip from the adhesive sheet, The pickup can be performed more satisfactorily. On the other hand, when the adhesive force after the energy beam irradiation is 250 mN / 25 mm or less, for example, when the glass chips are picked up individually, the glass chips can be picked up well without breakage, Can be effectively suppressed.

In the present specification, the adhesive strength is determined by an adhesive force (mN / 25 mm) measured by a 180 deg. Peel method according to JIS Z0237: 2009, using alkali-free glass as an adherend, As shown in Fig.

5. Manufacturing method of pressure-sensitive adhesive sheet for glass dicing

The production method of the pressure-sensitive adhesive sheet for glass dicing is not particularly limited as long as the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition described above can be laminated on one surface of the substrate.

As an example of a production method of a pressure-sensitive adhesive sheet for glass dicing, a coating composition containing the above-mentioned pressure-sensitive adhesive composition and, if desired, a solvent or a dispersion medium is first prepared. Next, the coating composition is coated on one side of the substrate by a die coater, a curtain coater, a spray coater, a slit coater, a knife coater or the like to form a coating film. Further, the pressure sensitive adhesive layer can be formed by drying the coating film. The properties of the coating composition are not particularly limited as far as they can be applied. The component for forming the pressure-sensitive adhesive layer may be contained in the coating composition as a solute or as a dispersion.

When the coating composition contains a crosslinking agent (C), the above drying conditions (temperature, time, etc.) may be changed or a heat treatment may be separately provided in order to form a crosslinked structure at a desired density. Sensitive adhesive sheet for glass dicing is laminated on the base material by the above-mentioned method or the like in order to sufficiently proceed the crosslinking reaction, and then the obtained pressure-sensitive adhesive sheet for glass dicing is subjected to heat treatment under the conditions of, for example, 23 DEG C and 50% relative humidity for 1 week to 2 weeks It may be cured.

As another example of the production method of the pressure-sensitive adhesive sheet for glass dicing, first, a coating composition is applied on the release 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 a pressure-sensitive adhesive layer and a release film. The surface of the pressure-sensitive adhesive layer of the laminate opposite to the release film is affixed to the substrate. Thus, a laminated product of a pressure-sensitive adhesive sheet for glass dicing and a release film can be obtained. The release film in this laminate may be peeled off as a process material, or the pressure-sensitive adhesive layer may be protected during adherence to an 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. The adhesive sheet for glass dicing according to the present embodiment can also be used for a series of processes including dicing of a glass plate and subsequent pick-up.

In the case of using in a series of processes including dicing and subsequent pick-up, first, the surface of the pressure-sensitive adhesive layer of the glass-dicing pressure-sensitive adhesive sheet according to the present embodiment opposite to the substrate (hereinafter referred to as " ) Is attached to a glass plate. When the release film is laminated on the adhesive surface, the release film is peeled off and the glass plate is attached to the exposed adhesive surface. On the other hand, the peripheral edge of the adhesive surface is affixed to an annular jig called a ring frame for carrying or fixing to the apparatus. It is preferable that the glass plate is left standing for 10 to 120 minutes, preferably 15 to 60 minutes, and more preferably 20 to 40 minutes, before the subsequent dicing step after attaching the glass plate. It is desirable to leave it to the station. By maintaining such a period of time, the adhesion between the glass plate and the pressure-sensitive adhesive sheet can be made sufficient.

Subsequently, a dicing step is performed. That is, a glass plate pasted on the adhesive sheet for glass dicing is cut using a dicing blade. Thereby, a plurality of glass chips pasted on the adhesive sheet for glass dicing can be obtained. In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the pressure-sensitive adhesive layer is relatively thick as described above, so that the tackiness is favorable. As a result, the glass chip is favorably held on the adhesive sheet, and chip scattering is suppressed. Further, in addition to the fact that the glass chips are kept well on the pressure-sensitive adhesive sheet due to the thickness of the pressure-sensitive adhesive layer, the chipping and die shift are suppressed when the thickness of the base material is in the above-mentioned range.

In the case where the pressure-sensitive adhesive layer is made of the above-described energy ray curable pressure-sensitive adhesive, after the dicing step is completed, the pressure-sensitive adhesive sheet to which a plurality of glass chips are attached is subjected to energy ray irradiation from the surface of the glass chip side or the substrate side. As a result, the polymerization reaction of the energy ray-curable group possessed by the (meth) acrylic acid ester copolymer (A) proceeds and the stickiness is lowered, and the succeeding pick-up process becomes easier.

The pickup process can be carried out by a general-purpose means such as a suction collet. At this time, in order to facilitate the pick-up, it is preferable to push up the glass chip as a target from a surface opposite to the pressure-sensitive adhesive layer on the substrate to a pin or a needle. In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, the thickness of the substrate is in the above-described range, so that the pressure-sensitive adhesive sheet has excellent flexibility. Further, when the thickness of the pressure-sensitive adhesive layer is in the above-mentioned range, the adhesive force of the pressure-sensitive adhesive sheet becomes a size suitable for picking up the glass chip. Thus, a good pickup can be performed. In the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, it is difficult to leave a pressure-sensitive adhesive derived from the pressure-sensitive adhesive layer on the picked-up glass chip. Particularly, when the pressure-sensitive adhesive layer is made of the X-type pressure-sensitive adhesive, the X-type pressure-sensitive adhesive does not contain a low molecular weight compound such as the energy ray curable compound (B), so that the compound does not remain on the glass chip. In addition, the pressure-sensitive adhesive composition for forming the X-type pressure-sensitive adhesive easily undergoes uniform cross-linking. As described above, the occurrence of residual adhesive is effectively suppressed.

Further, it is preferable to carry out the expanding process before the pickup process. In this case, the adhesive sheet for glass dicing is stretched in the plane direction. As a result, the interval between the glass chips is widened, and pickup becomes easy. The degree of elongation may be suitably set in consideration of a preferable interval, a tensile strength of the substrate, and the like. Further, the expanding step may be performed before the energy ray irradiation.

In the case of dicing the glass plate using a glass adhesive sheet for dicing according to this embodiment, the area of the plane of the glass chip is obtained, and preferably from ^{1 × 10 -6 ㎟ ~ 1 ㎟} , 1 × 10 -4 Mm 2 to 0.25 mm 2, more preferably 2.5 × 10 ^-3 mm 2 to 0.09 mm 2, further preferably 0.01 mm 2 to 0.03 mm 2. According to the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, since the thickness of the pressure-sensitive adhesive layer is relatively thick and good tackiness can be exhibited, the occurrence of chip scattering, chipping and die shift can be suppressed even in a small glass chip having the above- .

In the case of dicing a glass plate using the adhesive sheet for glass dicing according to the present embodiment, the thickness of the glass plate used as a work is preferably 50 to 10000 m, more preferably 100 to 5000 m, more preferably 300 To 800 m. In the present specification, the term " work " refers to an adherend to which the adhesive sheet for glass dicing according to the present embodiment is adhered or a workpiece to be processed using the adhesive sheet. According to the pressure-sensitive adhesive sheet for glass dicing according to the present embodiment, since the thickness of the pressure-sensitive adhesive layer is comparatively large and a good tack can be exhibited, even a thin glass plate having a thickness of 50 占 퐉 can be diced while suppressing the occurrence of chipping.

The above-described embodiments are described for the purpose of facilitating understanding of the present invention and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design modifications and equivalents falling within the technical scope of the present invention.

For example, another layer may be interposed between the substrate and the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet for glass dicing.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope of the present invention is not limited to these Examples and the like. In the following description, the base material of the mass portion 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). The molecular weight of the obtained acrylic copolymer (AP) was measured, and as a result, the weight average molecular weight (Mw) was 700,000. The weight average molecular weight (Mw) in this example is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) (GPC measurement).

2-methacryloyloxyethyl isocyanate (MOI) as the energy ray-curable group-containing compound (A3) was added to the obtained acrylic copolymer (AP) in the presence of a zirconium chelate catalyst (Matsumoto Fine Chemicals Co., ZC-700 "). Thus, a (meth) acrylic acid ester copolymer (A) having an energy radiation curable group (methacryloyl group) introduced into the side chain was obtained. At this time, both were reacted such that the MOI was 60 mol (60 mol%) per 100 mol of 2-hydroxyethyl acrylate unit of the acrylic copolymer (AP). The blending amount of the organometallic catalyst (D) was 0.1 part by mass relative to 100 parts by mass of the acrylic copolymer (AP).

(2) Preparation of pressure-sensitive adhesive composition

100 parts by mass of the (meth) acrylic acid ester copolymer (A) obtained in the above step (1) and 3.0 parts by mass of? -Hydroxycyclohexyl phenyl ketone (product name: "Irgacure 184" And 0.2 parts by mass of trimethylolpropane-modified tolylene diisocyanate (product name: " Coronate L ", manufactured by Tosoh Corporation) as a crosslinking agent (C) were mixed in a solvent to obtain a coating solution of a pressure- Further, by using this pressure-sensitive adhesive composition, an X-type pressure-sensitive adhesive can be obtained.

(3) Production of adhesive sheet for glass dicing

The coating solution of the pressure-sensitive adhesive composition obtained in the above step (2) was applied to the release treatment surface of a release film (product name: "SP-PET381031", thickness: 38 μm) obtained by peeling one surface of a polyethylene terephthalate film with a silicone- By a die coater. Subsequently, the coating film was treated at 100 DEG C for 1 minute to dry the coating film and proceed with the crosslinking reaction. Thus, a laminate comprising a release film and a pressure-sensitive adhesive layer having a thickness of 10 占 퐉 was obtained. Further, a polyethylene terephthalate (PET) film (product name: "A-4100", manufactured by Toyobo Co., Ltd., thickness: 100 μm) as a substrate was bonded to the side of the pressure-sensitive adhesive layer side of the laminate. Thus, a pressure-sensitive adhesive sheet for glass dicing, in which a substrate, a pressure-sensitive adhesive layer and a release film were laminated in this order, was obtained.

[Examples 2 to 11]

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

[Comparative Examples 1 to 3]

Except that the thickness of the substrate, the kind of the organic metal catalyst (D) used for forming the pressure-sensitive adhesive layer, and the thickness of the pressure-sensitive adhesive layer were changed as shown in Table 1, .

[Comparative Example 4]

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

Details of the abbreviations and the like in Table 1 are as follows.

[Material of substrate]

PET (thickness: 100 占 퐉): polyethylene terephthalate film (trade name: A-4100, manufactured by Toyobo Co., Ltd.)

PET (thickness: 50 占 퐉): polyethylene terephthalate film (trade name: A-4100, manufactured by Toyobo Co., Ltd.)

PET (thickness: 188 占 퐉): polyethylene terephthalate film (product name: A-4100, manufactured by Toyobo Co., Ltd.)

PO: polyolefin film (product name "ADN09-100T-M8", manufactured by Riken Technos Co., Ltd.)

PP: polypropylene film (product name: PL109, manufactured by Dia Plus Film Co., Ltd.)

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

[Organometallic Catalyst]

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

Sn: Dibutyl tin Laurelite catalyst ("BXX-3778" manufactured by Toyochem Co., Ltd.)

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

With respect to the substrates used in Examples and Comparative Examples, the storage modulus at 23 占 폚 was measured by the following apparatus and conditions. The results are shown in Table 1.

Measuring apparatus: dynamic elastic modulus measuring apparatus, manufactured by TA Instruments Co., Ltd., product name "DMA Q800"

Test start temperature: 0 ° C

Test end temperature: 200 ° C

Heating rate: 3 ° C / min

Frequency: 11 Hz

Amplitude: 20 탆

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

The coating solution of the pressure-sensitive adhesive composition used in Examples and Comparative Examples was coated on the release surface of a 38 占 퐉 -thick first release film (product name "SP-PET381031", manufactured by Lin Tec Co., Ltd.). The obtained coating film was kept at 100 DEG C for 1 minute to dry the coating film. Thus, a pressure-sensitive adhesive layer having a thickness of 40 占 퐉 was formed on the first release film. Further, a peeling-treated surface of a 38 占 퐉 -thick second peeling film (trade name: SP-PET381031, manufactured by Lin Tec Co., Ltd.) was adhered to the surface of the pressure-sensitive adhesive layer opposite to the first peeling film, A laminate having a film and a pressure-sensitive adhesive layer having a thickness of 40 占 퐉 and a second release film laminated in this order was obtained. A plurality of pressure-sensitive adhesive layers obtained by the above procedure were laminated so as to have a thickness of 800 mu m. The resulting mixture was pulverized in a circular form having a diameter of 10 mm from a laminate having a thickness of 800 탆 and used as a sample for measurement. The sample was subjected to a deformation at a frequency of 1 Hz by a viscoelasticity measuring apparatus (manufactured by TA Instruments, Inc., product name "ARES") and the storage elastic modulus at -50 to 150 ° C was measured. Respectively. The results are shown in Table 1. When a plurality of pressure-sensitive adhesive layers were laminated, the laminate was allowed to stand for 1 week under an environment of a temperature of 23 占 폚 and a humidity of 50% after the formation of the pressure-sensitive adhesive layer.

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

A plurality of pressure-sensitive adhesive layers were laminated so as to have a thickness of 200 占 퐉 according to the same procedure as in Test Example 2.

Subsequently, ultraviolet (UV) irradiation (illuminance: 230 mW / cm 2, light quantity: 190 mJ / cm 2) was performed using an ultraviolet irradiator (product name "RAD-2000" . Further, the test piece was cut into 15 mm x 140 mm to obtain a test piece.

The peeled film was peeled off from the obtained test piece, and the tensile elastic modulus at 23 캜 was measured for the cured pressure-sensitive adhesive layer in accordance with JIS K7161: 1994 and JIS K7127: 1999. Specifically, a tensile test was carried out at a speed of 200 mm / min after setting the distance between chucks to 100 mm with a tensile tester (product name: "Autograph AG-IS 500N", manufactured by Shimadzu Corporation) Were measured. The results are shown in Table 1.

[Test Example 4] (Measurement of tack value)

The surface of the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet prepared in the examples and the comparative examples was measured with a probe with a diameter of 5 mm (5 mmφ) using a probe tester (product name: "RPT-100" The tack values were measured. The measuring method was as described in the JIS regulation, while changing the peeling speed to 1 mm / min in the method described in JIS Z0237: 2009, the load was 100 gf / cm 2, and the contact time was 1 second. The measured energy amount (peak integrated value) was obtained, and this was regarded as a tack value (unit: mJ / 5 mmφ). The results are shown in Table 1. Further, in the measurement, a pressure-sensitive adhesive sheet which was allowed to stand for 1 week under an environment of a temperature of 23 캜 and a humidity of 50% after the formation of the pressure-sensitive adhesive layer was used.

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

The release film was peeled off from the pressure-sensitive adhesive sheet for glass dicing, which was prepared in Examples and Comparative Examples at room temperature under the conditions of a temperature of 23 캜 and a humidity of 50% for one week. The exposed surface of the pressure-sensitive adhesive layer was superimposed on one surface of a 6-inch non-alkali glass plate, and a 2 kg roller was reciprocated one by one to give a load, and left for 20 minutes. Thereafter, the adhesive sheet for glass-dicing was peeled off from the alkali-free glass plate at a peeling speed of 300 mm / min and a peeling angle of 180 deg. By the 180 deg. Peeling method according to JIS Z0237: 2009, and the adhesive force (mN / 25 mm) Respectively. This measured value was regarded as the adhesion before ultraviolet irradiation. The results are shown in Table 1.

In the same manner as described above, the pressure-sensitive adhesive sheet for glass dicing prepared in Examples and Comparative Examples was laminated with a 6-inch non-alkali glass plate and left for 20 minutes. Thereafter, from the substrate side of the pressure-sensitive adhesive sheet for glass dicing, Ultraviolet (UV) irradiation (light intensity: 200 mW / cm 2, light quantity: 180 mJ / cm 2) was performed using a light source (trade name: RAD- Thereafter, the adhesive force (mN / 25 mm) was measured in the same manner as described above. This measured value was regarded as the adhesion after ultraviolet irradiation. The results are shown in Table 1.

[Test 6] (Evaluation of chip scattering, chipping and die shift)

The release film was peeled off from the pressure-sensitive adhesive sheet for glass dicing, which was left in an environment of a temperature of 23 DEG C and a humidity of 50% for one week in Examples and Comparative Examples, and the release film was peeled off using a tape mounter (trade name: Adwill RAD2500m / 12 ), A 6-inch-thick non-alkali glass plate having a thickness of 550 탆 and a ring frame for dicing were affixed to the exposed surface of the pressure-sensitive adhesive layer. Subsequently, the pressure-sensitive adhesive sheet for glass dicing was cut in accordance with the outer diameter of the ring frame. Further, dicing was performed using a dicing machine (product name: "DFD-651" manufactured by DISCO Corporation) under the following dicing conditions from the side of the glass plate to obtain a glass chip having a width of 0.6 mm.

<Dicing Condition>

Dicing device: DFD-651 manufactured by DISCO Corporation

Blade: NBC-2H 2050 27HECC manufactured by DISCO Corporation

Blade width: 0.025 to 0.030 mm

· Extrusion amount of blade edge: 0.640 ~ 0.760 mm

· Number of revolutions of blade: 30000 rpm

· Cutting speed: 80 ㎜ / sec

· Substrate infeed depth: 20 ㎛

· Cutting water amount: 1.0 l / min

· Cutting temperature: 20 ℃

Dicing size: 0.6 mm (area of flat surface: 0.36 mm 2)

The adhesive sheet having the glass chips obtained by the dicing step was observed with naked eyes to count the number of glass chips dropped from the adhesive sheet during the dicing process and the number of the glass chips was divided by the number of divisions in the dicing step, Chip scattering rate (unit:%) was obtained. On the basis of this calculation result, chip scattering was evaluated based on the following. The evaluation results are shown in Table 1.

?: Chip scattering rate is less than 0.1%.

?: Chip scattering rate is 0.1% or more and less than 5%.

DELTA: chip scattering rate is 5% or more and less than 10%.

X: chip scattering rate is 10% or more.

The presence or absence and shape of the ends of the glass chips located at and near the center of the adhesive sheet for glass dicing after the dicing were observed. Concretely, 50 chips were changed in the flow direction (MD direction) at the time of production of the base material, and the number of chips changed in the MD direction was measured using an electron microscope (product name: "VHZ-100" (CD direction). The defects having a width or depth of 20 mu m or more were determined by chipping, and the number of defects was counted. Based on these results, chipping was evaluated based on the following. The evaluation results are shown in Table 1.

?: The number of chips in which chipping occurred is less than five.

A: The number of chips in which chipping occurred was 5 or more and less than 50.

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

For all the glass chips obtained by the dicing, the length of the four sides when viewed in a plane is measured, and a chip (hereinafter referred to as &quot; NG chip &quot;) having a difference between the maximum value and the minimum value of 10% ) Are counted. Based on these results, the die shift was evaluated based on the following. The evaluation results are shown in Table 1.

?: The number of NG chips is less than 50.

?: The number of NG chips is 50 or more and less than 500.

X: The number of NG chips is 500 or more.

[Test Example 7] (evaluation of pickup)

100 glass chips were picked up from the pressure-sensitive adhesive sheet for dicing by dicing in Test Example 6. At this time, the pushing up was carried out by the needle from the surface opposite to the surface to which the glass chip was attached in the adhesive sheet for glass dicing (needle number: 4, push-up speed: 0.3 mm / sec, Height: 1.5 mm). For the glass chip obtained by picking up, the number (NG number) of breakage of the glass chip was counted, and the pick-up was evaluated according to the following criteria. The results are shown in Table 1.

&Amp; cir &amp;: No breakage of the glass chip was observed.

○: There were 1 or 2 glass chip breakage.

X: There were three or more glass chips broken.

[Test Example 8] (Evaluation of adhesive residue)

The adhesion of the pressure-sensitive adhesive derived from the pressure-sensitive adhesive layer of the glass dicing pressure-sensitive adhesive sheet to the 5000 glass chips picked up by the method shown in Test Example 7 was measured with an electron microscope (product name: "VHZ-100" 300 times). The number of glass chips to which a pressure-sensitive adhesive having a maximum width of 30 占 퐉 or more was attached was counted, and the residual adhesive was evaluated according to the following criteria.

?: The number of glass chips to which the adhesive was attached was less than 50.

?: The number of glass chips to which a pressure-sensitive adhesive was attached was 50 or more and less than 500.

X: The number of glass chips to which an adhesive was attached was 500 or more.

As can be seen from Table 1, according to the pressure-sensitive adhesive sheet related to the examples, occurrence of chip scattering, chipping, die shift and adhesive remnants can be suppressed and good pickup can be achieved.

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

Claims (13)

A pressure-sensitive adhesive sheet for glass dicing comprising a base material and a pressure-sensitive adhesive layer laminated on at least one surface of the base material,
The thickness of the substrate is not less than 30 占 퐉 and less than 130 占 퐉,
Wherein the thickness of the pressure-sensitive adhesive layer is more than 9 탆 and not more than 40 탆
Wherein the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet for glass dicing. The method according to claim 1,
Wherein the pressure-sensitive adhesive layer comprises an energy ray curable pressure-sensitive adhesive. 3. The method of claim 2,
Wherein the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive formed from a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced into its side chain. The method according to claim 1,
The amount of energy measured in the pressure-sensitive adhesive layer using the probe under the condition of changing the peeling speed to 1 mm / min in the method described in JIS Z0237: 1991 is from 0.01 to 5 mJ / 5 mm Wherein the pressure-sensitive adhesive sheet is a glass-dicing pressure-sensitive adhesive sheet. The method according to claim 1,
Wherein the pressure-sensitive adhesive layer has a storage elastic modulus at 23 占 폚 of 30 to 100 占 퐉. The method according to claim 1,
The adhesive force of the pressure-sensitive adhesive sheet for glass dicing to the alkali-free glass after the surface of the pressure-sensitive adhesive layer opposite to the substrate is stuck to the alkali-free glass and allowed to stand for 20 minutes is preferably 8000 to 25000 mN / 25 mm. &Lt; / RTI &gt; 3. The method of claim 2,
The adhesive force of the pressure sensitive adhesive sheet for glass dicing to the non-alkali glass after attaching the surface of the pressure sensitive adhesive layer on the side opposite to the substrate to the alkali - free glass and irradiating the energy ray to the pressure sensitive adhesive layer is preferably 50 to 250 mN / 25 mm. &lt; / RTI &gt; 3. The method of claim 2,
Wherein the pressure-sensitive adhesive layer has a tensile modulus of elasticity of 15 to 1500 MPa at 23 deg. C after irradiation with energy rays. The method according to claim 1,
Wherein the substrate has a storage elastic modulus at 23 占 폚 of 100 to 8000 MPa. The method of claim 3,
Wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent (C). The method according to claim 1,
Wherein the glass sheet is for dicing into a glass chip having a flat surface with an area of 1 x 10 ^-6 mm 2 to 1 mm 2. A method of producing a pressure-sensitive adhesive sheet for glass dicing according to claim 3,
An acrylic copolymer (AP) obtained by copolymerizing at least a (meth) acrylic acid alkyl ester monomer (A1) and a functional group-containing monomer having a reactive functional group (A2)
(A3) having a functional group capable of reacting with the functional group of the functional group-containing monomer (A2) and an energy ray-curable group having an energy ray-curable carbon-
(Meth) acrylic acid ester copolymer (A) having an energy ray-curable group introduced into its side chain, and
A step of laminating a pressure-sensitive adhesive layer on at least one surface of a substrate using a pressure-sensitive adhesive composition containing the (meth) acrylic acid ester copolymer (A)
The method of producing a pressure-sensitive adhesive sheet for glass dicing according to claim 1, 13. The method of claim 12,
Wherein the reaction of the acrylic copolymer (AP) with the energy ray-curable group-containing compound (A3) is carried out in the presence of at least one organosilicon compound selected from organic compounds containing zirconium, organic compounds containing titanium and organic compounds containing tin In the presence of the metal catalyst (D).