JP5027321B2 - Semiconductor processing tape - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tape for semiconductor processing in which adhesion of cutting chips to an adhesive layer is reduced in the pickup process while keeping adhesive force sufficient for preventing the chips from flying at the time of dicing, a sufficient adhesive force to a substrate is ensured in the subsequent die bonding process, and process problems such as package crack can be reduced sharply. <P>SOLUTION: In the tape for semiconductor processing having an adhesive layer on a base material resin film, the adhesive layer is composed of a radiation curing resin composition containing, for 100 pts.mass of acrylic adhesive, 0.1-50 pts.mass of polymer (X) having, as a component, a compound having a structure represented by a general formula (1) or a compound(B) represented by the general formula (1). CH<SB POS="POST">2</SB>=CR<SP POS="POST">1</SP>-COO-R<SP POS="POST">2</SP>-O-CH=CHR<SP POS="POST">3</SP>.....(1) [In the general formula (1), R<SP POS="POST">1</SP>represents a hydrogen atom or methyl. R<SP POS="POST">2</SP>represents an organic residue of 2-20C. R<SP POS="POST">3</SP>represents an organic residue of 1-11C.] <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a semiconductor processing tape used in a dicing process for cutting and separating a semiconductor wafer into semiconductor elements. The present invention also relates to a semiconductor processing tape used for obtaining a semiconductor element with an adhesive layer in a dicing process and obtaining a semiconductor element that can be used in a subsequent die bonding process or mounting process.

  In a manufacturing process of a semiconductor device such as an IC, a process of attaching a sticky and stretchable semiconductor processing tape to the back surface of a semiconductor wafer on which a circuit pattern is formed, and then cutting (dicing) the semiconductor wafer into chips. In addition, a process for picking up the cut chip, and a die bonding (mounting) process for bonding the picked-up chip to a lead frame, a package substrate, etc., or stacking and bonding semiconductor chips together in a stacked package Is done.

As the semiconductor processing tape, in the process of dicing the semiconductor wafer, the semiconductor wafer (chip) requires a high adhesive force to firmly fix the semiconductor wafer and the chip so that the cut semiconductor element (chip) is not scattered. In the process of picking up, low adhesive strength that can be easily peeled off from the chip is required.
For example, in Patent Document 1, by using a radiation curable pressure-sensitive adhesive layer, radiation is applied after dicing, and the viscosity of the pressure-sensitive adhesive layer is reduced before being subjected to a pick-up process. An adhesive tape for fixing a semiconductor wafer that has both adhesive strength and low adhesive strength required at the time of pickup has been proposed.
In addition, dicing die bonding tapes (for example, Patent Documents 2 and 3) in which a thermosetting adhesive layer containing an epoxy resin component is laminated on a radiation curable pressure-sensitive adhesive layer have been proposed.

Japanese Patent No. 2661950 JP 2002-226996 A JP 2005-303275 A

In an assembly process of a semiconductor device such as an IC, a process of cutting and separating (dicing) a semiconductor wafer after pattern formation into individual chips, a process of mounting the chips on a substrate, and a process of sealing with a resin or the like It is made up of. When the dicing die-bonding tape is used, in the dicing step, the semiconductor wafer is previously attached and fixed to the adhesive layer of the semiconductor processing tape, and then dicing is performed along the scribe line. In the subsequent mounting process, the adhesive layer and the pressure-sensitive adhesive tape are configured to be peelable, and the chip with the adhesive is peeled off (pick-up) from the pressure-sensitive adhesive tape and fixed to the substrate or the like with the adhesive for fixing the adhesive attached to the chip. .
However, those described in Patent Documents 1 and 2 require sufficient adhesive strength that the wafer does not peel when dicing, and cannot sufficiently meet the requirement of being easily peelable when picking up. there were. This is because the curing reaction of the pressure-sensitive adhesive progresses due to radiation irradiation, and even if the pressure-sensitive adhesive force is sufficiently reduced, the semiconductor wafer, the adhesive, This is because cutting waste such as a pressure-sensitive adhesive or a base film may be entangled with the adhesive and hinder peeling. Further, even if the chip can be picked up, process defects such as package cracks may occur due to the cutting waste adhering to the adhesive layer adhering to the substrate.
Similarly, for semiconductor processing tapes that are not laminated with an adhesive layer, similarly, cutting of semiconductor wafers, adhesives, base films, etc. on the scribe line by means of a blade used in the dicing process when dividing into chips. Debris entangled with the pressure-sensitive adhesive and hindered peeling, and contaminants caused by these cutting wastes or the like adhered to the chip surface, resulting in peeling failure.

The object of the present invention is to reduce the adhesion of cutting waste to the adhesive layer during expansion in the pickup process while maintaining sufficient adhesive strength to prevent chip skipping during dicing, and in the subsequent die bonding process, It is an object of the present invention to provide a semiconductor processing tape that has sufficient adhesive strength and can significantly reduce process defects such as package cracks.
Further, an object of the present invention is to reduce the adhesion of cutting waste to the adhesive layer during expansion in the pickup process while maintaining sufficient adhesive strength to prevent chip skipping during dicing, and to adhere contaminants. An object of the present invention is to provide a semiconductor processing tape capable of significantly reducing the above.

As a result of intensive studies in view of the above problems, the inventors of the present invention are semiconductor processing tapes having a pressure-sensitive adhesive layer on a base resin film, wherein the pressure-sensitive adhesive layer is intramolecular with respect to the acrylic copolymer. A semiconductor processing tape comprising a radiation curable resin composition containing a compound having a specific structure having at least one (meth) acryloyl group and at least one vinyl ether group is The present inventors have found that the upper cutting waste can be peeled off from the semiconductor chip without being taken into the pressure-sensitive adhesive layer or the adhesive layer formed on the pressure-sensitive adhesive layer. The present invention has been made based on this finding.
The object of the present invention has been achieved by the following means.

<1> A semiconductor processing tape having an adhesive layer on a base resin film,
The semiconductor processing tape is used in a process of picking up a semiconductor chip by fixing and dicing a semiconductor wafer and then reducing the adhesive strength of the adhesive layer by irradiating ultraviolet rays when manufacturing a semiconductor manufacturing apparatus. Is,
The pressure-sensitive adhesive layer has, as a constituent component, a compound having a structure represented by the following general formula (1) or a compound (B) represented by the following general formula (1) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. A semiconductor processing tape comprising a radiation curable resin composition containing 0.1 to 50 parts by mass of coalesced (X).
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CHR 3 ····· (1)
[In General Formula (1), R ¹ represents a hydrogen atom or methyl. R ² represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. ]
<2> The semiconductor processing tape according to <1>, wherein the polymer (X) has a molecular weight of 5,000 to 100,000.
<3> The polymer (X) contains a radical polymerizable compound C1 as a constituent other than the constituent from the compound (B) in an amount of 90% by mass or less in the polymer <1> Or the tape for semiconductor processing of <2> description.
<4> The polymer (X) contains 90% by mass or less of the cationic polymerizable compound C2 as a constituent component other than the constituent component from the compound (B). <1> Or the tape for semiconductor processing of <2> description.
<5> The tape for semiconductor processing characterized by including 3-30 mass parts of polymers (X) of any one of <1>-<4> with respect to 100 mass parts of acrylic adhesives.
<6> The semiconductor according to any one of <1> to <5>, wherein the acrylic pressure-sensitive adhesive contains a compound having a radiation-curable carbon-carbon double bond having an iodine value of 10 or less. Tape for processing.
<7> The semiconductor processing tape according to any one of <1> to <6>, wherein the resin composition of the pressure-sensitive adhesive layer has a gel fraction of 50% or more.
<8> A tape for semiconductor processing, further comprising an adhesive layer on the pressure-sensitive adhesive layer of the tape for semiconductor processing according to any one of <1> to <7>.
<9> The semiconductor processing tape according to <8>,
When manufacturing a semiconductor manufacturing apparatus , the semiconductor processing tape fixes and dices a semiconductor wafer, and then reduces the adhesive strength of the adhesive layer by irradiating with ultraviolet rays, picks up a semiconductor chip, and leads to a lead frame or semiconductor. Used to adhere to the chip ,
In the tape for semiconductor processing, an adhesive layer and an adhesive layer are provided in this order on a base resin film, and in the pick-up process after the dicing process that separates the semiconductor wafer along the scribe line, the individual pieces after expansion For semiconductor processing, wherein the contact area (a) between the adhesive layer and the pressure-sensitive adhesive layer on the formed semiconductor chip is smaller than the contact area (b) between the adhesive layer and the pressure-sensitive adhesive layer before expansion tape.
<10> The semiconductor processing tape according to <9>, wherein an adhesive layer attached to the separated semiconductor chip is on an inner side than the scribe line.
<11> The adhesive layer is laminated on a pressure-sensitive adhesive layer where a semiconductor wafer is bonded, and has no adhesive layer on a pressure-sensitive adhesive layer where a semiconductor wafer is not bonded. The tape for semiconductor processing as described in <9> or <10> .
<12> The step of dicing the semiconductor wafer to which the semiconductor processing tape according to any one of <1> to <11> is bonded, the adhesive layer is irradiated with ultraviolet rays, and the adhesive strength of the adhesive layer is increased. A method for manufacturing a semiconductor device, comprising a step of reducing and a step of picking up a semiconductor chip.
<13> The method for manufacturing a semiconductor device according to <12>, including a step of bonding the picked-up semiconductor chip to a lead frame or a semiconductor chip.

  According to the present invention, while maintaining sufficient adhesive force to prevent chip skipping during dicing, the chip can be easily removed without being entangled with the cutting waste on the scribe line and the adhesive and adhesive during pickup. Can be peeled off.

It is sectional drawing which shows typically the tape for semiconductor processing which has an adhesive bond layer on the adhesive layer which is one embodiment of this invention. It is sectional drawing which shows typically a mode that the semiconductor wafer was bonded to the tape for semiconductor processing of one embodiment of this invention. It is sectional drawing which shows typically a mode that a dicing process is performed using the tape for semiconductor processing of one embodiment of this invention. It is sectional drawing which shows typically a mode that an expand process is performed using the tape for semiconductor processing of one embodiment of this invention. It is sectional drawing which shows typically a mode that a pick-up process is performed using the tape for semiconductor processing of one embodiment of this invention. It is sectional drawing which shows typically the tape for semiconductor processing of one other embodiment of this invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
[Tape for semiconductor processing]
(1) Dicing die bonding tape As shown in FIG. 1, the dicing die bonding tape 10 which is one embodiment of the semiconductor processing tape of the present invention has an adhesive layer 12b on a base resin film 12a. Further, an adhesive layer 13b is provided on the pressure-sensitive adhesive layer. A release liner 13a is provided so as to cover the pressure-sensitive adhesive layer 12b and the adhesive layer 13b. The release liner is preferably used to protect the pressure-sensitive adhesive layer 12b and the adhesive layer 13b.
The dicing / die bonding tape 10 may be cut (precut) into a predetermined shape in advance according to the use process or apparatus, or may be cut for each semiconductor wafer, or in a long roll shape. May be present.

(2) Dicing tape The semiconductor processing tape of the present invention includes a dicing tape which is another embodiment. As shown in FIG. 6, the dicing tape is provided with a pressure-sensitive adhesive layer 12b ′ on a base resin film 12a ′. A semiconductor chip can be obtained by bringing a semiconductor wafer into close contact with the pressure-sensitive adhesive layer and passing through a dicing process, an expanding process, and a pick-up process. Since the adhesive layer is not laminated on the obtained semiconductor chip, a process such as using an adhesive is required in the die bonding step.

[How to use dicing die bonding tape]
In manufacturing a semiconductor device, a dicing die bonding tape 10 which is an embodiment of the semiconductor processing tape of the present invention can be used.
First, the release liner 13 a is removed from the dicing die bonding tape 10, and as shown in FIG. 2, the adhesive layer 13 b is attached to the semiconductor wafer 1 and the side portions of the adhesive tape 12 are fixed by the ring frame 20. The ring frame 20 is an example of a dicing frame. The adhesive layer 13b is laminated on a portion of the dicing die bonding tape 10 to which the semiconductor wafer 1 is bonded. It is preferable that the adhesive film 13 is not present at a portion where the dicing die bonding tape 10 is in contact with the ring frame 20.
Thereafter, as shown in FIG. 3, the semiconductor wafer 1 is diced into a predetermined size using a thin grindstone 21 while the lower surface of the dicing die bonding tape 10 is sucked and fixed by the suction table 22 to manufacture a plurality of semiconductor chips 2. To do.
Thereafter, as shown in FIG. 4, with the dicing die bonding tape 10 fixed by the ring frame 20, the push-up member 30 is raised, the central portion of the tape 12 is bent upward, and radiation such as ultraviolet rays is emitted. The tape 10 (adhesive layer 12b) is irradiated to weaken the adhesive strength of the adhesive layer 12b.
Thereafter, as shown in FIG. 5, the push-up pin 31 is raised at a position corresponding to each semiconductor chip 2, and the semiconductor chip 2 is picked up by the suction collet 32.
Thereafter, the picked-up semiconductor chip 2 is bonded (die-bonded) to a support member such as a lead frame or another semiconductor chip 2, and a semiconductor device is obtained through steps such as attaching a gold wire and heat curing.

  The semiconductor processing tape of the present invention is a compound having a specific structure in which the pressure-sensitive adhesive layer has at least one (meth) acryloyl group and at least one vinyl ether group in the molecule with respect to the acrylic copolymer. It is comprised with the radiation-curable resin composition containing this. For this reason, the dicing die-bonding tape of the present invention has an adhesive force enough to prevent chip jumping even when the semiconductor wafer 2 is obtained by cutting the semiconductor wafer 1 in the dicing process. On the other hand, since the adhesive layer 12b has a three-dimensional network structure and has flexibility after irradiation, the adhesive force can be stably reduced regardless of the surface properties of the semiconductor wafer 1. Furthermore, even if the cutting waste generated in the dicing process remains in the pickup process, the cutting waste is not taken into the adhesive layer and the cutting waste does not adhere to the semiconductor chip. For this reason, the chip can be easily peeled off without being affected by the cutting waste accumulated on the scribe line, and an excellent effect is obtained in that it has a good adhesive force in the subsequent die bonding step.

When the semiconductor processing tape of the present invention is used, the adhesive on the separated semiconductor chip after expansion in the pick-up process in which radiation irradiation is further performed after the dicing process for dividing the semiconductor wafer along the scribe line The contact area (a) of the layer can be made smaller than the contact area (b) of the adhesive layer before expanding.
For each semiconductor chip that has been diced using the semiconductor processing tape of the present invention, the contact area (b) between the adhesive layer and the pressure-sensitive adhesive layer before expansion, the adhesive layer and the pressure-sensitive adhesive layer after expansion, It can be observed that the size of the contact area (a) is a <b, that is, the presence or absence of peeling at the adhesive layer / pressure-sensitive adhesive layer interface.
The reason for this is not clear, but by using the semiconductor processing tape of the present invention, the curing shrinkage of radiation rays such as ultraviolet rays is smaller than when a conventional radiation curable resin composition is used for the pressure-sensitive adhesive layer. This is because the anchor effect of the pressure-sensitive adhesive layer can be reduced.

  Hereinafter, as will be described, with respect to the dicing die bonding tape and the dicing tape, configurations other than the adhesive layer can be similarly used. Then, each structure of the dicing die bonding tape 10 is demonstrated in order.

[Base resin film (12a)]
The base resin film 12a is preferably radiolucent, and specifically, radiolucent plastic or rubber can be usually used. When the pressure-sensitive adhesive is cured by ultraviolet irradiation, a substrate resin film having good light transmittance can be selected.

  Examples of polymers that can be selected as such a substrate include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-acrylic. Homopolymer or copolymer of α-olefin such as ethyl acid copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer, or a mixture thereof, polyethylene terephthalate, polycarbonate, polymethyl methacrylate Engineering plastics such as polyurethane, thermoplastic elastomers such as polyurethane, styrene-ethylene-butene or pentene copolymers, polyamide-polyol copolymers, and mixtures thereof.

In the expanding process, in order to increase the gap between the semiconductor chips obtained by the dicing process, necking (occurrence of partial elongation due to poor force propagation when the base film 12a is radially stretched) is possible. Less is preferred. Examples of the base resin film include polyurethane, styrene-ethylene-butene or pentene copolymer having a specific range of molecular weight and styrene content. In order to prevent elongation or deflection during dicing, it is preferable to use a cross-linked base resin film. The thickness of the base resin film 12a is preferably 30 to 300 [mu] m from the viewpoint of strong elongation characteristics and radiation transparency.
Blocking can be prevented by subjecting the surface of the base resin film 12a opposite to the surface having the pressure-sensitive adhesive layer 12b to a texture or a lubricant coating. In addition, by performing these processes, the dicing die bonding tape 10 is radially extended in the expanding process, and when the gap between the semiconductor chips is widened, the friction between the tape 10 and the jig is reduced. The necking of the material resin film 12a can be prevented.

[Adhesive layer (12b)]
(1) Acrylic adhesive (A)
The pressure-sensitive adhesive layer 12b contains an acrylic pressure-sensitive adhesive. Specifically, the pressure-sensitive adhesive layer 12b constitutes the compound (B) represented by the following general formula (1) or the compound (B) represented by the following general formula (1) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. It is comprised using the radiation-curable resin composition containing 0.1-50 mass parts of polymer (X) which has as a component. The polymer (X) preferably has a molecular weight of 5,000 to 100,000. It is preferable that polymer (X) contains 3-30 mass parts with respect to 100 mass parts of acrylic adhesives.
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CHR 3 ····· (1)
[In General Formula (1), R ¹ represents a hydrogen atom or methyl. R ² represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. ]

  Examples of the acrylic pressure-sensitive adhesive (A) contained in the pressure-sensitive adhesive layer 12b include a homopolymer mainly composed of an ester of acrylic acid or methacrylic acid, acrylic acid, methacrylic acid or an ester thereof, or an acid amide thereof. Examples thereof include copolymers with other monomers and mixtures of these polymers. Examples of the monomer that is a constituent component of the copolymer include alkyl esters of acrylic acid or methacrylic acid, such as methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, lauryl ester, glycidyl ester. , Hydroxymethyl ester, 2-hydroxyethyl ester, hydroxypropyl ester, amides of acrylic acid or methacrylic acid and N-substituted amides (for example, N-hydroxymethylacrylic acid amide or methacrylic acid amide).

(2) Compound having a radioactive carbon-carbon double bond The acrylic pressure-sensitive adhesive (A) may have a compound having a radiation-curable carbon-carbon double bond having an iodine value of 10 or less in the molecule. Good. Here, the radiation refers to light rays such as ultraviolet rays or ionizing radiations such as electron beams. The introduction amount of the radiation curable carbon-carbon double bond is 10 or less, preferably 5 or less, more preferably 3 or less, and still more preferably 0 in terms of iodine value. When a compound having an iodine value of 10 or more is used, the curing reaction proceeds excessively, so that the cohesive force is increased, and the adhesive force after irradiation may be increased.

  The compound having a radiation curable carbon-carbon double bond preferably has a glass transition point of -70 ° C to 0 ° C, more preferably -66 ° C to -28 ° C. If the glass transition point (hereinafter also referred to as “Tg”) is −70 ° C. or higher, the heat resistance against heat associated with radiation irradiation is sufficient, and if it is 0 ° C. or lower, after dicing on a wafer having a rough surface state. The effect of preventing scattering of the element is sufficiently obtained.

  The compound having a radiation curable carbon-carbon double bond may be produced by any method. As the compound, an acrylic copolymer (Aa) in which a residue having a (meth) acrylic monomer part having a radiation-curable carbon-carbon double bond-containing group is bonded to a repeating unit of the main chain. Is preferred. This (meth) acrylic copolymer is, for example, a compound having a radiation curable carbon-carbon double bond such as an acrylic copolymer or a methacrylic copolymer and having a functional group (Aa-1 ) And a compound (Aa-2) having a functional group capable of reacting with the functional group. The compound (Aa-1) having a radiation curable carbon-carbon double bond and a functional group is a monomer having a radiation curable carbon-carbon double bond such as an alkyl acrylate ester or an alkyl methacrylate ester (Aa- 1-1) and a monomer (Aa-1-2) having a functional group can be copolymerized.

  As a monomer (Aa-1-1), it is C6-C12 hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, decyl acrylate, lauryl acrylate, or carbon number 5 or less. Examples of the monomer include pentyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, and methacrylates similar to these.

  As the monomer (Aa-1-1) is used, the glass transition point becomes lower as the monomer having a larger carbon number is used, so that the desired glass transition point can be produced. In addition to the glass transition point, a monomer (Aa-1-1) may be blended with a low molecular compound having a carbon-carbon double bond such as vinyl acetate, styrene, or acrylonitrile for the purpose of improving compatibility and various performances. ) In the range of 5% by mass or less of the total mass.

  Examples of the functional group that the monomer (Aa-1-2) has include a carboxyl group, a hydroxyl group, an amino group, a cyclic acid anhydride group, an epoxy group, and an isocyanate group, and the monomer (Aa-1- Specific examples of 2) include acrylic acid, methacrylic acid, cinnamic acid, itaconic acid, fumaric acid, phthalic acid, 2-hydroxyalkyl acrylates, 2-hydroxyalkyl methacrylates, glycol monoacrylates, glycol monomethacrylates. N-methylolacrylamide, N-methylolmethacrylamide, allyl alcohol, N-alkylaminoethyl acrylates, N-alkylaminoethyl methacrylates, acrylamides, methacrylamides, maleic anhydride, itaconic anhydride, fumaric anhydride, Phthalic anhydride, glycidyl anhydride Listed are lylate, glycidyl methacrylate, allyl glycidyl ether, and those obtained by urethanizing a part of the isocyanate group of a polyisocyanate compound with a monomer having a hydroxyl group or a carboxyl group and a radiation-curable carbon-carbon double bond. .

  In the compound (Aa-2), the functional group used is the compound (Aa-1), that is, when the functional group of the monomer (Aa-1-2) is a carboxyl group or a cyclic acid anhydride group. Can include a hydroxyl group, an epoxy group, an isocyanate group, and in the case of a hydroxyl group, it can include a cyclic acid anhydride group, an isocyanate group, and the like, and in the case of an amino group, an epoxy group, an isocyanate group In the case of an epoxy group, a carboxyl group, a cyclic acid anhydride group, an amino group, and the like can be mentioned. Specific examples of the monomer (Aa-1-2) The same thing as what was enumerated by can be enumerated.

  In the reaction of the compound (Aa-1) and the compound (Aa-2), by leaving an unreacted functional group, what is prescribed in the present invention can be produced with respect to characteristics such as acid value or hydroxyl value.

In the synthesis of the compound (Aa), as the organic solvent when the reaction is carried out by solution polymerization, ketone, ester, alcohol, and aromatic solvents can be used, among which toluene, ethyl acetate, A good solvent for an acrylic polymer such as isopropyl alcohol, benzene, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, and the like, and preferably a solvent having a boiling point of 60 to 120 ° C. The polymerization initiator is α, α′-azobisisobutyl. A radical generator such as an azobis type such as nitrile or an organic peroxide type such as benzoyl peroxide is usually used. At this time, a catalyst and a polymerization inhibitor can be used together as necessary, and the compound (A) having a desired molecular weight can be obtained by adjusting the polymerization temperature and the polymerization time. In terms of adjusting the molecular weight, it is preferable to use a mercaptan or carbon tetrachloride solvent. This reaction is not limited to solution polymerization, and other methods such as bulk polymerization and suspension polymerization may be used.

  As described above, the compound (Aa) can be obtained. In the present invention, the molecular weight of the compound (Aa) is preferably about 200,000 to 2,000,000. If it is less than 200,000, the cohesive force due to radiation irradiation becomes small, and when the wafer is diced, the element is likely to be displaced, and image recognition may be difficult. In order to prevent the deviation of the element as much as possible, the molecular weight is preferably 400,000 or more. Further, if the molecular weight exceeds 2 million, there is a possibility of gelation during synthesis and coating. In addition, the molecular weight in this invention is a weight average molecular weight of polystyrene conversion.

  In addition, it is preferable that the compound (Aa) has an OH group having a hydroxyl value of 5 to 100 mgKOH / g because the risk of pick-up mistakes can be further reduced by reducing the adhesive strength after radiation irradiation. Moreover, it is preferable that a compound (Aa) has a COOH group used as the acid value of 0.5-30 mgKOH / g.

  Here, if the hydroxyl value of the compound (Aa) is too low, the effect of reducing the adhesive strength after irradiation is not sufficient, and if it is too high, the fluidity of the adhesive after irradiation tends to be impaired. If the acid value is too low, the effect of improving the tape restoring property is not sufficient, and if it is too high, the fluidity of the pressure-sensitive adhesive tends to be impaired.

(3) Compound (B), polymer (X)
The pressure-sensitive adhesive layer 12b is composed of the compound (B) represented by the following general formula (1) or the compound (B) represented by the following general formula (1) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive (A). It is comprised using the radiation-curable resin composition containing 0.1-50 mass parts of polymers (X) which have as a structural component. In the case of a polymer, it is preferable to contain 3 to 30 parts by mass of a polymer having a molecular weight of 5,000 to 100,000.
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CHR 3 ····· (1)
[In General Formula (1), R ¹ represents a hydrogen atom or methyl. R ² represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. ]
Examples of the organic residue having 2 to 20 carbon atoms represented by R ² in the general formula (1) include a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, an ether bond in the structure, and An alkylene group having 2 to 20 carbon atoms having an oxygen atom by an ester bond and an optionally substituted aromatic group having 6 to 11 carbon atoms are preferable. Among these, an alkylene group having 2 to 6 carbon atoms and an alkylene group having 2 to 9 carbon atoms having an oxygen atom by an ether bond in the structure are more preferable.

Examples of the organic residue having 1 to 11 carbon atoms represented by R ³ in the general formula (1) include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and 6 to 11 carbon atoms. An aromatic group which may be substituted is preferred. Among these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 8 carbon atoms are more preferable.

  Examples of the compound (B) represented by the general formula (1) include the following. (Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acrylic acid 3-methyl-3-vinyloxypropyl, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, ( (Meth) acrylic acid 2-vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (Meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyloxyhexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) 2- (vinyloxyethoxy) ethyl acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxy) (meth) acrylate (Ethoxy) isopropyl, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, ( (Meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) ethyl 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, (meta ) 2- (vinyloxyethoxyethoxyethoxy) ethyl acrylate, polyethylene glycol monovinyl ether (meth) acrylate, polypropylene glycol monovinyl ether (meth) acrylate.

  Among these, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, (meth ) 4-vinyloxybutyl acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethyl (meth) acrylate Cyclohexylmethyl, p-vinyloxymethyl phenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxy) ethyl is more preferred Arbitrariness.

As a synthesis method of the polymer (X) having the compound (B) as a constituent component, it can be obtained by a conventional method. (B) is polymerized at the portion of acryloyl group or vinyl ether group. For example, when the acryloyl group is polymerized, a polymer (X) having a structure in which the vinyl ether group is suspended in a pendant form can be obtained. Further, when the vinyl ether group is polymerized, a polymer (X) having a structure in which the acryloyl group is arranged pendant can be obtained. As will be described later, when these polymers (X) are irradiated with radiation, the acryloyl group in the molecule undergoes a radical reaction, and the vinyl ether group undergoes cationic polymerization to further increase the molecular weight.
The polymer (X) can be synthesized by cationic polymerization, radical polymerization, or the like. Further, it can be copolymerized with other monomers having other cationic polymerization properties and other monomers having radical polymerization properties.

The polymer (X) is obtained by copolymerizing the radically polymerizable compound (C1) as a constituent component other than the constituent components from the compound (B), and containing the component (C1) as 90% by mass or less. Can do. As the component (C1), for example, hexyl acrylate having 6 to 12 carbon atoms, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, decyl acrylate, lauryl acrylate, or a monomer having 5 or less carbon atoms. There can be listed pentyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, methyl acrylate, or similar methacrylates. Among these, n-butyl acrylate and ethyl acrylate are preferable from the viewpoint of compatibility with the acrylic pressure-sensitive adhesive.
By using the copolymer having the component (C1) as a constituent component in the polymer (X), the compatibility with the acrylic pressure-sensitive adhesive is improved, so that the transition to the adhesive side is suppressed, Effects such as excellent stability can be obtained. The component (C1) is not necessarily used, but when used, it is preferably 5 to 90% by mass, and more preferably 10 to 50% by mass. When there are too many (C1) components, sufficient effect will not be acquired with respect to the adhesive force fall after radiation irradiation.

The polymer (X) is obtained by copolymerizing the cationically polymerizable compound (C2) as a constituent component other than the constituent components from the compound (B) and containing the component (C2) as 90% by mass or less. Can do. As the component (C2), for example, a hexyl vinyl ether having 6 to 12 carbon atoms, n-octyl vinyl ether, isooctyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, decyl vinyl ether, lauryl vinyl ether or a monomer having 5 or less carbon atoms. Specific examples include pentyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, methyl vinyl ether, and the like. Among these, n-butyl vinyl ether and ethyl vinyl ether are preferable from the viewpoint of compatibility with the acrylic pressure-sensitive adhesive.
By using the copolymer having the component (C2) as a constituent component in the polymer (X), the compatibility with the acrylic pressure-sensitive adhesive is improved, so that the shift to the adhesive side is suppressed, Effects such as excellent stability can be obtained. The component (C2) is not necessarily used, but when used, it is preferably 5 to 90% by mass, more preferably 10 to 50% by mass. When there are too many (C2) components, sufficient effect will not be acquired with respect to the adhesive force fall after radiation irradiation.

The molecular weight of the polymer (X) is preferably a weight average molecular weight of 5,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 20,000 to 50,000. preferable. If the weight average molecular weight of the polymer is too high, the compatibility with the acrylic pressure-sensitive adhesive will deteriorate, and if the weight average molecular weight is too low, it will precipitate on the surface of the pressure-sensitive adhesive due to bleed-out, adversely affecting the package reliability of the adhesive. give.
Here, the weight average molecular weight of the polymer refers to a value obtained as a weight average molecular weight in terms of polystyrene, for example, by the following method.
(Measurement conditions for weight average molecular weight)
GPC device: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Column: TSK gel SuperHM-H / H4000 / H3000 / H2000 (trade name, manufactured by Tosoh Corporation)
Flow rate: 0.6 mL / min,
Concentration: 0.3% by mass
Injection volume: 20 μL,
Column temperature: 40 ° C
Developing solvent: Chloroform

When the compound (B) or the polymer (X) is irradiated with radiation, the acryloyl group in the molecule undergoes a radical reaction, and the vinyl ether group undergoes cationic polymerization to further increase the molecular weight. By using a polymer for the acrylic pressure-sensitive adhesive and irradiating with radiation, the cohesive force of the pressure-sensitive adhesive layer can be improved and the pressure-sensitive adhesive layer can be easily peeled off.
As addition amount of a compound (B) or polymer (X), it is preferable to set it as 3-30 mass parts with respect to 100 mass parts of acrylic adhesives, and it is more preferable to set it as 5-20 mass parts. More preferably, it is made into 15 mass parts. If the amount is too small, it is not preferable because a sufficient effect cannot be obtained with respect to the decrease in adhesive strength after radiation irradiation. If the amount is too large, the cohesive force of the adhesive increases and the amount of cure shrinkage increases, and the anchor On the contrary, the adhesive force may increase due to the effect, the adhesive may become too brittle due to the curing reaction, the adhesive layer may be cracked, or the adhesive layer may be peeled off from the base resin film. It is not preferable because contaminants due to the layer adhere.

(4) Curing agent (D)
A hardening agent (D) can be mix | blended with the radiation-curable resin composition which comprises the adhesive layer of this invention. As a hardening | curing agent (D), the acrylic adhesive and the hardening | curing agent which has a functional group which reacts with the functional group in the compound which has a radioactive carbon-carbon double bond can be selected suitably, and can be mix | blended. For example, at least one compound (D) selected from polyisocyanates, melamine / formaldehyde resins, and epoxy resins can be used alone or in combination of two or more. This compound (D) acts as a crosslinking agent, and as a result of reacting with the acrylic pressure-sensitive adhesive or a compound having a radioactive carbon-carbon double bond, the pressure-sensitive adhesive layer 12b forms a three-dimensional network structure. The curing agent (D) improves the cohesive strength of the pressure-sensitive adhesive after application of the pressure-sensitive adhesive by the crosslinked structure formed as a result of reacting with the acrylic pressure-sensitive adhesive, the compound having a radioactive carbon-carbon double bond, or the base resin film 12a. Can be made.

The polyisocyanates are not particularly limited, and examples thereof include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′-[2,2-bis (4 -Phenoxyphenyl) propane] aromatic isocyanate such as diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate Lysine diisocyanate, lysine triisocyanate and the like. Specifically, Coronate L (Nippon Polyurethane Co., Ltd. product name) etc. can be used as a commercial item.
As the melamine / formaldehyde resin, specifically, Nicalac MX-45 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Melan (trade name, manufactured by Hitachi Chemical Co., Ltd.) and the like can be used as commercially available products.
Furthermore, as the epoxy resin, TETRAD-X (registered trademark, manufactured by Mitsubishi Chemical Corporation) or the like can be used.
In the present invention, it is particularly preferable to use polyisocyanates.

  As addition amount of a hardening | curing agent (D), it is preferable to set it as 0.01-20 mass parts with respect to 100 mass parts of acrylic adhesives, and it is more preferable to set it as 0.1-10 mass parts, especially. Preferably it is 0.4-3 mass parts. If the amount of the curing agent is too small, the cohesive force improving effect is not sufficient, and if the amount of the curing agent is too large, the curing reaction proceeds rapidly during the blending and coating operation of the adhesive, and a crosslinked structure is formed. Workability may be impaired.

(5) Polymerization initiator (E)
The pressure-sensitive adhesive layer 12b preferably contains at least one of a thermal polymerization initiator and a photopolymerization initiator. It is also preferable to add a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator and the like.
There is no restriction | limiting in particular as a thermal-polymerization initiator, A conventionally well-known thing can be used. For example, as the thermal polymerization initiator, metal soap such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate, benzoyl peroxide, and / or the catalytic action of amine compounds and the like are effective. A compound capable of generating a radical, 2,2′-azobisisobutyronitrile, and 2,2′-azobis (2,4-dimethylvaleronitrile) are preferable.

As the thermal cationic polymerization initiator, for example, the following compounds can be used. Lewis acids (eg, boron trifluoride, titanium chloride, ferrous chloride, ferric chloride, zinc chloride, stannous chloride, stannic chloride, dibutylstannic dichloride, tetrabutyltin, triethylaluminum , Diethylaluminum chloride, etc.) and electron donating compounds (for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide, trimethyl phosphate, triethyl phosphate, etc. ); Complex acids; protonic acids (eg, halogenocarboxylic acids, sulfonic acids, sulfuric monoesters, phosphoric monoesters, phosphoric diesters, polyphosphoric esters, boric monoesters, boric diesters, etc.) Base (e.g., ammonia, monoethylamine, diethylamine, tri Ethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, compounds neutralized with butylamine).
Among these, amine complexes of various protonic acids are preferable because a good pot life can be secured.

  As the photopolymerization initiator, for example, the following compounds can be used. Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1 Acetophenones such as [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoyl Methyl perfume, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone Benzophenones such as 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl- 9H-thioxanthone-9 Thioxanthones such as Onmesokurorido.

  Among these photopolymerization initiators, acetophenones, benzophenones, and acylphosphine oxides are preferable. In particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1one are preferable.

Examples of the photocationic polymerization initiator include arylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, (tolylcumyl) iodonium tetrakis ( Aryliodonium salts such as pentafluorophenyl) borate; aryldiazonium salts such as phenyldiazonium tetrafluoroborate.
Of these, arylsulfonium salts and diazonium salts are preferred. In particular, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate is preferable. These can be used alone or in combination of two or more.

  As addition amount of a polymerization initiator (E), it is preferable to set it as 0.01-20 mass parts with respect to 100 mass parts of said polymers, and it is more preferable to set it as 0.01-10 mass parts.

  Furthermore, the radiation-curable pressure-sensitive adhesive used in the present invention can be blended with a tackifier, a tackiness modifier, a surfactant, etc., as required, or other modifiers and conventional components. The thickness of the pressure-sensitive adhesive layer 12b is not particularly limited, but is usually 2 to 50 μm.

  In the present invention, the gel fraction of the pressure-sensitive adhesive layer can be adjusted by the weight-average molecular weight of the acrylic pressure-sensitive adhesive or the compound having a radioactive carbon-carbon double bond, and the curing agent content, but the gel fraction. Is preferably 50% or more, and more preferably 80% or more. When the gel fraction is too small, the pressure-sensitive adhesive component tends to flow slightly at the adhesion interface, and it is difficult to obtain stability over time of the peeling force.

[Adhesive film (13)]
As the adhesive film 13, for example, a film obtained by applying an adhesive usually used for die bonding, such as a film adhesive mainly composed of an epoxy resin, to the release liner 13a can be used. For the purpose of imparting electrical conductivity and thermal conductivity, metal fine powder and other materials having excellent electrical conductivity or thermal conductivity can be added to the adhesive film. To the adhesive film, a fine powder such as a metal oxide or glass can be added for the purpose of improving thermal stability. More specifically, an epoxy group-containing acrylic resin having a weight average molecular weight of 100,000 or more containing 0.5 to 6% by weight of epoxy resin (a), phenol resin (b) having a hydroxyl group equivalent of 150 g / eq or more, glycidyl acrylate or glycidyl methacrylate. What formed the adhesive bond layer 13b by the composition containing a copolymer (c), a filler (d), and a hardening accelerator (e) can be used. As the details of each component constituting the adhesive layer 13b and the characteristics of the adhesive film 13, those described in JP-A-2005-303275 (paragraphs 0034 to 0068 etc.) can be used.

  The adhesive layer 13b is prepared by dissolving or dispersing the material contained in the adhesive layer 13b in a solvent to form a varnish, and applying and heating the release liner 13a such as a polytetrafluoroethylene film or a polyethylene terephthalate film whose surface has been subjected to a release treatment. It is formed on the release liner 13a by drying and removing the solvent. As heating conditions in this case, for example, it is preferable that the temperature is about 80 to 250 ° C. and about 10 minutes to 20 hours.

  As the release liner 13a, a plastic film such as a polytetrafluoroethylene film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polymethylpentene film, or a polyimide film can be used. Can also be used.

  The adhesive film 13 can be peeled off the release liner 13a at the time of use to use only the adhesive layer 13b, or can be used together with the release liner 13a and removed later.

  As a method for applying the varnish to the release liner 13a, a known method can be used. Examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. .

  The thickness of the adhesive layer 13b is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, still more preferably 10 to 200 μm, and 20 to 100 μm. It is particularly preferred that If it is thinner than 3 μm, the stress relaxation effect tends to be poor, and if it is thicker than 300 μm, it is not economical.

  The solvent for varnishing is not particularly limited, but in consideration of volatility during film production, methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, xylene, butyl cellosolve, methanol, ethanol, It is preferable to use a solvent having a relatively low boiling point such as 2-methoxyethanol. For the purpose of improving the coating properties, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone can be added.

  In forming the adhesive layer 13b, in consideration of the dispersibility of the filler (d), it is preferable to use a raking machine, a three-roll, a ball mill, a bead mill, or the like. it can. Moreover, the mixing time can be shortened by mixing the filler and the low molecular weight compound in advance and then blending the high molecular weight compound. In addition, after forming the varnish, it is preferable to remove bubbles in the varnish by vacuum degassing or the like. Moreover, in this invention, after mixing an epoxy resin (a) and a phenol resin (b), and a filler (d), an epoxy-group-containing acrylic copolymer (c) and a hardening accelerator (e) are added to those mixtures. It is preferable to employ a method for producing an adhesive composition by mixing. Further, two or more of the adhesive layers 13b of the present invention can be bonded together in order to obtain a desired thickness. In this case, the bonding is performed so that the adhesive layers 13b are not separated from each other.

[Manufacturing method of dicing die bonding tape]
In producing the pressure-sensitive adhesive tape 12, for example, the pressure-sensitive adhesive composition is directly applied onto the base film 12a and dried to form the pressure-sensitive adhesive layer 12b on the base film 12a. The application and drying can be performed in the same manner as the method for forming the adhesive layer 13b on the release liner 13a in the adhesive film 13.

Then, the adhesive film 13 (adhesive layer 13b) is laminated | stacked on the adhesive layer 12b. In this case, for example, the release liner 13a (adhesive film 13) on which the adhesive layer 13b is formed in advance and the base film 12a (adhesive tape 12) on which the adhesive layer 12b is formed are bonded to the surface of the adhesive layer 12b. Lamination is performed so that the surface of the agent layer 13b is in contact. The laminating condition is preferably a linear pressure of 0.1 to 100 kgf / cm at 10 to 100 ° C.
Further, it is preferable to store in a low temperature environment so that the curing of the adhesive layer does not proceed. As storage conditions, refrigerated storage at 0 ± 5 ° C. is preferable. This is because the curing progresses in an environment higher than that, and peeling occurs in the package reliability test due to a decrease in embedding on the substrate. Below that, the adhesive layer / Peeling at the adhesive layer interface may occur.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.
(1) Production of Tape for Semiconductor Processing The tape for semiconductor processing shown in Tables 1-1 to 1-3 was produced, the performance test was performed, and the performance was evaluated. The evaluation results are shown in Tables 2-1 and 2-2.
(1.1) Example 1
n-Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, a mixture of benzoyl peroxide as a polymerization initiator, adjust the dropping amount appropriately, adjust the reaction temperature and reaction time An acrylic copolymer (acrylic pressure-sensitive adhesive A1 having a mass average molecular weight of 700,000 and a glass transition temperature of −40 ° C. was prepared.
Thereafter, 30 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate (referred to as B1A) is added as a compound (B1) having a structure represented by the general formula (1) to 100 parts by mass of the acrylic pressure-sensitive adhesive. , Irgacure 184 (Nippon Ciba Geigy) against 5 parts by mass of polyisocyanate compound Coronate L (manufactured by Nippon Polyurethane Co., Ltd., trade name) as a curing agent and 100 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate as a photopolymerization initiator. 5 parts by weight, manufactured by Co., Ltd., was added to obtain a radiation curable resin composition pressure-sensitive adhesive.

  Further, an ethylene-ionomer copolymer (trade name HiMilan 1706 manufactured by Mitsui DuPont Chemical Co., Ltd.) was melt-kneaded and molded to obtain a base resin film having a thickness of 100 μm and a width of 300 mm.

  Thereafter, the adhesive is applied to the base resin film with a gravure coater, dried in a hot air drying furnace, and a laminated body of an adhesive layer having a thickness of 10 μm after drying and a base film. The dicing tape of Example 1 was obtained. Then, the 20-micrometer-thick adhesive film (13-1) produced beforehand as follows was bonded together on the adhesive layer of an adhesive tape, and the dicing die-bonding tape of Example 1 was produced.

(Preparation of adhesive film (13-1))
50 parts by mass of a cresol novolac type epoxy resin (epoxy equivalent 197, molecular weight 1200, softening point 70 ° C.) as an epoxy resin, 1.5 parts by mass of γ-mercaptopropyltrimethoxysilane as a silane coupling agent, γ-ureidopropyltriethoxysilane Cyclohexanone was added to a composition composed of 3 parts by mass and 30 parts by mass of silica filler having an average particle size of 16 nm, and the mixture was stirred and mixed, and further kneaded for 90 minutes using a bead mill.
To this, 100 parts by mass of acrylic resin (mass average molecular weight: 800,000, glass transition temperature-17 ° C), 5 parts of dipentaerythritol hexaacrylate as a hexafunctional acrylate monomer, 0.5 part of an adduct of hexamethylene diisocyanate as a curing agent, 2.5 parts of Cureazole 2PZ (trade name, 2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.) was added, mixed with stirring and vacuum degassed to obtain an adhesive.
This adhesive was applied onto a 25 μm thick release-treated polyethylene terephthalate film, dried by heating at 110 ° C. for 1 minute to form a coating film having a thickness of 20 μm, and an adhesive film (13 -1) was produced.

(1.2) Example 2
In the sample preparation of Example 1, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above except that the addition amount of 2- (vinyloxyethoxy) ethyl acrylate was changed to 0.1 parts by mass. These were used as the dicing tape of Example 2 and the dicing die bonding tape of Example 2, respectively.

(1.3) Example 3
In the sample preparation of Example 1, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above except that the addition amount of 2- (vinyloxyethoxy) ethyl acrylate was changed to 50 parts by mass. Were used as the dicing tape of Example 3 and the dicing die bonding tape of Example 3, respectively.

(1.4) Example 4
In the sample preparation of Example 1, in place of Irgacure 184 (trade name, manufactured by Ciba Geigy Japan, Inc.), photocationic polymerization was initiated with respect to 100 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate as a photocationic polymerization initiator. 5 parts by mass of the agent ESACURE 1064 (trade name, manufactured by Nippon Shibel Hegner) was added. Otherwise, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 4 and the dicing die bonding tape of Example 4, respectively.

(1.5) Example 5
In the sample preparation of Example 1, as a photocationic polymerization initiator, 5 parts by mass of a photocationic polymerization initiator ESACURE 1064 (trade name, manufactured by Nippon Siebel Hegner) was added to 100 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate. It was. Except for this, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 5 and the dicing die bonding tape of Example 5, respectively.

(1.6) Example 6
A polymer (B2AO) was obtained by cationic polymerization using 2- (vinyloxyethoxy) ethyl acrylate as a monomer component. The molecular weight of the polymer was 3000, and the degree of dispersion was 1.5. Here, the molecular weight and the degree of dispersion refer to values obtained as polystyrene-reduced weight average molecular weight and degree of dispersion by the following methods.
(Measurement condition)
GPC device: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Column: TSK gel SuperHM-H / H4000 / H3000 / H2000 (trade name, manufactured by Tosoh Corporation)
Flow rate: 0.6 ml / min,
Concentration: 0.3% by mass
Injection volume: 20 μl,
Column temperature: 40 ° C
Developing solvent: chloroform In the following Examples and Comparative Examples, the molecular weight and the degree of dispersion of the polymer (X) were measured in the same manner.
In the sample preparation of Example 1, 20 parts by mass of the polymer (B2AO) was added instead of 2- (vinyloxyethoxy) ethyl acrylate, and the photopolymerization initiator was added to 100 parts by mass of the polymer (B2AO). 5 parts by weight of Irgacure 184 (Nippon Ciba Geigy Co., Ltd., trade name) was added. Otherwise, a dicing tape and a dicing die bonding tape were prepared in exactly the same manner as described above, and these were prepared as the dicing tape of Example 6 and the dicing die bonding tape of Example 6, respectively. did.

(1.7) Example 7
A polymer (B2BO) was obtained by radical polymerization using 2- (vinyloxyethoxy) ethyl acrylate as a monomer component. The molecular weight of the polymer was 3000, and the degree of dispersion was 1.6.
In the sample preparation of Example 1, in place of 2- (vinyloxyethoxy) ethyl acrylate, 20 parts by mass of the polymer (B2BO) was added, and photocationic polymerization was started with respect to 100 parts by mass of the polymer (B2BO). As an agent, 5 parts by mass of ESACURE 1064 (trade name, manufactured by Nippon Shibel Hegner) was added. Except for this, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 7 and the dicing die bonding tape of Example 7, respectively.

(1.8) Example 8
A polymer (B2AP) was obtained by cationic polymerization using 2- (vinyloxyethoxy) ethyl acrylate as a monomer component. The polymer had a molecular weight of 100,000 and a dispersity of 2.5.
In the sample preparation of Example 1, 20 parts by mass of the polymer (B2AP) was added instead of 2- (vinyloxyethoxy) ethyl acrylate, and the photopolymerization initiator was added to 100 parts by mass of the polymer (B2AP). 5 parts by mass of Irgacure 184 (Nippon Ciba Geigy Co., Ltd., trade name) was added. Otherwise, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 8 and the dicing die bonding tape of Example 8, respectively.

(1.9) Example 9
A polymer (B2BP) was obtained by radical polymerization using 2- (vinyloxyethoxy) ethyl acrylate as a monomer component. The polymer had a molecular weight of 100,000 and a dispersity of 2.7.
In the sample preparation of Example 1, 20 parts by mass of the polymer (B2BP) was added instead of 2- (vinyloxyethoxy) ethyl acrylate, and photocationic polymerization was started with respect to 100 parts by mass of the polymer (B2AP). As an agent, 5 parts by mass of ESACURE 1064 (trade name, manufactured by Nippon Shibel Hegner) was added. Otherwise, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 9 and the dicing die bonding tape of Example 9, respectively.

(1.10) Example 10
A polymer (B2AQ) was obtained by cationic polymerization using 80 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate and 20 parts by mass of n-butyl vinyl ether as monomer components. The molecular weight of the polymer was 80,000, and the degree of dispersion was 2.6.
In the sample preparation of Example 1, 20 parts by mass of the polymer (B2AQ) was added instead of 2- (vinyloxyethoxy) ethyl acrylate, and the photopolymerization initiator was added to 100 parts by mass of the polymer (B2AQ). 5 parts by mass of Irgacure 184 (Nippon Ciba Geigy Co., Ltd., trade name) was added. Except for this, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 10 and the dicing die bonding tape of Example 10, respectively.

(1.11) Example 11
A polymer (B2BQ) was obtained by radical polymerization using 80 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate and 20 parts by mass of n-butyl acrylate as monomer components. The polymer had a molecular weight of 100,000 and a dispersity of 2.8.
In the sample preparation of Example 1, in place of 2- (vinyloxyethoxy) ethyl acrylate, 20 parts by mass of the polymer (B2BQ) was added, and photocationic polymerization was started with respect to 100 parts by mass of the polymer (B2BQ). As an agent, 5 parts by mass of ESACURE 1064 (trade name, manufactured by Nippon Shibel Hegner) was added. Otherwise, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 11 and the dicing die bonding tape of Example 11, respectively.

(1.12) Example 12
n-Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, a mixture of benzoyl peroxide as a polymerization initiator, adjust the dropping amount appropriately, adjust the reaction temperature and reaction time The compound (A2-1) which has a functional group was produced.
Next, in this polymer solution, 2-hydroxyethyl methacrylate separately synthesized from methacrylic acid and ethylene glycol as a compound having a radiation curable carbon-carbon double bond and a functional group, hydroquinone as a polymerization inhibitor is appropriately converted into A2-1. Acrylic copolymer having a radiation-curable carbon-carbon double bond-containing group having a mass average molecular weight of 650,000, a glass transition temperature of −35 ° C., and an iodine value of 5 by adjusting the dropping amount and the reaction temperature and reaction time. Polymer A2 was obtained.
Then, 30 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate (B1A) as a compound (B1) having a structure represented by the general formula (1) is added to 100 parts by mass of the acrylic pressure-sensitive adhesive and cured. 5 parts by mass of polyisocyanate compound Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) as an agent, and Irgacure 184 (Japan) as a photopolymerization initiator with respect to 100 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate (B1A). Ciba Geigy Co., Ltd., trade name) 5 parts by mass was added to obtain a radiation curable resin composition pressure-sensitive adhesive.
Otherwise, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above, and these were used as the dicing tape of Example 12 and the dicing die bonding tape of Example 12, respectively.

(1.13) Example 13
To the polymer solution of A2-1 obtained in Example 12, 2-hydroxyethyl methacrylate and the amount of hydroquinone added as a polymerization inhibitor were adjusted as appropriate, the reaction temperature and reaction time were adjusted, and the mass average molecular weight was 700,000. An acrylic copolymer compound A3 having a glass transition temperature of −35 ° C. and an iodine value of 10 was produced.
In Example 12, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 12 except that A3 was used instead of A2, and these were respectively used as the dicing tape of Example 13 and Example. 13 dicing die bonding tapes were obtained.

(1.14) Example 14
To the polymer solution of A2-1 obtained in Example 12, 2-hydroxyethyl methacrylate and a dropwise addition amount of hydroquinone as a polymerization inhibitor were added as appropriate, the reaction temperature and reaction time were adjusted, and the mass average molecular weight was 720,000. An acrylic copolymer compound A4 having a glass transition temperature of −40 ° C. and an iodine value of 20 was produced.
In Example 12, a dicing tape and a dicing die bonding tape were produced in the same manner as in Example 12 except that A4 was used in place of A2, and these were respectively used as the dicing tape of Example 14 and Example. 14 dicing die bonding tapes were obtained.

(1.15) Example 15
In the sample preparation of Example 1, trimethylolpropane triacrylate was added as a photopolymerizable curing agent to the acrylic pressure-sensitive adhesive A1 to obtain a pressure-sensitive adhesive A5 of a radiation curable resin composition having an iodine value of 10.
Then, 30 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate (B1A) as a compound (B1) having a structure represented by the general formula (1) is added to 100 parts by mass of the acrylic pressure-sensitive adhesive and cured. 5 parts by mass of polyisocyanate compound coronate L (manufactured by Nippon Polyurethane Co., Ltd., trade name) as an agent, and Irgacure 184 (Nippon Ciba Geigy Corporation) as a photopolymerization initiator with respect to 100 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate Product, trade name) 5 parts by weight were added to obtain a pressure-sensitive adhesive for the radiation curable resin composition.
Other than that, a dicing tape and a dicing die bonding tape were produced in the same manner as in Example 1, and these were used as the dicing tape of Example 15 and the dicing die bonding tape of Example 15, respectively.

(1.16) Example 16
In the sample preparation of Example 1, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 1 except that the adhesive film 13-2 was changed. The dicing die bonding tape of Example 16 was obtained.

(1.17) Example 21
n-Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, a mixture of benzoyl peroxide as a polymerization initiator, adjust the dropping amount appropriately, adjust the reaction temperature and reaction time An acrylic copolymer (acrylic pressure-sensitive adhesive A1) having a weight average molecular weight of 600,000 and a glass transition temperature of −35 ° C. was produced.
Thereafter, polymer (X) (B1AP) was obtained by cationic polymerization using 2- (vinyloxyethoxy) ethyl acrylate as the component (B) in the general formula (1). The polymer had a molecular weight of 20,000 and a dispersity of 2.4. Here, the molecular weight and the degree of dispersion refer to values obtained as polystyrene-reduced weight average molecular weight and degree of dispersion by the following methods. Also in the following examples and comparative examples, the molecular weight and the degree of dispersion of the polymer were measured by the same method as described above.
(Measurement condition)
GPC device: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Column: TSK gel SuperHM-H / H4000 / H3000 / H2000 (trade name, manufactured by Tosoh Corporation)
Flow rate: 0.6 mL / min,
Concentration: 0.3% by mass
Injection volume: 20 μL,
Column temperature: 40 ° C
Developing solvent: Chloroform

  15 parts by mass of the polymer (B1AP) is added to 100 parts by mass of the acrylic pressure-sensitive adhesive (A1), 6 parts by mass of a polyisocyanate compound coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.) as a curing agent, and light. As a polymerization initiator, 5 parts by mass of Irgacure 184 (trade name, manufactured by Nippon Ciba Geigy Co., Ltd.) was added per 100 parts by mass of the polymer (B1AP) to obtain a pressure-sensitive adhesive for the radiation curable resin composition.

  Further, an ethylene-ionomer copolymer (trade name HiMilan 1706 manufactured by Mitsui DuPont Chemical Co., Ltd.) was melt-kneaded and molded to obtain a base resin film having a thickness of 100 μm and a width of 300 mm.

Thereafter, the adhesive is applied to the base resin film with a gravure coater, dried in a hot air drying furnace, and a laminated body of an adhesive layer having a thickness of 10 μm after drying and a base film. The dicing tape of Example 21 was obtained.
Then, the 20-micrometer-thick adhesive film (13-1) produced previously as follows was bonded on the adhesive layer of an adhesive tape, and the dicing die-bonding tape of Example 21 was produced.
50 parts by mass of cresol novolac type epoxy resin (epoxy equivalent 197, molecular weight 1300, softening point 70 ° C.) as an epoxy resin, 1.5 parts by mass of γ-mercaptopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane as a silane coupling agent Cyclohexanone was added to a composition composed of 3 parts by mass and 30 parts by mass of silica filler having an average particle size of 16 nm, and the mixture was stirred and mixed, and further kneaded for 90 minutes using a bead mill.
100 parts by mass of acrylic resin (mass average molecular weight: 800,000, glass transition temperature-17 ° C), 6 parts of dipentaerythritol hexaacrylate as a hexafunctional acrylate monomer, 0.5 part of an adduct of hexamethylene diisocyanate as a curing agent, 3 parts of Curazole 2PZ (trade name, 2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.) were added, mixed by stirring, and vacuum degassed to obtain an adhesive.
This adhesive was applied onto a 25 μm thick release-treated polyethylene terephthalate film, dried by heating at 110 ° C. for 1 minute to form a coating film having a thickness of 20 μm, and an adhesive film (13 -1) was produced.

(1.18) Example 22
In the sample preparation of Example 21, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 21 except that the addition amount of B1AP was changed to 3 parts by mass. The dicing tape and the dicing die-bonding tape of Example 22 were used.

(1.19) Example 23
In the sample preparation of Example 21, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 21 except that the addition amount of B1AP was changed to 30 parts by mass. The dicing tape and the dicing die bonding tape of Example 23 were used.

(1.20) Example 24
In the sample preparation of Example 21, as a photopolymerization initiator, 5 parts by mass of Irgacure 184 (trade name, manufactured by Ciba Geigy Co., Ltd.) per 100 parts by mass of the polymer (X) (B1AP) and a photocationic polymerization initiator ESACURE 1064 5 parts by mass (trade name, manufactured by Nippon Shibel Hegner) was added. Other than that, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 21, and these were used as the dicing tape of Example 24 and the dicing die bonding tape of Example 24, respectively.

(1.21) Example 25
Polymer (X) (B1AO) was obtained by cationic polymerization using 2- (vinyloxyethoxy) ethyl acrylate as the component (B) in the general formula (1). The molecular weight of the polymer was 5,000, and the degree of dispersion was 1.6.
In the sample preparation of Example 21, in place of B1AP, 30 parts by mass of the polymer (B1AO) was added, and Irgacure 184 (manufactured by Ciba Geigy Japan Co., Ltd.) as a photopolymerization initiator per 100 parts by mass of the polymer (B1AO). Product name) 5 parts by mass were added. Other than that, a dicing tape and a dicing die bonding tape were prepared in exactly the same manner as in Example 21, and the dicing tape and dicing die bonding tape in Example 25 and Dicing die bonding in Example 25, respectively. Tape.

(1.22) Example 26
Polymer (X) (B1AP2) was obtained by cationic polymerization using 2- (vinyloxyethoxy) ethyl acrylate as the component (B) in the general formula (1). The polymer had a molecular weight of 100,000 and a dispersity of 2.7.
In the sample preparation of Example 21, in place of B1AP, 15 parts by mass of the polymer (B1AP2) was added, and Irgacure 184 (manufactured by Ciba Geigy Japan) as a photopolymerization initiator per 100 parts by mass of the polymer (B1AP2). Product name) 5 parts by mass were added. Except for this, a dicing tape and a dicing die bonding tape were prepared in exactly the same manner as in Example 1, and the dicing tape and dicing die bonding tape in Example 26 were produced respectively. Tape.

(1.23) Example 27
Polymer (X) (B2AQ) was obtained by cationic polymerization using 10% by mass of 2- (vinyloxyethoxy) ethyl acrylate and 90% by mass of n-butyl vinyl ether as the component (B) of the general formula (1). The molecular weight of the polymer was 30,000, and the degree of dispersion was 2.6.
In the sample preparation of Example 21, instead of B1AP, 15 parts by mass of the polymer (B2AQ) was added, and Irgacure 184 (manufactured by Ciba Geigy Japan Co., Ltd.) as a photopolymerization initiator per 100 parts by mass of the polymer (B2AQ). Product name) 5 parts by mass were added. Other than that, a dicing tape and a dicing die bonding tape were produced in the same manner as in Example 21, and these were used as the dicing tape of Example 27 and the dicing die bonding tape of Example 27, respectively.

(1.24) Example 28
Polymer (X) (B2BQ) was obtained by radical polymerization using 10 parts by mass of 2- (vinyloxyethoxy) ethyl acrylate and 90 parts by mass of n-butyl acrylate as the component (B) in the general formula (1). . The molecular weight of the polymer was 30,000, and the degree of dispersion was 2.8.
In the preparation of the sample of Example 21, instead of B1AP, 15 parts by mass of the polymer (B2BQ) was added, and ESACURE 1064 (manufactured by Nippon Sebel Hegner, Inc., product) as a photocationic polymerization initiator per 100 parts by mass of the polymer (B2BQ). Name) 5 parts by mass were added. Other than that, a dicing tape and a dicing die bonding tape were produced in the same manner as in Example 21, and these were used as the dicing tape of Example 28 and the dicing die bonding tape of Example 28, respectively.

(1.25) Example 29
Polymer (X) (B3AP) was obtained by radical polymerization using 2- (vinyloxyethoxy) ethyl methacrylate as the component (B) in the general formula (1). The molecular weight of the polymer was 20,000, and the degree of dispersion was 2.7.
In the sample preparation of Example 21, instead of B1AP, 15 parts by mass of the polymer (B3AP) was added, and Irgacure 184 (manufactured by Ciba Geigy Japan Co., Ltd.) as a photopolymerization initiator per 100 parts by mass of the polymer (B3AP). Product name) 5 parts by mass were added. Otherwise, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 21, and these were used as the dicing tape of Example 29 and the dicing die bonding tape of Example 29, respectively.

(1.26) Example 30
Polymer (X) (B4AP) was obtained by cationic polymerization using 2- (vinyloxyisopropoxy) propyl acrylate as the component (B) in the general formula (1). The polymer had a molecular weight of 20,000 and a dispersity of 2.6.
In the sample preparation of Example 21, instead of B1AP, 15 parts by mass of the polymer (B4AP) was added, and Irgacure 184 (manufactured by Ciba Geigy Japan Co., Ltd.) as a photopolymerization initiator per 100 parts by mass of the polymer (B4AP). Product name) 5 parts by mass were added. Other than that, a dicing tape and a dicing die bonding tape were prepared in exactly the same manner as in Example 21, and these were used as the dicing tape of Example 30 and the dicing die bonding tape of Example 30, respectively.

(1.27) Example 31
n-Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, a mixture of benzoyl peroxide as a polymerization initiator, adjust the dropping amount appropriately, adjust the reaction temperature and reaction time The compound (A7-1) which has a functional group was produced.
Next, in this polymer solution, 2-hydroxyethyl methacrylate separately synthesized from methacrylic acid and ethylene glycol as a compound having a radiation curable carbon-carbon double bond and a functional group, hydroquinone as a polymerization inhibitor is appropriately added to A7-1. Acrylic copolymer having a radiation-curable carbon-carbon double bond-containing group having a mass average molecular weight of 650,000, a glass transition temperature of −35 ° C., and an iodine value of 10 by adjusting the dropping amount and the reaction temperature and reaction time. Polymer A7 was obtained.
Thereafter, 15 parts by mass of the polymer (X) (B1AP) prepared in Example 21 was added to 100 parts by mass of the acrylic pressure-sensitive adhesive (A7), and a polyisocyanate compound coronate L (manufactured by Nippon Polyurethane Co., Ltd.) was used as a curing agent. (Trade name) 6 parts by mass, and further, as a photopolymerization initiator, 5 parts by mass of Irgacure 184 (trade name, manufactured by Nippon Ciba-Geigy Co., Ltd.) is added per 100 parts by mass of the polymer (B1AP). A product adhesive was obtained.
Other than that, a dicing tape and a dicing die bonding tape were prepared in the same manner as described above and in Example 21, and these were used as the dicing tape of Example 31 and the dicing die bonding tape of Example 31, respectively.

(1.28) Example 32
In the sample preparation of Example 21, a dicing tape and a dicing die bonding tape were prepared in exactly the same manner except that the adhesive film (13-2) was used as follows. And the dicing die bonding tape of Example 32.
Adhesive film (13-2):
Production of the adhesive film (13-1) except that 50 parts by mass of a cresol novolac type epoxy resin (epoxy equivalent 197, molecular weight 1300, softening point 70 ° C.) as an epoxy resin and 1 part of an adduct of hexamethylene diisocyanate as a curing agent The adhesive film (13-2) was produced in exactly the same manner as in Example 1.

(1.34) Comparative Example 1
In the sample preparation of Example 1, a dicing tape and a dicing die bonding tape were prepared without adding 2- (vinyloxyethoxy) ethyl acrylate and Irgacure 184 to the pressure-sensitive adhesive. And a dicing die bonding tape of Comparative Example 1.

(1.35) Comparative Example 2
In the sample preparation of Example 1, the addition amount of 2- (vinyloxyethoxy) ethyl acrylate was changed to 0.08 parts by mass to prepare a dicing tape and a dicing die bonding tape. And a dicing die bonding tape of Comparative Example 2.

(1.36) Comparative Example 3
In the sample preparation of Example 1, the addition amount of 2- (vinyloxyethoxy) ethyl acrylate was changed to 60 parts by mass to prepare a dicing tape and a dicing die bonding tape. The tape and the dicing die bonding tape of Comparative Example 3 were used.

(1.37) Comparative Example 4
In the sample preparation of Example 12, a dicing tape and a dicing die bonding tape were prepared without adding 2- (vinyloxyethoxy) ethyl acrylate at all, and these were respectively compared with the dicing tape of Comparative Example 4 and the Comparative Example. No. 4 dicing die bonding tape.

(1.38) Comparative Example 5
In the sample preparation of Example 15, a dicing tape and a dicing die bonding tape were prepared without adding 2- (vinyloxyethoxy) ethyl acrylate at all, and these were respectively compared with the dicing tape of Comparative Example 5 and the Comparative Example. No. 5 dicing die bonding tape.

(1.39) Comparative Example 21
In the sample preparation of Example 21, a dicing tape and a dicing die bonding tape were prepared without adding B1AP and Irgacure 184 to the adhesive, and the dicing tape of Comparative Example 21 and the dicing of Comparative Example 21, respectively, were prepared. -Die bonding tape.

(1.40) Comparative Example 22
In the sample preparation of Example 21, instead of B1AP, 15 parts by mass of trimethylolpropane triacrylate was added as a photopolymerizable curing agent, and Irgacure 184 (Nippon Ciba Geigy) as a photopolymerization initiator per 100 parts by mass of trimethylolpropane triacrylate. 5 parts by weight (trade name, manufactured by Co., Ltd.) Except that, a dicing tape and a dicing die bonding tape were prepared in the same manner as in Example 21, and these were used as the dicing tape of Comparative Example 22 and the dicing die bonding tape of Comparative Example 22, respectively.

(2) Sample evaluation (2.1) Measurement of adhesive strength In the dicing die bonding tape of each sample, ultraviolet rays were irradiated to the dicing die bonding tape initially or refrigerated for 6 months in an environment of 0 ± 5 ° C. Then, the adhesive strength before and after UV irradiation was measured based on JIS-Z0237. Measurement was performed at 90 ° peeling and a peeling speed of 50 mm / min. A high-pressure mercury lamp (80 mw / cm ² , irradiation distance 10 cm) was used as the ultraviolet lamp, and the irradiation intensity was 200 mJ / cm ² . The measurement results are shown in Tables 2-1 and 2-2.

(2.2) Gel fraction About 0.05 g of the pressure-sensitive adhesive layer was weighed and immersed in 50 mL of xylene at 120 ° C. for 24 hours, and then filtered through a 200-mesh stainless steel wire mesh to remove the insoluble matter on the wire mesh by 110. Dry at 120 ° C. for 120 minutes. Next, the mass of the dried insoluble matter was weighed, and the gel fraction was calculated by the following formula. The results are shown in Tables 2-1 and 2-2.
Gel fraction (%) = (mass of insoluble matter / mass of weighed pressure-sensitive adhesive layer) × 100

(2.3) Presence / absence of chip jumping The dicing tape of each sample was heat bonded to a silicon wafer at 70 ° C. for 1 minute, and then the wafer was diced to 5 mm × 5 mm. Then, the chip | tip after dicing was observed, the presence or absence of the chip | tip jump at the time of dicing was observed, and the thing without a chip | tip jump was set as the pass. The evaluation results are shown in Tables 2-1 and 2-2.

(2.4) Contact Area between Adhesive Layer and Adhesive Layer A silicon wafer having a thickness of 50 μm was heat bonded to the dicing die bonding tape of each sample at 70 ° C. for 10 seconds, and then diced to 10 mm × 10 mm.
Thereafter, the adhesive layer was irradiated with ultraviolet rays of 200 mJ / cm ² by an air-cooled high-pressure mercury lamp (80 mw / cm ² , irradiation distance 10 cm), and then expanded by a die picker apparatus (trade name CAP-300II manufactured by Canon Machinery Co., Ltd.). The amount of expansion (push-up amount) of 3, 5 and 8 mm was carried out by pressing down and pressing the portion of the wafer processing tape that did not overlap the wafer outer periphery of the wafer bonding site against a circular push-up member. The amount of expansion is the amount of change in the relative position between the ring frame and the push-up member before and after pressing. At that time, for each silicon chip, the size relationship between the contact area (b) of the adhesive layer and the pressure-sensitive adhesive layer before expansion, and the contact area (a) of the adhesive layer and the pressure-sensitive adhesive layer after expansion, a <b, that is, the presence or absence of peeling at the adhesive layer / adhesive layer interface was observed. As a result, those satisfying a <b were considered acceptable. In Tables 2-1 and 2-2, “OK” is shown as pass and “X” is shown as fail.

(2.5) Pick-up property A silicon wafer having a thickness of 50 μm with respect to the dicing die bonding tape of each sample, which was refrigerated for 1, 3, 5, or 6 months in an initial or 0 ± 5 ° C. environment. Was bonded by heating at 70 ° C. for 10 seconds, and then diced to 10 mm × 10 mm.
After that, the adhesive layer was irradiated with ultraviolet rays of 200 mJ / cm ² with an air-cooled high-pressure mercury lamp (80 mw / cm ² , irradiation distance 10 cm), and then a die picker device (product made by Canon Machinery Co., Ltd., product) A pickup test according to name CAP-300II) was performed, and the success rate of pickup in terms of the number of pickup chips was obtained.
At that time, in the picked-up element, the pick-up success rate was calculated by assuming that the pick-up was successful when the adhesive layer peeled from the pressure-sensitive adhesive layer was retained. The calculation results are shown in Tables 2-1 and 2-2. ◎, ○, △, ×, XX criteria (pickup property criteria) are as follows, ◎ and ○ are accepted, and the results are shown in Tables 2-1 and 2-2.

“◎”: The success rate of pick-up at the push-up heights of 0.7 mm, 0.5 mm, 0.3 mm, and 0.1 mm by the push-up pin is 100%. “◯” ... Push-up height 0.7 mm, 0.5 mm, 0 The pickup success rate at 3 mm is 100%, and the pickup success rate at a push-up height of 0.1 mm is less than 100%. “△”… The pickup success rate at a push-up height of 0.7 mm and 0.5 mm is 100%. In addition, the pickup success rate is less than 100% at a push-up height of 0.3 mm and 0.1 mm. “X”: The pickup success rate is less than 100% at a push-up height of 0.7 mm, 0.5 mm, and 0.3 mm. "XX" ... Pickup success rate is not 100% at push-up heights of 0.7mm, 0.5mm, 0.3mm, 0.1mm Be

(2.6) Package Reliability The dicing die bonding tape of each sample is 1 at 70 ° C. compared to the dicing die bonding tape initially or refrigerated for 1, 3, 5, or 6 months in an environment of 0 ± 5 ° C. After heat bonding to the wafer for 1 minute, the wafer was diced to 10 mm × 10 mm. Thereafter, the adhesive layer was irradiated with ultraviolet rays of 200 mJ / cm ² with an air-cooled high-pressure mercury lamp (80 mW / cm ² , irradiation distance 10 cm), and then a pick-up test was performed with a die bonder device (trade name CPS-100FM, manufactured by NEC Machinery). A simulated element in which an aluminum wiring is formed on a silicon chip of a picked-up adhesive-attached chip is die-bonded on a silver-plated FR4 substrate via a sheet-like adhesive, and formed at 175 ° C., 70 kgf / cm ² , molding time. Twenty BGA packages with a thickness of 1.0 mm were molded under a condition of 120 seconds, post-cured at 180 ° C. for 4 hours, and used as an evaluation package.
Then, after immersing the obtained package in a solder bath adjusted to 260 ° C. for 10 seconds in advance, the presence or absence of package cracks was confirmed by a transmission method using an ultrasonic exploration device (Hyper manufactured by Hitachi Construction Machinery Co., Ltd.). evaluated. The evaluation results are shown in Tables 2-1 and 2-2. Here, the evaluation was made based on the number of cracked defective packages among the 20 evaluation packages. Of the 20 evaluation packages, any defective package with one crack was rejected.

(3) Summary From the results of Tables 2-1 and 2-2, the samples of the examples all have extremely high adhesive strength before ultraviolet irradiation, and very low adhesive strength after ultraviolet irradiation. There is no occurrence of flying, and further, the contact area between the chip and the adhesive layer and the dicing tape divided into pieces before and after the expansion is such that the contact area before the expansion (b)> the contact area after the expansion (a). Even after 6 months, the pickup and package reliability were excellent.
On the other hand, Comparative Examples 1 and 2 containing a compound having a structure represented by the general formula (1) or a polymer having the compound represented by the general formula (1) as a constituent component or a small amount Then, the adhesive strength after ultraviolet irradiation was not sufficiently lowered, and the pickup property was inferior. Further, in Comparative Examples 4 and 5 not containing the above-described compound or polymer, the adhesive strength after ultraviolet irradiation was reduced, but the cutting waste was entangled with the adhesive layer, hindering peeling, and the pick-up property was inferior. Even if it could be picked up, process defects such as package cracks occurred due to the attachment of cutting waste to the adhesive layer during die bonding. In Comparative Example 3 in which the compounding amount of the compound is too large, the pressure-sensitive adhesive becomes too brittle due to the curing reaction, and as a result of the occurrence of glue cracking, peeling from the base film, etc., contaminating the chip, package cracking occurs and package reliability is improved. Remarkably reduced.
Moreover, in the comparative example 21 which does not contain the polymer which has a compound represented by the said General formula (1) as a structural component, the adhesive strength after ultraviolet irradiation did not fully fall, but was inferior to pick-up property.
From the above, the tape for semiconductor processing using the acrylic pressure-sensitive adhesive in which a specific amount of the polymer having the compound represented by the general formula (1) as a constituent component is mixed in the pressure-sensitive adhesive layer is used to prevent chip skipping and pickup characteristics. This proves useful in terms of package reliability.

DESCRIPTION OF SYMBOLS 1 Semiconductor wafer 2 Semiconductor chip 10 Dicing die-bonding tape 11 Dicing tape 12a, 12a 'Base resin film 12b, 12b' Adhesive layer 13 Adhesive film 13a Release liner 13b Adhesive layer 20 Ring frame 21 Thin grindstone 22 Adsorption table 30 Push-up member 31 Push-up pin 32 Adsorption collet

Claims (13)

A semiconductor processing tape having an adhesive layer on a base resin film,
The semiconductor processing tape is used in a process of picking up a semiconductor chip by fixing and dicing a semiconductor wafer and then reducing the adhesive strength of the adhesive layer by irradiating ultraviolet rays when manufacturing a semiconductor manufacturing apparatus. Is,
The pressure-sensitive adhesive layer has, as a constituent component, a compound having a structure represented by the following general formula (1) or a compound (B) represented by the following general formula (1) with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. A semiconductor processing tape comprising a radiation curable resin composition containing 0.1 to 50 parts by mass of coalesced (X).
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CHR 3 ····· (1)
[In General Formula (1), R ¹ represents a hydrogen atom or methyl. R ² represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. ]   The semiconductor processing tape according to claim 1, wherein the polymer (X) has a molecular weight of 5,000 to 100,000.   3. The polymer (X) contains a radical polymerizable compound C1 as a constituent component other than the constituent component from the compound (B) in an amount of 90% by mass or less in the polymer. Tape for semiconductor processing.   The polymer (X) contains a cationic polymerizable compound C2 as a constituent component other than the constituent component from the compound (B) in an amount of 90% by mass or less in the polymer. Tape for semiconductor processing.   A semiconductor processing tape comprising 3 to 30 parts by mass of the polymer (X) according to any one of claims 1 to 4 with respect to 100 parts by mass of an acrylic pressure-sensitive adhesive.   The semiconductor processing tape according to claim 1, wherein the acrylic pressure-sensitive adhesive contains a compound having a radiation curable carbon-carbon double bond having an iodine value of 10 or less.   The semiconductor processing tape according to claim 1, wherein a gel fraction of the resin composition of the pressure-sensitive adhesive layer is 50% or more.   A tape for semiconductor processing, further comprising an adhesive layer on the pressure-sensitive adhesive layer of the tape for semiconductor processing according to claim 1. The semiconductor processing tape according to claim 8,
When manufacturing a semiconductor manufacturing apparatus , the semiconductor processing tape fixes and dices a semiconductor wafer, and then reduces the adhesive strength of the adhesive layer by irradiating with ultraviolet rays, picks up a semiconductor chip, and leads to a lead frame or semiconductor. Used to adhere to the chip ,
In the tape for semiconductor processing, an adhesive layer and an adhesive layer are provided in this order on a base resin film, and in the pick-up process after the dicing process that separates the semiconductor wafer along the scribe line, the individual pieces after expansion For semiconductor processing, wherein the contact area (a) between the adhesive layer and the pressure-sensitive adhesive layer on the formed semiconductor chip is smaller than the contact area (b) between the adhesive layer and the pressure-sensitive adhesive layer before expansion tape.   The semiconductor processing tape according to claim 9, wherein an adhesive layer attached to the singulated semiconductor chip is inside the scribe line. The adhesive layer is laminated on a pressure-sensitive adhesive layer where a semiconductor wafer is bonded, and does not have an adhesive layer on a pressure-sensitive adhesive layer where a semiconductor wafer is not bonded. Or a tape for semiconductor processing according to 10 . The process of dicing the semiconductor wafer with which the semiconductor processing tape of any one of Claims 1-11 was bonded, the process of irradiating an adhesive layer with an ultraviolet-ray, and reducing the adhesive force of an adhesive layer, and A method for manufacturing a semiconductor device, comprising a step of picking up a semiconductor chip. The method for manufacturing a semiconductor device according to claim 12, comprising a step of bonding the picked-up semiconductor chip to a lead frame or a semiconductor chip.

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