JP5424941B2 - Radiation curable adhesive composition, adhesive film for dicing using the same, and method for producing cut pieces - Google Patents

Description

  The present invention relates to a radiation-curable pressure-sensitive adhesive composition, a dicing pressure-sensitive adhesive film using the same, and a method for producing a cut piece. More specifically, the present invention relates to a dicing pressure-sensitive adhesive film suitably used for cutting a workpiece such as a semiconductor wafer or a semiconductor package having an active surface.

  2. Description of the Related Art Conventionally, semiconductor-related materials for semiconductor wafers and semiconductor packages are cut using a cutting blade such as a rotary blade and separated into small semiconductor elements and IC components. For example, a semiconductor wafer made of silicon, germanium, gallium-arsenide, or the like is manufactured in a large diameter state and then back-grinded (back grind) until a predetermined thickness is obtained. Back surface processing (etching processing, polishing processing, etc.) is performed. Next, the semiconductor wafer is cut and separated (diced) into element pieces, and then transferred to the subsequent process. In this manufacturing process, the mounting step of pasting the semiconductor wafer to the adhesive film for dicing in advance, the dicing step of dicing the semiconductor wafer into semiconductor element pieces in a state where the adhesive film is pasted on the semiconductor wafer, the cleaning step, the expanding step, Various processes such as a pickup process are performed. In the pick-up step, the dicing adhesive film is stretched to some extent, the dicing adhesive film below the semiconductor element to be picked up is lifted in a dotted or linear shape, and the semiconductor element and the dicing adhesive film are peeled off. A system in which a semiconductor element is obtained by picking up from the upper part by vacuum suction or the like while being promoted is employed.

  The dicing pressure-sensitive adhesive film generally has a configuration in which a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition is formed on a substrate such as a plastic film. When manufacturing a semiconductor element, the dicing adhesive film does not peel from the adhesive film even if water pressure of washing water is applied during dicing in order to suppress the detachment and scattering of the semiconductor element from the adhesive film in the dicing process. While a high level of adhesive strength is required, it is easy to peel off in the pick-up process, so that the adhesive layer does not damage the semiconductor wafer. It is required to have low contamination.

  Radiation-curable pressure-sensitive adhesive composition comprising a (meth) acrylic polymer having a radiation-reactive carbon-carbon double bond on a radiation-transmissive substrate, for example, as a dicing pressure-sensitive adhesive film that satisfies the above characteristics A pressure-sensitive adhesive film for dicing having a pressure-sensitive adhesive layer made of a material is used. In this kind of pressure-sensitive adhesive film for dicing, the radiation-curable pressure-sensitive adhesive composition has a high adhesive strength before being cured by radiation, and therefore, desorption and scattering of the semiconductor element can be suppressed in the dicing process. Further, when radiation is applied to the pressure-sensitive adhesive layer, the radiation-curable pressure-sensitive adhesive composition is cured and the adhesive strength is remarkably reduced, so that the semiconductor element can be easily peeled from the dicing pressure-sensitive adhesive film in the pickup process.

  By the way, in recent years, in the semiconductor manufacturing process, after the back surface grinding process or the back surface grinding process and the back surface process have been completed for the purpose of improving the tact time and preventing damage due to the thinning of the semiconductor wafer (for example, 100 μm or less). Thereafter, dicing adhesive films are often bonded to semiconductor wafers within a short time. After such back surface grinding processing, or after back surface grinding processing and back surface processing, when bonding a thin semiconductor wafer and a dicing adhesive film within a short time, the adhesive force between the semiconductor wafer and the adhesive layer is There is a problem that it becomes high and peeling after curing by radiation becomes difficult and pick-up property is lowered. This is because the natural oxide film is not sufficiently formed on the entire surface of the semiconductor wafer on the processed surface where the backside grinding process or the backside processing of the semiconductor wafer is performed, and the surface of the semiconductor wafer is not oxidized in the active atoms (for example, Therefore, when a dicing adhesive film is bonded to the active surface, the unoxidized active atom and the radiation-curable adhesive composition of the adhesive layer are formed. It is inferred that a chemical bond is generated between the non-oxidized active atom and the radiation curable pressure-sensitive adhesive composition upon contact.

  In particular, when synthesizing a (meth) acrylic polymer having a radiation-reactive carbon-carbon double bond as described above, a copolymerization monomer component having an alkyl group and a copolymerization monomer having a functional group such as a hydroxyl group. A base polymer is synthesized by copolymerizing the components, and a functional group that reacts with the functional group and a radiation-reactive compound having a radiation-reactive carbon-carbon double bond and the base polymer are subjected to condensation or addition reaction. Therefore, it is necessary to introduce a functional group for reacting with the radiation-reactive compound into the base polymer, and in order to increase the cohesive strength of the adhesive layer by increasing the molecular weight of the (meth) acrylic polymer. When an agent is used, it is necessary to introduce a functional group for reacting with the crosslinking agent into the base polymer. If all the functional groups introduced into such a base polymer can be completely reacted with the radiation-reactive compound or the crosslinking agent, it is sufficient to introduce the functional group amount equivalent to the functional group amount of these compounds into the base polymer. . However, since the reactivity varies depending on the types of copolymerizable monomer components, radiation-reactive compounds and crosslinking agents of the base polymer, and the types of functional groups they have, the base polymer has a larger amount of functional groups than these compounds have. It is necessary to introduce a functional group amount. As a result, an unreacted functional group remains in the (meth) acrylic polymer, a chemical bond is generated between the functional group and the active atom as described above, and light peelability is likely to be reduced.

  For example, in Patent Document 1, a hydroxy compound such as polyalkylene glycol is used together with a radiation curable adhesive in order to solve the problem of adhesiveness between a semiconductor wafer having an active surface and an adhesive film for dicing in the pickup process as described above. A pressure-sensitive adhesive film for dicing having a pressure-sensitive adhesive layer containing benzene has been proposed. According to this dicing pressure-sensitive adhesive film, when a dicing pressure-sensitive adhesive film is attached to a semiconductor wafer having an active surface, the presence of a predetermined amount of a hydroxy compound on the surface of the pressure-sensitive adhesive layer causes the active atom and the radiation-curable pressure-sensitive adhesive. Chemical bonding with the agent is suppressed or prevented, thereby ensuring light release in the pickup process.

JP 2008-60434 A

  However, since the hydroxy compound as described above is not itself sticky and is a low molecular compound having a number average molecular weight of 3,000 or less, the semiconductor wafer and the dicing adhesive film in the dicing process There is a problem that the adhesiveness is lowered. In particular, in the dicing process, cleaning water is supplied to the semiconductor wafer to which the adhesive film for dicing has been applied in order to remove frictional heat during dicing and to prevent attachment of cutting waste. Although it is required that the pressure-sensitive adhesive layer can maintain a high adhesive strength, there is a problem that the adhesive strength when the washing water and the pressure-sensitive adhesive layer come into contact with each other tends to decrease due to the use of the low molecular weight hydroxy compound as described above. is there. Furthermore, in Patent Document 1, it is necessary to add 2 to 12% by mass of the hydroxy compound with respect to the total solid content in the pressure-sensitive adhesive layer in order to ensure light releasability after radiation irradiation. There is also a problem that the curability of the pressure-sensitive adhesive composition tends to be lowered, and such a low molecular weight component tends to remain on the semiconductor element at the time of pickup.

  The present invention solves the above-mentioned problems, and an object of the present invention is to provide a radiation-curable pressure-sensitive adhesive composition that has high adhesive strength before curing with radiation and that significantly decreases adhesive strength after curing with radiation. In addition, by using the radiation curable pressure-sensitive adhesive composition, the work to be processed having a high adhesive force in the dicing process and suppressing the detachment and scattering of the cut pieces such as semiconductor elements, and having an active surface in the pick-up process. An object of the present invention is to provide a dicing pressure-sensitive adhesive film having a pressure-sensitive adhesive layer capable of obtaining excellent light peelability and low contamination with respect to products.

The present invention is a (meth) acrylic polymer obtained by reacting a base polymer having a hydroxyl group with a radiation reactive compound having a radiation reactive carbon-carbon double bond and a functional group that reacts with the hydroxyl group in the molecule. As well as polyfunctional monomers,
The base polymer is a linear or branched alkyl group-containing (meth) acrylic monomer having a carbon number of 2 to 8, a hydroxyl group-containing (meth) acrylic monomer, and a linear chain having a carbon number of 14 to 18 as a copolymerization monomer component. Having at least an alkyl group-containing (meth) acrylic monomer,
The content of the linear or branched alkyl group-containing (meth) acrylic monomer having 2 to 8 carbon atoms is 30 to 80% by mass relative to the total amount of the copolymerizable monomer component, and the hydroxyl group-containing (meth) acrylic monomer The content is 5 to 20% by mass, the content of the linear alkyl group-containing (meth) acrylic monomer having 14 to 18 carbon atoms is 10 to 60% by mass,
The radiation-curable pressure-sensitive adhesive composition has a content of the radiation-reactive compound of 5 to 25 parts by mass with respect to 100 parts by mass of the base polymer.

  The radiation curable pressure-sensitive adhesive composition preferably contains 5 to 30 parts by mass of the polyfunctional monomer with respect to 100 parts by mass of the base polymer. Moreover, the said radiation-curable adhesive composition may contain a crosslinking agent and a photoinitiator further.

And this invention is a pressure-sensitive adhesive film for dicing having a base material and an adhesive layer on at least one surface of the base material,
The pressure-sensitive adhesive layer is a dicing pressure-sensitive adhesive film containing the radiation curable pressure-sensitive adhesive composition.

Further, the present invention attaches the dicing adhesive film to one surface of the workpiece,
The workpiece to which the adhesive film for dicing is attached is cut and separated into cut pieces,
Radiation is applied to the adhesive layer attached to the cut piece to reduce the adhesive strength of the adhesive layer,
It is the manufacturing method of the cut piece which picks up the said cut piece from the adhesive film for dicing which reduced the said adhesive force. In particular, when the workpiece is a semiconductor wafer having an active surface, the method for manufacturing the cut piece is effective.

  According to the present invention, since the pressure-sensitive adhesive layer contains the radiation-curable pressure-sensitive adhesive composition described above, the pressure-sensitive adhesive layer has a high pressure-sensitive adhesive force before being cured by radiation and has a low pressure-sensitive adhesive force after being cured by radiation. An adhesive film for dicing can be provided. This can reduce the separation and scattering of the cut pieces in the dicing step, and can easily peel the cut pieces from the dicing adhesive film in the pickup step, and can further reduce contamination after peeling.

FIG. 1 is a schematic cross-sectional view showing an example of a dicing adhesive film according to an embodiment of the present invention.

  The radiation-curable pressure-sensitive adhesive composition according to the present embodiment includes, as a copolymerization monomer component, a linear or branched alkyl group-containing (meth) acrylic monomer having 2 to 8 carbon atoms, a hydroxyl group-containing (meth) acrylic monomer, And a base polymer having at least a (meth) acrylic monomer having a linear alkyl group having 14 to 18 carbon atoms and a radiation reactive compound having a radiation reactive carbon-carbon double bond in the molecule. Containing (meth) acrylic polymer. In the present specification, (meth) acryl means acryl or methacryl.

  Specific examples of the (meth) acrylic monomer having a linear or branched alkyl group having 2 to 8 carbon atoms, which is one of the copolymerization monomer components used for synthesizing the base polymer, include, for example, (meth) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, (meta ) T-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Etc. These may be used alone or in combination. Among these, one selected from the group consisting of octyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate containing a linear or branched alkyl group having 8 carbon atoms is preferable. More preferred is 2-ethylhexyl (meth) acrylate.

  The content of the linear or branched alkyl group-containing (meth) acrylic monomer having 2 to 8 carbon atoms in the base polymer is 30 to 80% by mass with respect to the total amount of copolymerization monomer components constituting the base polymer, Preferably it is 40-80 mass%. When the content of the linear or branched alkyl group-containing (meth) acrylic monomer having 2 to 8 carbon atoms is less than 30% by mass, the adhesive strength of the (meth) acrylic polymer before curing by radiation tends to be reduced. On the other hand, when the content of the linear or branched alkyl group-containing (meth) acrylic monomer having 2 to 8 carbon atoms is more than 80% by mass, the content of the hydroxyl group-containing (meth) acrylic monomer which is another copolymerization monomer component The amount decreases. Therefore, the number of hydroxyl groups required to react with the radiation-reactive compound and introduce a radiation-reactive carbon-carbon double bond into the (meth) acrylic polymer is reduced, and the curability is likely to be lowered. Moreover, since the introduction amount of a linear alkyl group having 14 to 18 carbon atoms is also reduced, light peelability is deteriorated.

  In addition, the base polymer contains a hydroxyl group-containing (meth) acrylic monomer as one of the copolymerization monomer components. By using a hydroxyl group-containing (meth) acrylic monomer as one of the copolymerization monomer components, the introduced hydroxyl group and the radiation reactive compound are reacted to have a radiation reactive carbon-carbon double bond in the molecule. A (meth) acrylic polymer can be obtained. In addition, when a crosslinking agent is used by introducing a hydroxyl group, a three-dimensional crosslinked structure can be formed by a crosslinking reaction between the (meth) acrylic polymer and the crosslinking agent, thereby improving the cohesive strength of the pressure-sensitive adhesive layer. be able to. Specific examples of such a hydroxyl group-containing (meth) acrylic monomer include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , (Meth) acrylic acid 6-hydroxyhexyl and the like. These may be used alone or in combination.

  The content of the hydroxyl group-containing (meth) acrylic monomer in the base polymer is 5 to 20% by mass, preferably 5 to 10% by mass, based on the total amount of copolymerization monomer components constituting the base polymer. When the content of the hydroxyl group-containing (meth) acrylic monomer is less than 5% by mass, the number of hydroxyl groups in the base polymer is decreased, so that the introduction amount of the radiation reactive carbon-carbon double bond cannot be increased, Curability tends to decrease. In addition, when the amount of radiation-reactive carbon-carbon double bonds introduced is increased in order to improve curability, when a cross-linking agent is used to increase the molecular weight, the number of hydroxyl groups that react with the cross-linking agent decreases, and aggregation occurs. The force is reduced, or unreacted components remain, and glue stains are likely to occur. On the other hand, when the content of the hydroxyl group-containing (meth) acrylic monomer is more than 20% by mass, active atoms and hydroxyl groups on the active surface of a semiconductor wafer or the like are bonded, and the adhesive force is sufficiently reduced even by curing with radiation. As a result, the light peelability is deteriorated, and adhesive stains are easily generated on the cut piece after peeling.

  Furthermore, a base polymer contains a C14-C18 linear alkyl group containing (meth) acrylic-type monomer as one of the copolymerization monomer components. In order to obtain high adhesive strength before curing by radiation, it is preferable to use a lot of (meth) acrylic monomers containing a short-chain alkyl group having 2 to 8 carbon atoms as a copolymerization monomer component. Since the (meth) acrylic polymer used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film requires a hydroxyl group in order to ensure curability as described above, the active surface and The adhesive strength of becomes higher. According to the study by the present inventors, when a (meth) acrylic monomer containing a linear alkyl group having 14 to 18 carbon atoms is used as one of the copolymerization monomer components, it has high adhesive strength before curing by radiation. A radiation-curable pressure-sensitive adhesive composition having a low adhesive strength after curing with radiation and using a pressure-sensitive adhesive film for dicing provided with a pressure-sensitive adhesive layer containing the radiation-curable pressure-sensitive adhesive composition Therefore, in the dicing process, desorption and scattering of cut pieces such as semiconductor elements can be suppressed, and in the pick-up process, excellent light peelability and low contamination can be obtained even when a workpiece having an active surface is used. Was found.

  The reason why the above characteristics can be obtained by introducing the linear alkyl group having 14 to 18 carbon atoms into the molecule of the (meth) acrylic polymer is not necessarily clear, but is estimated as follows. First, when each of the above (meth) acrylic monomers is copolymerized in order to synthesize a base polymer, the (meth) acrylic monomer having a linear alkyl group having 14 to 18 carbon atoms is the (meta) ) Polymerization reaction between acrylic monomers and other copolymerization monomer components such as linear or branched alkyl group-containing (meth) acrylic monomers or hydroxyl group-containing (meth) acrylic monomers having 2 to 8 carbon atoms, or the number of carbon atoms Since the polymerization reaction between 2-8 linear or branched alkyl group-containing (meth) acrylic monomers and hydroxyl group-containing (meth) acrylic monomers is not significantly hindered, it has a low adverse effect on adhesive properties such as reduced adhesive strength. The residual amount of the molecular component of the monomer and the amount of the oligomer component produced are suppressed, and a high molecular weight base polymer can be obtained. In addition, if a linear alkyl group having 14 to 18 carbon atoms is introduced into the molecule of the (meth) acrylic polymer, the hydrophobicity of the (meth) acrylic polymer is improved and the pressure-sensitive adhesive layer and the washing water are in contact with each other. Even in this case, it is considered that the decrease in adhesive strength can be suppressed. Further, when a cross-linking agent is used, the reaction between the hydroxyl group of the (meth) acrylic polymer and the cross-linking agent is not greatly inhibited as long as it is a linear alkyl group having 14 to 18 carbon atoms. For this reason, a radiation-curable pressure-sensitive adhesive composition having a high adhesive force before curing with radiation can be obtained. On the other hand, the degradation of the peelability between the workpiece such as a semiconductor wafer having an active surface and the (meth) acrylic polymer was exposed on the polar surface of the (meth) acrylic polymer such as a hydroxyl group or an ester site and the surface of the active surface. This is due to the bond with the active atom. Therefore, if the (meth) acrylic polymer has a linear alkyl group having 14 to 18 carbon atoms at the side chain or terminal in the molecule, the long chain alkyl group exists in a free state in the molecule, It is thought that polar sites such as hydroxyl groups are concealed by the alkyl group, thereby preventing contact between the polar sites and the active atoms. For this reason, the (meth) acrylic polymer is sufficiently cured by curing with radiation, and the adhesive force can be significantly reduced. As a result, if a dicing adhesive film having an adhesive layer containing the radiation-curable adhesive composition of the present embodiment is used, a high adhesive force can be obtained for a workpiece such as a semiconductor wafer in the dicing process. Even if cleaning water is supplied, it is possible to reduce detachment and scattering of a cut piece such as a semiconductor element. In addition, the cut piece such as a semiconductor element and the adhesive film can be easily peeled off in the pick-up process, and the remaining adhesive composition on the cut piece can be reduced. If only a (meth) acrylic monomer containing an alkyl group having less than 14 carbon atoms is used as a copolymerization monomer component having a long-chain alkyl group, polar sites such as hydroxyl groups cannot be sufficiently concealed. Even after curing by radiation, the decrease in adhesive strength is insufficient, and the pick-up property decreases. On the other hand, a (meth) acrylic monomer having more than 18 carbon atoms has few choices of the monomer itself, and it becomes difficult to synthesize a high molecular weight (meth) acrylic polymer. As such a (meth) acrylic monomer containing a linear alkyl group having 14 to 18 carbon atoms, a monofunctional (meth) acrylic monomer is preferable, and specifically, for example, tetradecyl (meth) acrylate (Myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and the like. These may be used alone or in combination. Among these, octadecyl (meth) acrylate is more preferable.

  The content of the linear alkyl group-containing (meth) acrylic monomer having 14 to 18 carbon atoms in the base polymer is 10 to 60% by mass with respect to the total amount of copolymerization monomer components constituting the base polymer, preferably It is 10-50 mass%. If the content of the linear alkyl group-containing (meth) acrylic monomer having 14 to 18 carbon atoms is less than 10% by mass, the concealment of polar sites such as hydroxyl groups may be insufficient, or the semiconductor wafer having an active surface may be used. When an adhesive film for dicing is attached to a workpiece, the adhesive strength is not sufficiently reduced after curing by radiation, and it becomes difficult to peel off the cut pieces, and the pick-up property tends to be lowered. On the other hand, when the content of the linear alkyl group-containing (meth) acrylic monomer having 14 to 18 carbon atoms is more than 60% by mass, the polymerization reaction during the synthesis of the base polymer does not proceed smoothly, and the high molecular weight (meth) Since it becomes difficult to obtain an acrylic polymer, the adhesive strength before curing by radiation tends to decrease. Moreover, it becomes easy to generate glue stains. Thus, paying attention to the number of alkyl groups and the structure of the copolymerization monomer component constituting the base polymer, a large amount of (meth) acrylic monomer having a linear alkyl group having 14 to 18 carbon atoms is included as a copolymerization monomer component. Decrease in adhesive strength due to contact between adhesive layer before curing by radiation and washing water using adhesive composition containing (meth) acrylic polymer obtained by reacting base polymer and radiation reactive compound So far, no examples have been found that specifically examine the light release property and low contamination property after curing by radiation on the workpiece such as a semiconductor wafer having an active surface.

  In the present embodiment, the base polymer may contain other copolymerization monomer components as necessary for the purpose of cohesion and heat resistance. As such other copolymerization monomer components, specifically, for example, an epoxy group-containing monomer such as glycidyl (meth) acrylate; (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, Carboxyl group-containing monomers such as isocrotonic acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N- Amide monomers such as methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, (meth) acrylic Acid N, N-dimethylaminoethyl, ) Amino group-containing monomers such as t-butylaminoethyl acrylate; Cyano group-containing monomers such as (meth) acrylonitrile; Olefin-based monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; Styrene, α-methylstyrene, vinyltoluene Styrene monomers such as vinyl ester monomers such as vinyl acetate and vinyl propionate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; methoxyethyl (meth) acrylate, Alkoxy group-containing monomers such as ethoxyethyl (meth) acrylate; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N- Contains nitrogen atoms such as nilpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N- (meth) acryloylmorpholine Monomers having a ring: (meth) acrylate nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate isodecyl, (meth) acrylate undecyl, (meth) acrylate dodecyl, (meth) Examples include (meth) acrylic acid esters such as tridecyl acrylate. Moreover, you may use a polyfunctional monomer as a copolymerization monomer component as needed. Furthermore, as a copolymerization monomer component, an ethylene-vinyl acetate copolymer, a vinyl acetate polymer, or the like may be used as necessary. These other copolymerizable monomer components may be used alone or in combination. However, if the content of these other comonomer components is too large, the adhesive strength tends to decrease, and light peelability and low contamination are likely to deteriorate. The amount is preferably 5% by mass or less based on the total amount of the copolymerizable monomer components.

  Examples of the polymerization method for synthesizing the base polymer include conventionally known solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method and the like. Among these, polymerization of the copolymerization monomer component of this embodiment is performed. A solution polymerization method in which the water vapor proceeds uniformly is preferable. Specific examples of the organic solvent for solution polymerization include ketone-based, ester-based, alcohol-based, and aromatic-based organic solvents. These organic solvents may be used alone or in combination. Among these, organic solvents having a boiling point of 60 to 120 ° C. are generally good solvents for the base polymer, such as toluene, ethyl acetate, isopropyl alcohol, benzene methyl cellosolve, ethyl cellosolve, acetone, and methyl ethyl ketone. Examples of the polymerization initiator include radical generators such as azobis type such as α, α′-azobisisobutylnitrile; organic peroxide type such as benzoperoxide. In the polymerization, a catalyst, a polymerization inhibitor or the like may be used as necessary.

  The (meth) acrylic polymer of the present embodiment reacts the base polymer obtained as described above with a radiation-reactive compound having a radiation-reactive carbon-carbon double bond, and the radiation-reactive carbon- It can be synthesized by introducing a carbon double bond.

  As the radiation-reactive compound, a compound having a radiation-reactive carbon-carbon double bond and a functional group that reacts with the hydroxyl group of the base polymer can be used. Specific examples include carboxyl group-containing monomers such as (meth) acrylic acid, cinnamic acid, itaconic acid, fumaric acid, and phthalic acid; and isocyanate group-containing monomers such as isocyanate ethyl (meth) acrylate. These radiation reactive compounds may be used alone or in combination. Among these, an isocyanate group-containing monomer that is excellent in reactivity with a hydroxyl group is preferable. In addition, when the base polymer contains an epoxy group-containing monomer, a carboxyl group-containing monomer, an acid anhydride group-containing monomer, or the like as a copolymerization monomer component, an epoxy group or a carboxylic acid introduced into the molecule by these copolymerization monomer components A hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate and hydroxyethyl (meth) acrylate having a functional group that reacts with a functional group such as a group or an acid anhydride group; glycidyl (meth) acrylate, (meta ) Epoxy group-containing monomers such as glycidyl acrylate; amino group-containing monomers such as aminoethyl (meth) acrylate may be used.

  Content of a radiation reactive compound is 5-25 mass parts with respect to 100 mass parts of base polymers, Preferably it is 6-23 mass parts. When the content of the radiation-reactive compound is less than 5 parts by mass, the introduction amount of the radiation-reactive carbon-carbon double bond is reduced and the curability is likely to be lowered. When there is more content of a radiation reactive compound than 25 mass parts, a low molecular-weight component will increase and the adhesive force before hardening will fall. Moreover, when there is much content of a radiation reactive compound, while sclerosis | hardenability will be saturated, the fluidity | liquidity after hardening by a radiation will fall, and the clearance gap between the cut pieces after extending | stretching will become inadequate. For this reason, it may be difficult to recognize the image of each cut piece during pickup. In addition, the stability of the (meth) acrylic polymer may be reduced, making it difficult to manufacture.

  The content of the radiation reactive compound is preferably smaller than that of the hydroxyl group-containing (meth) acrylic monomer used for the synthesis of the base polymer. If the content of the radiation-reactive compound is less than the content of the hydroxyl group-containing (meth) acrylic monomer, a hydroxyl group that reacts with the crosslinking agent can be secured when a crosslinking agent is used to increase the molecular weight. As a result, it is possible to further suppress a decrease in the adhesive strength when the pressure-sensitive adhesive layer and the washing water come into contact with each other before curing.

  Examples of the method for synthesizing the (meth) acrylic polymer include a method in which the base polymer and the radiation-reactive compound are subjected to a condensation reaction or an addition reaction while maintaining the radiation reactivity of the carbon-carbon double bond. In these reactions, it is preferable to use a polymerization inhibitor so that the radiation reactivity of the carbon-carbon double bond is maintained. As such a polymerization inhibitor, a quinone polymerization inhibitor such as hydroquinone monomethyl ether is preferable. The amount of the polymerization inhibitor is not particularly limited, but is usually 0.01 to 0.1 parts by mass with respect to the total amount of the base polymer and the radiation reactive compound.

  The weight average molecular weight of the (meth) acrylic polymer obtained as described above is preferably 300,000 to 2,000,000, more preferably 400,000 to 1,500,000. When the weight average molecular weight is less than 300,000, paste stains are likely to occur on the cut piece. In addition, the cohesive force of the (meth) acrylic polymer is reduced, and the position of the workpiece is likely to shift during dicing. On the other hand, if the weight average molecular weight is larger than 2 million, gelation may occur during synthesis and coating. In addition, the said weight average molecular weight is a polystyrene conversion weight average molecular weight by GPC (gel permeation chromatography) (solvent: tetrahydrofuran). The (meth) acrylic polymer preferably has a glass transition temperature of −60 ° C. or higher.

  The radiation-curable pressure-sensitive adhesive composition of the present embodiment further contains a polyfunctional monomer having a plurality of radiation-reactive carbon-carbon double bonds in the molecule. By using a (meth) acrylic polymer obtained by using a base polymer having a long-chain alkyl group and a polyfunctional monomer, the (meth) acrylic polymer is not only polymerized and cured by irradiation with radiation. Since polyfunctional monomers having a plurality of radiation-reactive carbon-carbon double bonds in the molecule also react with each other, the polymer of (meth) acrylic polymer is constrained by the reactant of the polyfunctional monomer. Furthermore, since both the (meth) acrylic polymer and the polyfunctional monomer have a radiation-reactive carbon-carbon double bond, the (meth) acrylic polymer and the polyfunctional monomer also react. Thereby, since a higher-density three-dimensional crosslinked structure is formed and the radiation-curable pressure-sensitive adhesive composition is cured and contracted, the adhesive force can be significantly reduced.

  The number of radiation-reactive carbon-carbon double bonds of the polyfunctional monomer is preferably 2 or more, more preferably 3 to 6, per molecule. If the number of radiation-reactive carbon-carbon double bonds is one, the molecular weight is not increased, so that the curing is insufficient and the adhesive strength is not sufficiently reduced. Specifically, as such a polyfunctional monomer, for example, 1,6-hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, Examples include epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, divinylbenzene, butyl di (meth) acrylate, and hexyl di (meth) acrylate. These may be used alone or in combination. Among these, at least one selected from the group consisting of trimethylolpropane tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate is preferable.

  The content of the polyfunctional monomer is preferably 3 to 35 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the base polymer. If content of a polyfunctional monomer is 3 mass parts or more, hardening will fully be accelerated | stimulated by irradiation of a radiation, and adhesive force can be reduced more. On the other hand, when the content of the polyfunctional monomer is 35 parts by mass or less, a decrease in adhesive strength before curing due to radiation due to low molecular weight components can be further suppressed, and paste stains after curing due to radiation can be further reduced. .

  The radiation curable pressure-sensitive adhesive composition of the present embodiment may further contain a crosslinking agent. Such a crosslinking agent is not particularly limited, and a known crosslinking agent can be used. Specifically, for example, polyisocyanate crosslinking agent, epoxy crosslinking agent, aziridine crosslinking agent, melamine resin crosslinking agent, urea resin crosslinking agent, acid anhydride compound crosslinking agent, polyamine crosslinking agent, carboxyl group-containing Examples thereof include a polymer-based crosslinking agent. These crosslinking agents may be used alone or in combination. The amount of the crosslinking agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. If the amount of the crosslinking agent is too large, depending on the type of (meth) acrylic polymer, the adhesive strength when applying the dicing adhesive film to the workpiece may be reduced, or uncrosslinked components may adhere to the cut pieces. , Glue stains may occur.

  The radiation-curable pressure-sensitive adhesive composition of the present embodiment may further contain a photopolymerization initiator when using ultraviolet rays as radiation. Specific examples of such photopolymerization initiators include benzoin alkyl ether initiators such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and benzoylbenzoic acid. Benzophenone initiators such as 3,3′-dimethyl-4-methoxybenzophenone and polyvinylbenzophenone; α-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -Hydroxy-α, α'-dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [ Aromatic ketone initiators such as-(methylthio) -phenyl] -2-morpholinopropane-1; aromatic ketal initiators such as benzyldimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethyl Thioxanthone initiators such as thioxanthone, 2-isopropylthioxanthone, 2-dodecylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; benzyl such as benzyl Benzoin initiators such as benzoin; α-ketol compounds such as 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1 Photoactive oxime compounds such as phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; camphorquinone compounds; halogenated ketone compounds: acyl phosphinoxide compounds; acyl phosphonate compounds Etc. These may be used alone or in combination. The blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer.

  If the radiation-curable pressure-sensitive adhesive composition of the present embodiment has the (meth) acrylic polymer and the polyfunctional monomer, a tackifier is used as necessary for the purpose of improving other characteristics. , Anti-aging agents, fillers, colorants, flame retardants, antistatic agents, softeners, UV absorbers, antioxidants, plasticizers, surfactants, and other known additives may be further contained. However, it is preferable that the number of low molecular compounds such as polyethylene glycol (for example, the number average molecular weight is 3,000 or less) is as small as possible, more preferably less than 2% by mass with respect to the total amount of the radiation curable pressure-sensitive adhesive composition. Most preferably, it is not contained. When the radiation curable pressure-sensitive adhesive composition of the present embodiment contains such a low molecular weight compound, it not only causes contamination of the workpiece, but also tends to reduce the adhesive force in the dicing process, and in the pickup process. Curability tends to decrease.

  The dicing pressure-sensitive adhesive film of the present embodiment can be produced by coating the radiation curable pressure-sensitive adhesive composition on at least one surface of a substrate by a known method. Moreover, when using the separator mentioned later, after coating a radiation-curable adhesive composition on one surface of a separator, you may adhere a base material to an adhesive layer. In addition, when using a crosslinking agent, you may further heat, after forming the adhesive layer containing a radiation-curable adhesive composition. As the substrate, any substrate can be used without particular limitation as long as it has a property of transmitting radiation (X-rays, ultraviolet rays, electron beams, etc.) at least partially. Examples of such a base material include base materials such as plastic, metal, and paper, and among these, a plastic base material is preferable. Specific examples of such plastic substrates include polyolefin resins (low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer). Polymerized polypropylene, homopolypropylene, polybutene, polymethylpentene, etc.), ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer (random) Copolymer, alternating copolymer, etc.), ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane resin, polyester resin (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphtha) Polyimide resin, polyamide resin, polyether ketone resin, polyether resin, polyether sulfone resin, polystyrene resin (polystyrene, etc.), polyvinyl chloride resin, polyvinylidene chloride resin, Groups consisting of constituent materials such as polyvinyl alcohol resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, polycarbonate resins, fluorine resins, silicone resins, cellulose resins, and cross-linked products of these resins Materials. These constituent materials may be used alone or in combination. The above-mentioned constituent materials may have a functional group as necessary. Further, a functional monomer or a modifying monomer may be grafted to the constituent material. Furthermore, the surface of the plastic substrate may be subjected to a known surface treatment method in order to improve the adhesion with an adjacent layer. Specific examples of such surface treatment include corona discharge treatment, ozone exposure treatment, high piezoelectric impact exposure treatment, and ionizing radiation treatment. In addition, the base material may be subjected to coating treatment with a primer, primer treatment, mat treatment, crosslinking treatment, and the like.

  The substrate may have a single layer form or may have a laminated form. Further, in the base material, as necessary, for example, known fillers, flame retardants, anti-aging agents, antistatic agents, softeners, ultraviolet absorbers, antioxidants, plasticizers, surfactants, etc. Additives may be included. Although the thickness of a base material is not specifically limited, Preferably it is 10-300 micrometers, More preferably, it is 30-200 micrometers.

  Although the thickness in particular of an adhesive layer is not restrict | limited, Preferably it is 3-50 micrometers, More preferably, it is 5-20 micrometers. If the thickness of the pressure-sensitive adhesive layer is 3 μm or more, a workpiece such as a semiconductor wafer can be reliably held by the pressure-sensitive adhesive film for dicing during dicing. Further, since a workpiece such as a semiconductor wafer vibrates in the dicing process, if the vibration width is large, a chip (chipping) is likely to occur in a cut piece such as a semiconductor element. However, if the thickness of the pressure-sensitive adhesive layer is 50 μm or less, it is possible to prevent the vibration width of vibrations generated during dicing from becoming too large, thereby reducing the above-described chipping.

  When a semiconductor wafer having an active surface (silicon mirror wafer) is used as a workpiece, the adhesive force of the adhesive layer on the semiconductor wafer before curing by radiation (peeling angle: 180 °, tensile speed: 300 mm / min, temperature) : 23 ± 3 ° C.) is preferably 0.5 (N / 10 mm width) or more, and more preferably 1.0 (N / 10 mm width) or more. If the adhesive force before curing by radiation is 0.5 (N / 10 mm width) or more, the detachment scattering of the semiconductor element in the dicing process can be sufficiently suppressed or prevented. Moreover, the adhesive force (peeling angle: 180 °, tensile speed: 300 mm / min, temperature: 23 ± 3 ° C.) after curing of the pressure-sensitive adhesive layer to the semiconductor wafer having an active surface (silicon mirror wafer) is preferably It is 0.15 (N / 10 mm width) or less, more preferably less than 0.05 (N / 10 mm width). If the pressure-sensitive adhesive layer has such a low adhesive strength after being cured by radiation, the pick-up property is good, and the adhesive residue (residual of the pressure-sensitive adhesive component) can also be reduced.

  FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the dicing adhesive film of the present embodiment. As shown in FIG. 1, the adhesive film 1 for dicing of this Embodiment has the structure by which the adhesive layer 3 containing said radiation curable adhesive composition was formed on one surface of the base material 2. As shown in FIG. ing. Moreover, as shown in FIG. 1, the separator 4 may be provided on the adhesive layer 3 as needed. The separator 4 is not particularly limited, and a known separator can be used. Specific examples of the constituent material of the separator 4 include papers; synthetic resins such as polyethylene, polypropylene, and polyethylene terephthalate. Moreover, in order to improve the peelability of the adhesive layer 3, the surface of the separator 4 may be subjected to treatments such as silicone treatment, long-chain alkyl treatment, and fluorine treatment as necessary. The thickness of the separator 4 is not particularly limited, but is usually 10 to 200 μm. The pressure-sensitive adhesive layer 3 may be a single layer or two or more layers. In FIG. 1, the pressure-sensitive adhesive layer 3 is provided only on one side of the base material 2, but the pressure-sensitive adhesive layer 3 may be provided on both sides of the base material 2. Moreover, although not shown in figure, according to the usage form, another adhesive layer, a mold release process layer, etc. may be formed on the other surface of the base material 2 instead of the separator 4. Specific examples of the pressure-sensitive adhesive composition for forming other pressure-sensitive adhesive layers include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polyamides. A pressure-sensitive adhesive composition containing a known pressure-sensitive adhesive such as a pressure-sensitive adhesive, an epoxy-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, or a fluorine-based pressure-sensitive adhesive can be used. The pressure-sensitive adhesive composition formed on the other surface of the substrate may contain various additives, a radiation curable component, a foaming agent, and the like as necessary. Specific examples of the release treatment agent (release agent) for forming the release treatment layer include, for example, a silicone release treatment agent, a long-chain alkyl release treatment agent, and a fluorine release treatment. A known release treatment agent such as an agent can be used. The dicing adhesive film may have a form wound in a roll shape or a form in which wide sheets are laminated. Further, it may be in the form of a sheet or tape cut into a predetermined size.

  The dicing adhesive film of this embodiment can be used when a workpiece is diced to produce a cut piece. In particular, it can be suitably used when a workpiece having an active surface is diced to produce a cut piece. Specific examples of such a workpiece include a semiconductor wafer, a semiconductor package, glass, and ceramics. These workpieces are composed of compounds such as silicon compounds, germanium compounds, and gallium-arsenic compounds, and active silicon atoms (Si) in an unoxidized state are exposed on the exposed surface by back grinding or the like. ), There are many unoxidized active atoms such as unoxidized active germanium atoms (Ge) and unoxidized active gallium atoms (Ga). Therefore, when a pressure-sensitive adhesive film for dicing is applied to a workpiece in order to dice the workpiece having such active atoms, it is introduced into the (meth) acrylic polymer contained as a main component in the pressure-sensitive adhesive layer. A polar site such as a hydroxyl group and an active atom are bonded to each other to exhibit high adhesive force even after curing by radiation, and it becomes difficult to separate the cut piece from the dicing adhesive film. However, according to the adhesive film for dicing of the present embodiment, even when the adhesive film for dicing is attached to the workpiece having the active surface, when the cut piece is peeled off from the adhesive film for dicing, Regardless, the adhesive force to the active surface can be sufficiently reduced by irradiation with radiation, and the cut piece can be easily peeled off. Therefore, according to the adhesive film for dicing of the present embodiment, for example, after the backside grinding process of the semiconductor wafer, or after the backside grinding process and the backside process of the semiconductor wafer, the adhesive film for dicing on the active surface exposed within a short time Even if affixed, it can be used effectively for a dicing process, a pick-up process, and the like to be performed thereafter.

  In the present embodiment, as a method of manufacturing a cut piece by dicing a workpiece, a mounting step of sticking a dicing adhesive film on one surface of the workpiece and a workpiece on which a dicing adhesive film is stuck From the dicing adhesive film for dicing, in which the adhesive force of the adhesive layer is reduced by irradiating the adhesive layer applied to the cut piece with radiation, and the dicing step of cutting the adhesive piece into pieces. A production method having at least a pick-up step for picking up the cut piece can be suitably used.

  In the mounting process in which a dicing adhesive film is attached to one surface of a workpiece, the workpiece such as a semiconductor wafer and the dicing adhesive film are usually stacked in a form in which the one surface of the workpiece and the adhesive layer are in contact with each other. The adhesive film for dicing is affixed on a to-be-processed object by match | combining and pressing this with well-known press means, such as a press means using a crimping | compression-bonding roll. Further, in a pressurizable container (for example, an autoclave), the work piece and the dicing adhesive film are overlapped in the same manner as described above, and the inside of the container is pressurized to dicing the work piece. An adhesive film may be affixed. Furthermore, a dicing adhesive film may be attached to the workpiece in the same manner as in the case of attachment by pressurization in a reduced pressure chamber (vacuum chamber).

  Next, in the dicing step, a workpiece such as a semiconductor wafer attached to the dicing adhesive film is diced by a dicing means such as a blade to produce a cut piece of the workpiece. In such a dicing process, a blade that rotates at high speed while supplying cleaning water to a workpiece such as a semiconductor wafer to which a pressure-sensitive adhesive film for dicing is usually attached in order to prevent the removal of frictional heat and adhesion of cutting waste. The workpiece is cut into a predetermined size. For this reason, although the adhesive strength of the adhesive layer is likely to decrease, the adhesive film for dicing of the present embodiment can maintain excellent adhesive strength even when the adhesive layer and the washing water come into contact with each other. It is possible to reduce the detachment scattering of the cut pieces from the film. The dicing apparatus is not particularly limited, and a conventionally known apparatus can be used. In addition, a washing | cleaning process, an expanding process, etc. may be performed after a dicing process as needed.

  In the pickup step, the adhesive layer of the dicing adhesive film is irradiated with radiation to reduce the adhesive strength of the adhesive layer, and then the cut piece is picked up from the dicing adhesive film. Examples of radiation include X-rays, electron beams, and ultraviolet rays. Among these, ultraviolet rays are preferable. Various conditions such as irradiation intensity and irradiation time when irradiating with radiation are not particularly limited, and can be set as appropriate. The pickup method is not particularly limited, and various conventionally known pickup methods can be employed. For example, there is a method in which individual cut pieces are pushed up by a needle from the dicing adhesive film side, and the pushed up cut pieces are picked up by a pickup device. The adhesive film for dicing according to the present embodiment can sufficiently reduce the adhesive force by radiation curing, so even in the case where a workpiece having an active surface is used, the above pick-up process can be easily performed. The cut piece can be peeled from the dicing adhesive film, and adhesion of the adhesive component to the cut piece after peeling can be reduced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following description, “part” means “part by mass”.

<Synthesis of (meth) acrylic polymer>
As a copolymerization monomer component, ethyl acrylate (EA) containing a linear alkyl group having 2 carbon atoms, 2-ethylhexyl acrylate (EHA) containing a branched alkyl group having 8 carbon atoms, acrylic acid 2 containing a hydroxyl group -Hydroxyethyl (HEA), myristyl acrylate containing a linear alkyl group having 14 carbon atoms (MA), octadecyl acrylate containing a linear alkyl group having 18 carbon atoms (STA), and 12 carbon atoms A dodecyl acrylate (LA) containing a linear alkyl group was prepared. These copolymerizable monomer components were mixed in the respective compounding amounts shown in Table 1, and solution radical polymerization was performed to synthesize each base polymer. In the polymerization, the reaction of the copolymerization monomer component was monitored by GPC, and the polymerization was terminated when the copolymerization monomer component disappeared.

  Next, with respect to 100 parts of each base polymer, 2-isocyanate ethyl methacrylate (IEM) containing a radiation-reactive carbon-carbon double bond was reacted with each compounding amount shown in Table 1, and each (meta) An acrylic polymer was synthesized. In the above reaction, 0.05 part of hydroquinone monomethyl ether (MEHQ) was used as a polymerization inhibitor. When the weight average molecular weight of each synthesized (meth) acrylic polymer was measured by GPC (solvent: tetrahydrofuran), it was 500,000 to 800,000.

<Preparation of adhesive film for dicing>
As polyfunctional monomers, pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., PE3A, trifunctional) and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, hexafunctional) were prepared. Each (meth) acrylic polymer obtained as described above, a polyfunctional monomer of each blending amount shown in Table 1, and 0.1 part of a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., Coronate L) as a crosslinking agent Then, 0.5 part of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure-184) was mixed as a photopolymerization initiator to prepare each radiation curable pressure-sensitive adhesive composition.

  Next, after each radiation-curable pressure-sensitive adhesive composition obtained as described above was applied on a polyethylene terephthalate separator (thickness: 38 μm) to a thickness of 10 μm to form a pressure-sensitive adhesive layer And heated at 100 ° C. for 3 minutes. Thereafter, a polyolefin film (thickness: 100 μm) having a corona discharge treatment on one side was bonded to the pressure-sensitive adhesive layer. The bonded samples were stored in a constant temperature bath at 40 ° C. for 72 hours to produce each dicing adhesive film.

  The following evaluation was performed using each dicing adhesive film produced as described above. Table 1 shows the composition of each radiation-curable pressure-sensitive adhesive composition and the results thereof.

[Evaluation]
(Adhesive strength before curing by radiation)
A measurement sample was prepared by bonding a dicing adhesive film cut into a 25 mm width strip to a 5-inch silicon mirror wafer immediately after mirror polishing in an atmosphere of 23 ° C., and allowing this to stand at room temperature for 30 minutes. Produced. The adhesive strength of this measurement sample was measured, and the adhesive strength before curing was evaluated according to the following criteria. The adhesive strength was measured at a peeling angle of 180 °, a peeling speed of 300 mm / min, and a temperature of 23 ± 3 ° C.
○: The measured value of adhesive strength is 1.0 N / 10 mm or more. Δ: The measured value of adhesive strength is 0.5 N / 10 mm or more and less than 1.0 N / 10 mm. X: The measured value of adhesive strength is 0.5 N / Less than 10mm

(Adhesive strength after curing by radiation)
A measurement sample similar to the measurement sample used in the measurement of the adhesive strength before curing by radiation was prepared. The measurement sample was irradiated with ultraviolet rays (irradiation intensity: 300 mJ / cm ² ) from the substrate side of the dicing adhesive film, and the adhesive strength after irradiation was measured in the same manner as the adhesive strength before curing with the above-mentioned radiation. The adhesive strength after curing was evaluated on the basis of
○: The measured value of adhesive force is less than 0.05 N / 10 mm. Δ: The measured value of adhesive force is 0.05 N / 10 mm or more and 0.15 N / 10 mm or less. X: The measured value of adhesive force is 0.15 N / Over 10mm

(Pickup property)
A 5-inch silicon mirror wafer having a thickness of 100 μm was mirror-polished, and then a dicing adhesive film was immediately bonded to the polished surface in an atmosphere at 23 ° C. The wafer was fully cut into a size of 3 mm × 3 mm while supplying cleaning water to the wafer with the adhesive film attached thereto.
Next, ultraviolet rays (irradiation intensity: 300 mJ / cm ² ) were irradiated from the substrate side of the adhesive film for dicing and expanded, and then the semiconductor element was peeled off from the adhesive film and picked up. When 100 arbitrary semiconductor elements are picked up, ◎, when 95 to 99 semiconductor elements are successfully picked up, ◯, when 50 to 94 semiconductor elements are picked up The pick-up property was evaluated as △ when the pick-up was successful, and × as the other pick-up.

  As is clear from Table 1, when a base polymer containing a copolymerizable monomer component having a long-chain alkyl group having 14 and 18 carbon atoms is used, the base polymer has high adhesive strength before curing and is adhesive after curing. It can be seen that the force is significantly reduced.

  In contrast, when a base polymer that does not contain a copolymer monomer component having a long-chain alkyl group is used, it can be seen that the adhesive strength before curing is high, but the adhesive strength is not sufficiently lowered after curing. For this reason, pick-up property fell.

  Moreover, even if the copolymerization monomer component of a base polymer is the same, when there is too much content of the copolymerization monomer component which has a long-chain alkyl group, it turns out that the adhesive force before hardening falls. On the other hand, if the content of the copolymer monomer component having a short-chain alkyl group is too large, the adhesive strength before curing is high, but the content of the copolymer monomer component having a hydroxyl group and a long-chain alkyl group decreases. It can be seen that the adhesive strength after curing increases.

  Furthermore, when there is too much content of a radiation reactive compound, since a base polymer and an unreacted low molecular weight component will increase, the adhesive force before hardening will fall. In addition, when this radiation curable pressure-sensitive adhesive composition was used, adhesive stains were observed on the surface of the obtained semiconductor element because of the increase in low molecular weight components. On the other hand, when there is too little content of a radiation reactive compound, hardening of a (meth) acrylic-type polymer will not fully advance, but the fall of the adhesive force after hardening will become inadequate.

  Then, a (meth) acrylic polymer obtained by reacting a certain amount of a copolymer monomer component having a long-chain alkyl group with a certain amount of radiation-reactive compound, and a radiation containing a certain amount of a polyfunctional monomer. When the curable pressure-sensitive adhesive composition is used, it can be seen that the adhesive strength is high before curing, and the adhesive strength is significantly reduced after curing. In particular, it can be seen that when 5 to 30 parts by mass of the polyfunctional monomer is used with respect to the base polymer, a pressure-sensitive adhesive layer having higher adhesive strength before curing and having lower adhesive strength after curing can be obtained. For this reason, when these radiation-curable pressure-sensitive adhesive compositions were used, no detachment scattering of the semiconductor elements was observed during dicing, and all the semiconductor elements could be picked up in the pick-up process. When a radiation curable pressure-sensitive adhesive composition containing 35 parts by mass of a polyfunctional monomer was used, some glue stains were observed on the surface of the obtained semiconductor element.

  On the other hand, even if the same (meth) acrylic polymer is used, the radiation-curable pressure-sensitive adhesive composition not containing a polyfunctional monomer has a certain decrease in adhesive strength after curing, but when a polyfunctional monomer is used in combination. It can be seen that there is little decrease in adhesive strength compared to.

DESCRIPTION OF SYMBOLS 1 Adhesive film for dicing 2 Base material 3 Adhesive layer 4 Separator

Claims (7)

A base polymer having a hydroxyl group, a radiation reactive carbon in the molecule - is obtained by reacting a radiation-reactive compound having a functional group reactive with the carbon-carbon double bond and the hydroxyl group (meth) acrylic polymers, as well as multi Contains functional monomers,
The base polymer is a linear or branched alkyl group-containing (meth) acrylic monomer having a carbon number of 2 to 8, a hydroxyl group-containing (meth) acrylic monomer, and a linear chain having a carbon number of 14 to 18 as a copolymerization monomer component. Having at least an alkyl group-containing (meth) acrylic monomer,
The content of the linear or branched alkyl group-containing (meth) acrylic monomer having 2 to 8 carbon atoms is 30 to 80% by mass relative to the total amount of the copolymerizable monomer component, and the hydroxyl group-containing (meth) acrylic monomer The content is 5 to 20% by mass, the content of the linear alkyl group-containing (meth) acrylic monomer having 14 to 18 carbon atoms is 10 to 60% by mass,
The radiation-curable pressure-sensitive adhesive composition, wherein the content of the radiation-reactive compound is 5 to 25 parts by mass with respect to 100 parts by mass of the base polymer. The radiation-curable pressure-sensitive adhesive composition according to claim 1, wherein the radiation-reactive compound contains at least a carboxyl group-containing monomer or an isocyanate group-containing monomer. The radiation-curable pressure-sensitive adhesive composition according to claim 1 or 2 , wherein a content of the polyfunctional monomer is 5 to 30 parts by mass with respect to 100 parts by mass of the base polymer. Furthermore, the radiation curable adhesive composition of any one of Claims 1-3 containing a crosslinking agent and a photoinitiator. A dicing adhesive film having a base material and an adhesive layer on at least one surface of the base material,
The said adhesive layer is an adhesive film for dicing containing the radiation-curable adhesive composition of any one of Claims 1-4 . Affixing the adhesive film for dicing according to claim 5 on one surface of the workpiece,
The workpiece to which the adhesive film for dicing is attached is cut and separated into cut pieces,
Radiation is applied to the adhesive layer attached to the cut piece to reduce the adhesive strength of the adhesive layer,
The manufacturing method of the cut piece which picks up the said cut piece from the adhesive film for dicing which reduced the said adhesive force. The method for manufacturing a cut piece according to claim 6 , wherein the workpiece is a semiconductor wafer having an active surface.

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