TW202000829A - Dicing-die bonding integrated film and tackifier film used for same - Google Patents

Abstract

A dicing-die bonding integrated film according to an aspect of the present disclosure has a structure in which at least a substrate layer, a tackifier layer, and an adhesive layer are sequentially laminated, wherein the tackifier layer contains a photopolymerization component and a photopolymerization initiator (D). The photopolymerization component contains a structural unit derived from a polymer (A) having a group containing a quaternary ammonium salt and a hydroxyl group, an energy-curable tackifier component (B) having a hydroxyl group, and a thermal crosslinking agent (C), wherein the structural unit is at least one of a structural unit in which the polymer (A) and the tackifier component (B) are linked via the thermal crosslinking agent (C) or a structural unit in which the tackifier component (B) is linked via the thermal crosslinking agent (C).

Description

Dicer-stick crystal integrated film and adhesive film using the same

The present disclosure relates to a slicing-sticking crystal integrated film and an adhesive film used therefor.

The semiconductor device is manufactured through the following steps. First, the dicing step is performed in a state where an adhesive film for dicing is attached to a wafer. Thereafter, an expansion step, a pickup step, a mounting step, a die bonding step, and the like are implemented.

In the manufacturing process of the semiconductor device, a film called a slicing-sticking integrated film is used. The film has a structure in which a base material layer, an adhesive layer, and an adhesive layer are sequentially stacked, and is used as follows, for example. First, the surface of the adhesive layer side is attached to the wafer, and the wafer is diced in a state where the wafer is fixed with a dicing ring. By this, the wafer is singulated into a large number of chips. Then, the adhesive layer is irradiated with ultraviolet rays, thereby weakening the adhesive force of the adhesive layer with respect to the adhesive layer, and then picking up the adhesive sheet and the wafer formed by singulation of the adhesive layer from the adhesive layer together. Thereafter, a semiconductor device is manufactured through a step of mounting a wafer on a substrate or the like via an adhesive sheet. In addition, the laminate including the wafer obtained through the crystal-cutting step and the adhesive sheet attached thereto is called a die attach film (DAF).

As described above, the adhesive layer (crystal-cut film) whose adhesive force is weakened by the irradiation of ultraviolet rays is called an ultraviolet (UV) curing type. In contrast, an adhesive layer that maintains a certain adhesive force without irradiating ultraviolet rays during the manufacturing process of the semiconductor device is called a pressure-sensitive type.

In addition, the film used in the manufacturing process of the semiconductor device is required to have antistatic properties. Patent Document 1 discloses a sheet for semiconductor processing including an adhesive layer formed by hardening an adhesive composition by irradiating energy rays, the adhesive composition containing a quaternary ammonium salt (antistatic agent) And energy ray hardening-based polymers, and energy ray hardening adhesive components (except for the polymers). According to this sheet for semiconductor processing, excellent antistatic properties can be exerted, and contamination of an adherend (wafer or wafer) during peeling can be suppressed (see Patent Document 1, paragraph [0020]). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-115385

[Problems to be solved by the invention] The sheet for semiconductor processing described in Patent Document 1 is not intended to be applied to a die-bonding integrated film. That is, the sheet for semiconductor processing is used as a back-grinding sheet (semiconductor wafer surface protection sheet), a diced wafer, or a sheet for transferring and picking up the wafer (see Patent Document 1, paragraph [0101]). That is, the adhesive layer of the semiconductor processing sheet uses a semiconductor wafer or a semiconductor wafer as an adherend. In contrast to this, the adhesive layer of the slicing-sticking integrated film uses the adhesive layer as the adherend. Since the adhesive layer and the adhesive layer arranged so as to be in contact with each other contain a resin component, the amount of bleed out of the low molecular weight component present at the interface of these layers tends to increase. As a result, the peel strength between the adhesive layer and the adhesive layer increases with time, and as a result, picking errors are likely to occur. The adhesive layer of the die-cut crystal integrated film is required to have the following characteristics: to suppress the decrease in peelability caused by the bleeding of the components contained therein.

In addition, the adhesive layer for the slicing-die bonding integrated film requires high adhesion with respect to the adhesive layer and the slicing ring in the slicing step. If the adhesive force of the adhesive layer is insufficient, the following phenomenon occurs: with the high-speed rotation of the dicing blade, the adhesive layer and the adhesive layer are peeled off, and the wafer and the adhesive sheet are scattered together (the following , Referred to as "DAF flying"); or, the phenomenon of peeling of the crystal ring from the adhesive layer due to the flow of cutting water (hereinafter, this phenomenon is referred to as "ring peeling"). The reason is presumed to be that the adhesive layer of the semiconductor processing sheet described in Patent Document 1 is hardened in advance by irradiation of energy rays. Therefore, if it is used as an adhesive layer of a die-bonded integrated film, the adhesive force Insufficient to cause DAF scattering and ring peeling during crystal cutting.

The present disclosure provides an adhesive film for a die-bonding integrated film that is excellent in antistatic properties and adhesion to a wafer in a dicing step, and is excellent in peeling from an adhesive layer in a pickup step. In addition, the present disclosure provides a die-bonding integrated film including the adhesive film. [Means to solve the problem]

One aspect of the present disclosure is to provide an adhesive film for a slicing-sticking crystal integrated film. The adhesive film includes at least a substrate layer and an adhesive layer provided on the substrate layer, and the adhesive layer contains the following photopolymerization components and a photopolymerization initiator (D). That is, the photopolymerization component includes structural units derived from a polymer (A), an energy-curable adhesive component (B) having a hydroxyl group, and a thermal crosslinking agent (C), the polymer (A) having a quaternary ammonium-containing The base of the salt and the hydroxyl group, and the structural unit is a structural unit in which the polymer (A) and the adhesive component (B) are connected via the thermal crosslinking agent (C), and the adhesive component (B) is connected to each other via the thermal crosslinking agent (C) At least one of the connected structural units.

By crosslinking the adhesive component (B) with the polymer (A) via the thermal crosslinking agent (C) or crosslinking the adhesive component (B) with the thermal crosslinking agent (C), even if a low molecular weight component is used as The sticky component (B) can also fully inhibit its exudation. In addition, the photopolymerization component contains structural units derived from the polymer (A), which exhibits antistatic properties, and the polymer (A) has a quaternary ammonium salt-containing group.

By irradiating active energy rays (for example, ultraviolet rays) to the adhesive layer, the photopolymerization component reacts with the photopolymerization initiator (D), and the adhesiveness decreases. In the manufacturing process of the semiconductor device, after the dicing step, the adhesive layer is irradiated with active energy rays, thereby improving the peelability of the DAF with respect to the adhesive layer, which can sufficiently reduce pickup errors in subsequent pickup steps. From the viewpoint of adhesiveness, the adhesive layer preferably has a storage elastic coefficient at 23° C. that is sufficiently small, and its value is, for example, 10 MPa to 60 MPa.

From the viewpoint of obtaining the above effect more stably, it is preferable that the adhesive composition (B) contains a resin having a functional group capable of chain polymerization, and the functional group is selected from the group consisting of acryl and methacryl At least one of them. From the same viewpoint, it is preferable to use a reactant of a polyfunctional isocyanate having two or more isocyanate groups in one molecule and a polyol having three or more OH groups in one molecule as the heat exchange Joint agent (C). As an example of the photopolymerization initiator (D), a photoradical polymerization initiator may be mentioned.

One aspect of the present disclosure is to provide a slicing-sticking crystal integrated film. The integrated film includes the adhesive film and an adhesive layer provided on the adhesive layer included in the adhesive film. According to this integrated film, the adhesive layer has excellent adhesiveness to the wafer in the dicing step, and has excellent peelability relative to the adhesive layer in the pickup step after active energy ray irradiation . When the adhesive layer is peeled off from the adhesive layer, the components of the adhesive layer can be suppressed from contaminating the adhesive layer, and therefore, a crystal bond with excellent reliability (excellent crystallinity) can be realized. [Effect of invention]

According to the present disclosure, there is provided an adhesive film for a die-bonding integrated film that is excellent in antistatic properties and adhesion to a wafer in a dicing step and is excellent in peeling from an adhesive layer in a pickup step. In addition, according to the present disclosure, there is provided a die-bonding integrated film including the adhesive film.

Hereinafter, the embodiments of the present disclosure will be described in detail while referring to the drawings. In the following description, the same or corresponding parts are marked with the same symbols, and repeated explanations are omitted. Furthermore, the present invention is not limited to the following embodiments. In this specification, (meth)acrylic acid means acrylic acid or methacrylic acid.

FIG. 1 is a cross-sectional view schematically showing a die-bonding integrated film of this embodiment. The die-bonding integrated film 10 shown in FIG. 1 (hereinafter, sometimes simply referred to as "film 10") includes: a substrate layer 1, an adhesive layer 3 provided on the substrate layer 1, and an adhesive layer Adhesive layer 5 on the agent layer 3. The adhesive layer 3 has an effect in the dicing step and the picking step of singulating the semiconductor wafer. The adhesive layer 5 has an effect in the step of attaching the semiconductor wafer obtained through the pickup step to the substrate or the like. As shown in FIG. 1, the diameter of the adhesive layer 3 is larger than that of the adhesive layer 5. The peripheral portion of the adhesive layer 3 not covered by the adhesive layer 5 is attached with a dicing ring for fixing the wafer during dicing.

<Adhesive layer> The adhesive layer 3 contains the following photopolymerization components and a photopolymerization initiator (D). That is, the photopolymerization component includes structural units derived from a polymer (A), an energy-curable adhesive component (B) having a hydroxyl group, and a thermal crosslinking agent (C), the polymer (A) having a quaternary ammonium-containing The salt group and the hydroxy group, and the structural unit is a structural unit in which the polymer (A) and the adhesive component (B) are connected by a thermal crosslinking agent (C), and the adhesive component (B) is thermally crosslinked with each other At least one of the structural units linked by the agent (C).

(Photopolymerization component) The photopolymerization component can be obtained, for example, by forming a composition containing a polymer (A), an adhesive component (B), and a thermal crosslinking agent (C) or forming the composition into a film shape The step in which the adult is placed in an environment of about 40°C (maturation step) within a predetermined period (for example, 3 days to 4 days), whereby the hydroxyl group of the polymer (A) and the hydroxyl group of the adhesive component (B) are used as cross The cross-linking agent (C) and these components are cross-linked. If the adhesive component (B) is cross-linked with the polymer (A) via the thermal cross-linking agent (C) or the adhesive component (B) is cross-linked with the thermal cross-linking agent (C) with each other, even if a low molecular weight component is used ( For example, the molecular weight of about 200 to 10,000) as the adhesive component (B) can also sufficiently suppress its bleeding. In addition, the photopolymerization component contains structural units derived from the polymer (A), which exhibits antistatic properties, and the polymer (A) has a quaternary ammonium salt-containing group.

From the viewpoint of adhesiveness, and more specifically from the viewpoint of suppressing DAF scattering and ring peeling, the storage elastic coefficient of the adhesive layer 3 at 23° C. is preferably sufficiently small, for example, in the range of 10 MPa to 60 MPa. It can be 15 MPa to 50 MPa or 20 MPa to 40 MPa. The storage elasticity coefficient can be appropriately set by, for example, selecting the type of polymer (A) or adjusting the amount of the thermal crosslinking agent (C) when preparing the photopolymerization component. Hereinafter, each component used in the preparation of the adhesive layer 3 will be described in detail.

[Polymer (A)] The polymer (A) is a polymer containing a quaternary ammonium salt-containing group and a hydroxyl group, and exhibits antistatic properties by containing a quaternary ammonium salt-containing group. The polymer (A) only needs to have a quaternary ammonium salt in the main chain or the side chain, and it is preferably in the side chain from the viewpoint of polymerizability and the like. The quaternary ammonium salt is composed of a quaternary ammonium cation and its opposite anion, specifically, it may be composed of a quaternary ammonium cation covalently bonded to the polymer (A) and its opposite anion, or may be composed of a covalent bond The anion bound to the polymer (A) is composed of the quaternary ammonium cation opposite to it.

The polymer (A) can be linked to the adhesive component (B) via the thermal crosslinking agent (C) by having a hydroxyl group as a crosslinking point, or the polymer (A) can be linked to each other.

The weight average molecular weight of the polymer (A) is, for example, 10,000 to 200,000, and may be 10,000 to 100,000 or 10,000 to 50,000. If the molecular weight is less than 10,000, the transfer of the polymer (A) component to the adhesive layer is likely to occur. On the other hand, if it exceeds 200,000, the viscosity of the adhesive layer tends to be insufficient. As a result, the adhesion of the adhesive layer is insufficient, and it is easy to cause defects such as DAF scattering or ring peeling.

The polymer (A) can be obtained by synthesis using a known method. Examples of the synthesis method include solution polymerization method, suspension polymerization method, emulsion polymerization method, bulk polymerization method, precipitation polymerization method, gas phase polymerization method, plasma polymerization method, and supercritical polymerization method. In addition, examples of the type of polymerization reaction include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, coordination polymerization, immortal polymerization, and the like. : Atom Transfer Radical Polymerization (ATRP) and Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT) and other methods. Among them, the case of using a solution polymerization method and synthesizing by radical polymerization has advantages such as good economy, high reaction rate, and easy polymerization control, etc., and also has advantages such that it can be directly prepared using a resin solution obtained by polymerization.

Examples of the acrylic monomer (hydroxyl group-containing monomer) having a hydroxyl group used in the synthesis of the polymer (A) include 2-hydroxyethyl (meth)acrylate and 2-hydroxyl (meth)acrylate. Propyl ester, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. (methyl ) Hydroxyalkyl acrylate, etc. Among these, in terms of reactivity with the adhesive component (B), 2-hydroxyethyl (meth)acrylate is preferred. These can be used alone or in combination of two or more.

[Sticky ingredient (B)] The adhesive component (B) has the property of reacting with the photopolymerization initiator (D) by irradiation of active energy rays (energy hardenability), and has a hydroxyl group as a crosslinking point. The adhesive component (B) can be linked to the polymer (A) via the thermal crosslinking agent (C) by having a hydroxyl group as a crosslinking point, or the adhesive component (B) can be linked to each other. As described above, by sticking the adhesive component (B) through the thermal crosslinking agent (C), even if a low-molecular-weight component is used as the adhesive component (B), its bleeding can be sufficiently suppressed. The weight average molecular weight of the adhesive component (B) is, for example, 10,000 to 2 million, and may be 100,000 to 1.5 million or 200,000 to 1 million. If the molecular weight is less than 10,000, there is a tendency that it is difficult to maintain the film shape, or the adhesion with the DAF becomes excessively strong. On the other hand, if the molecular weight exceeds 2 million, the adhesive force tends to become insufficient. Hereinafter, a method of obtaining a (meth)acrylic resin by radical polymerization using a solution polymerization method will be described in detail as an example of the synthesis method of the adhesive component (B).

The monomer used when synthesizing the (meth)acrylic resin is not particularly limited as long as it has one acryl group and methacryl group in one molecule. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and third butyl (meth)acrylate. , Butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, ( Octylheptyl meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate , Myristyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate , Methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) Aliphatic (meth)acrylates such as acrylate, mono(2-(meth)acryloyloxyethyl) succinate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, Cyclopentyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrophthalic acid mono(2-( Alicyclic (meth)acrylates such as meth)acryloyloxyethyl) ester, hexahydrophthalic acid mono(2-(meth)acryloyloxyethyl) ester; (meth)acrylic acid Benzyl ester, phenyl (meth)acrylate, o-biphenyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, (methyl) Phenoxyethyl acrylate, p-cumylphenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 1-naphthoxyethyl (meth)acrylate, (meth Group) 2-naphthoxyethyl acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) Acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, 2-hydroxy (meth)acrylate Aromatic (meth)acrylates such as -3-(1-naphthyloxy)propyl ester, (meth)acrylic acid 2-hydroxy-3-(2-naphthyloxy)propyl ester; (meth)acrylic acid 2- Heterocyclic formulas such as tetrahydrofurfuryl ester, N-(meth)acryloyloxyethylhexahydrophthalimide, 2-(meth)acryloyloxyethyl-N-carbazole Meth) acrylate, these modified caprolactone, ω-carboxy-polycaprolactone mono(meth)acrylate, glycidyl (meth)acrylate, α-ethyl (meth)acrylate Glycidyl ester, (meth)acrylic acid α-propyl glycidyl ester, (meth)acrylic acid α-butyl glycidyl ester, (meth)acrylic acid 2-methylglycidyl ester, (meth)acrylic acid 2- Ethyl glycidyl ester, 2-propyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth) acrylate, (A Group) 3,4-epoxyheptyl acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, o-vinyl Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and other compounds having an ethylenically unsaturated group and an epoxy group; (meth)acrylic acid (2-ethyl-2- Oxetanyl) methyl ester, (meth)acrylic acid (2-methyl-2-oxetanyl) methyl ester, (meth)acrylic acid 2-(2-ethyl-2-oxetanyl) Ethyl), 2-(2-methyl-2-oxetanyl)ethyl (meth)acrylate, 3-(2-ethyl-2-oxetanyl) (meth)acrylate Compounds with ethylenic unsaturated groups and oxetanyl groups such as propyl ester, 3-(2-methyl-2-oxetanyl) propyl (meth)acrylate; 2-(meth)acryloyl Compounds with ethylenically unsaturated groups and isocyanate groups such as oxyethyl isocyanate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Ester, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate and other compounds having an ethylenically unsaturated group and a hydroxyl group can be obtained by combining these appropriately. Base) acrylic resin.

The (meth)acrylic resin preferably has one or more aromatic rings. In this case, as the monomer for synthesizing (meth)acrylic resin, it is preferable to use one kind selected from the following monomers alone, or two or more kinds in combination: styrene, α-methylstyrene, α -Ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-butylstyrene, α-isobutylstyrene, α-third butylstyrene, 2-methylbenzene Ethylene, 4-methylstyrene, 2-ethylstyrene, 4-ethylstyrene, 2-propylstyrene, 4-propylstyrene, 2-isopropylstyrene, 4-isopropylstyrene Styrene, 2-butylstyrene, 4-butylstyrene, 2-isobutylstyrene, 4-isobutylstyrene, 2-third butylstyrene, 4-third butylstyrene , Benzyl (meth)acrylate, phenyl (meth)acrylate, o-biphenyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate Ester, phenoxyethyl (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 1-naphthyloxy (meth)acrylate Ethyl ester, 2-naphthoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, phenoxy Polypropylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(o-phenylphenoxy)propyl (meth)acrylate, (meth Group) 2-hydroxy-3-(1-naphthyloxy)propyl acrylate, 2-hydroxy-3-(2-naphthyloxy)propyl (meth)acrylate.

The (meth)acrylic resin preferably has at least one functional group selected from a hydroxyl group, a glycidyl group, an amine group, and the like as a reaction point (crosslinking point) with a functional group-introducing compound or crosslinking agent described later. Examples of monomers for synthesizing (meth)acrylic resins having hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-(meth)acrylic acid. Hydroxybutyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate and other compounds having an ethylenically unsaturated group and a hydroxyl group, these can be used alone or in combination Two or more.

As a monomer for synthesizing a (meth)acrylic resin having a glycidyl group, glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, (meth)acrylic acid can be cited. α-propyl glycidyl ester, (meth)acrylic acid α-butyl glycidyl ester, (meth)acrylic acid 2-methyl glycidyl ester, (meth)acrylic acid 2-ethyl glycidyl ester, (meth) ) 2-propyl glycidyl acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, α-ethyl-6 (meth)acrylate, 7-epoxyheptyl ester, 3,4-epoxycyclohexyl methyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Compounds having an ethylenic unsaturated group and an epoxy group may be used alone or in combination of two or more.

The (meth)acrylic resin synthesized from these monomers preferably contains a functional group capable of chain polymerization. The functional group capable of chain polymerization is, for example, at least one selected from the group consisting of acryl and methacryl. The functional group capable of chain polymerization can be introduced into the (meth)acrylic resin by reacting the following compound (functional group introducing compound) with the (meth)acrylic resin synthesized as described above, for example. Specific examples of the functional group-introducing compound include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, alkene Propyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; by diisocyanate compound or polyisocyanate compound, and hydroxyethyl (meth)acrylate or 4-hydroxy (meth)acrylate Acryloyl monoisocyanate compound obtained by reacting butyl ethyl ester; acryloyl monoisocyanate obtained by reacting diisocyanate compound or polyisocyanate compound, polyol compound, and hydroxyethyl (meth)acrylate Compounds etc. Among these, particularly preferred is 2-methacryloyloxyethyl isocyanate. These compounds may be used alone or in combination of two or more.

[Thermal Crosslinking Agent (C)] The thermal crosslinking agent (C) is used, for example, for the purpose of controlling the elastic coefficient and/or adhesiveness of the adhesive layer 3. The thermal cross-linking agent (C) has at least one function selected from the group consisting of hydroxyl groups, glycidyl groups, and amine groups, which can be possessed by two or more polymers (A) or adhesive components (B) in one molecule. It is sufficient if the compound reacts with a functional group. Examples of the bond formed by the reaction of the thermal crosslinking agent (C) with the polymer (A) or the adhesive component (B) include: ester bond, ether bond, amide bond, amide imide bond, and aminomethyl Acid ester bond, urea bond, etc.

In the present embodiment, a compound having two or more isocyanate groups in one molecule is preferably used as the thermal crosslinking agent (C). If such a compound is used, it can easily react with the hydroxyl group, glycidyl group, and amine group of the polymer (A) or the adhesive component (B), and a strong cross-linked structure can be formed.

Examples of the compound having two or more isocyanate groups in one molecule include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylene. Diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophor Isocyanate compounds such as ketone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and amine acid isocyanate.

As the thermal crosslinking agent (C), a reactant (isocyanate group-containing oligomer) of the isocyanate compound and a polyol having two or more OH groups in one molecule can be used. Examples of the polyol having two or more OH groups in one molecule include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, and 1,9 -Nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, glycerin, pentaerythritol, dipentaerythritol, 1,4-cyclohexanedione Alcohol, 1,3-cyclohexanediol.

Among these, as the thermal crosslinking agent (C), it is more preferable to react a polyfunctional isocyanate having two or more isocyanate groups in one molecule with a polyol having three or more OH groups in one molecule. Substances (oligomers containing isocyanate groups). By using such an isocyanate group-containing oligomer as the thermal crosslinking agent (C), the adhesive layer 3 forms a dense crosslinked structure, whereby the adhesion of the adhesive to the adhesive layer can be sufficiently suppressed in the pickup step 5 situation.

(Synthesis of photopolymerization components) As described above, the photopolymerization component is obtained by forming an adhesive composition containing a polymer (A), an adhesive component (B), and a thermal crosslinking agent (C) or forming the composition into a film form. During the period (for example, 3 days to 4 days), it is synthesized in a step (aging step) placed in an environment of about 40°C. Based on the total mass of the adhesive composition, the content of the polymer (A) in the adhesive composition is, for example, 1 to 50% by mass, or 5 to 40% by mass or 10 to 30% by mass quality%. Based on the total mass of the adhesive composition, the content of the adhesive component (B) in the adhesive composition is, for example, 30% by mass to 98% by mass, 50% by mass to 90% by mass, or 60% by mass to 85% quality%.

The content of the thermal crosslinking agent (C) in the adhesive composition may be appropriately set according to the cohesive force and elongation at break required for the adhesive layer 3 and the adhesion with the adhesive layer 5. Specifically, the content of the thermal crosslinking agent (C) is, for example, 3 parts by mass to 30 parts by mass, preferably 5 parts by mass relative to 100 parts by mass of the total amount of the polymer (A) and the adhesive component (B). 15 parts by mass, more preferably 7 parts by mass to 10 parts by mass. By setting the content of the thermal crosslinking agent to the above range, the characteristics required for the adhesive layer 3 in the crystal cutting step and the characteristics required for the adhesive layer 3 in the crystal bonding step can be balanced well. And it can also achieve excellent pickup.

If the content of the thermal crosslinking agent (C) is less than 3 parts by mass with respect to 100 parts by mass of the total content of the polymer (A) and the adhesive component (B), the formation of the crosslinked structure tends to become insufficient. Therefore, the interface adhesion force with the adhesive layer 5 in the pickup step is not sufficiently reduced, and defects are likely to occur during pickup. On the other hand, if the content of the thermal crosslinking agent (C) exceeds 30 parts by mass with respect to the total amount of 100 parts by mass of the polymer (A) and the adhesive component (B), the adhesive layer 3 tends to become excessively hard, resulting from Therefore, the semiconductor wafer is easily peeled off during the expansion step.

The adhesive composition undergoes a cross-linking reaction through the aging step to synthesize a photopolymerization component. Although it is difficult to ascertain the structure of the photopolymerization component as a polymer, it is possible to grasp the synthesized light by measuring the amount of the polymer (A) and the adhesive component (B) remaining separately in the adhesive composition after the aging step Polymerized components. The amount of the adhesive component (B) alone present in the adhesive composition (adhesive layer 3) after the aging step may be reduced as compared with the input amount (the amount before the aging step). The amount of the polymer (A) alone present in the adhesive composition (adhesive layer 3) after the aging step may be reduced as compared with the input amount (the amount before the aging step).

(Photopolymerization initiator (D)) Next, the photopolymerization initiator (D) contained in the adhesive layer 3 together with the photopolymerization component will be described. As the photopolymerization initiator (D), if it is an active species capable of performing chain polymerization by irradiating active energy rays (at least one selected from ultraviolet rays, electron beams, and visible rays), it is not particularly limited. For example, a photo radical polymerization initiator can be mentioned. Here, the active species capable of chain polymerization refers to a person who starts a polymerization reaction by reacting with a functional group capable of chain polymerization.

Examples of photo radical polymerization initiators include: benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one Etc. α-hydroxyketone; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 1,2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinylpropan-1-one and other α-aminoketones; 1-[4-(phenylthio)phenyl]-1,2-octanedione-2- (Benzyl) oxime esters such as oxime; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, bis(2,6-dimethoxybenzyl)-2, Phosphorus oxides such as 4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzyl diphenylphosphine oxide; 2-(o-chlorophenyl)-4,5-diphenyl Imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer Body, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. 2, 4,5-triarylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4 Benzophenone compounds such as'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-third butyl Anthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone , 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone and other quinone compounds; benzoin methyl ether , Benzoin ether, benzoin phenyl ether and other benzoin ethers; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; benzyl compounds such as benzyl dimethyl ketal; 9-phenylacridine, 1,7-bis (9 , 9'-acridinyl heptane) and other acridine compounds; N-phenylglycine, coumarin.

The content of the photopolymerization initiator (D) in the adhesive layer 3 is, for example, 0.1 to 30 parts by mass, preferably 0.3 to 10 parts by mass, more preferably 100 parts by mass of the photopolymerization component It is 0.5 to 5 parts by mass. If the content of the photopolymerization initiator (D) is less than 0.1 parts by mass, the adhesive layer 3 is insufficiently hardened after being irradiated with active energy rays, and is likely to cause poor pickup. If the content of the photopolymerization initiator (D) exceeds 30 parts by mass, contamination of the adhesive layer (transfer of the photopolymerization initiator to the adhesive layer) is likely to occur.

The thickness of the adhesive layer 3 may be appropriately set according to the conditions (temperature, tension, etc.) of the expansion step, for example, 1 μm to 200 μm, preferably 5 μm to 50 μm, and more preferably 10 μm to 20 μm. If the thickness of the adhesive layer 3 is less than 1 μm, the adhesiveness tends to be insufficient, and if it exceeds 200 μm, the cut-off property at the time of cool expansion tends to be insufficient.

The adhesive layer 3 is formed on the substrate layer 1. As a method of forming the adhesive layer 3, a known method can be used. For example, the laminate of the base material layer 1 and the adhesive layer 3 can be formed by a double-layer extrusion method, or a varnish for forming the adhesive layer 3 can be prepared and applied to the surface of the base material layer 1, or An adhesive layer 3 is formed on the release-treated film and transferred to the base material layer 1.

The varnish for forming the adhesive layer 3 is preferably prepared using an organic solvent that can dissolve the photopolymerization component and the photopolymerization initiator (D) and evaporates by heating. Specific examples of organic solvents include aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cumene; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; methanol, ethanol, and isopropyl Alcohol, butanol, ethylene glycol, propylene glycol and other alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and other ketones; methyl acetate Ester, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone and other esters; ethyl carbonate, propyl carbonate and other carbonates; ethylene glycol monomethyl ether, ethylene glycol mono Ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethyl ether Glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and other polyol alkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether ether Ester, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. Alcohol alkyl ether acetate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amides.

Among these, from the viewpoint of solubility and boiling point, for example, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl acetate are preferred , Ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether acetate, N,N-dimethylacetamide. These organic solvents may be used alone or in combination of two or more. The solid content concentration of the varnish is usually preferably 10% by mass to 60% by mass.

<Base layer> As the base material layer 1, a known polymer can be used. Specifically, examples of the base material layer 1 include crystalline polypropylene, amorphous polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, and low-density linear polymer. Polyolefins such as ethylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random , Alternate) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate and other polyesters, polycarbonate , Polyimide, Polyetheretherketone, Polyimide, Polyetherimide, Polyamide, Fully Aromatic Polyamide, Polyphenylene Sulfide, Aromatic Polyamide (aramid) (Paper) , Glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, silicone resin, or a mixture of these with a plasticizer, or by irradiation with an electron beam Cross-linked hardened product.

The base material layer 1 preferably has a surface having at least one resin selected from polyethylene, polypropylene, polyethylene-polypropylene random copolymer, and polyethylene-polypropylene block copolymer as a main component, and the surface It is in contact with the adhesive layer 3. These resins are also good base materials from the viewpoints of Young's modulus, characteristics such as stress relaxation and melting point, price, and recycling of waste materials after use. The base material layer 1 may be a single layer, and may have a multi-layer structure in which layers including different materials are laminated as needed. In order to control the adhesiveness with the adhesive layer 3, the surface of the base material layer 1 may be subjected to surface roughening treatments such as matting treatment and corona treatment.

<Adhesive layer> For the adhesive layer 5, an adhesive composition that constitutes a known crystal bonding film can be applied. Specifically, the adhesive composition constituting the adhesive layer 5 preferably contains an epoxy group-containing acrylic copolymer, an epoxy resin, and an epoxy resin hardener. The adhesive layer 5 containing these components has the following characteristics: excellent adhesion between wafers/substrates and wafers/wafers; in addition, electrode embedding, wire embedding, etc. can be imparted to the crystal bonding step It can be adhered at a low temperature and obtains excellent hardening in a short period of time, and after molding with a sealant, it has excellent reliability, etc., which is preferable.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, and phenol novolac. Varnish-type epoxy resin, cresol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, diglycidyl etherate of biphenol, diglycidyl etherate of naphthalene diphenol, diglycidyl ether of phenols Difunctional epoxy resins such as ethers, diglycidyl ethers of alcohols, and alkyl substituents, halides, and hydrides of these, and novolac-type epoxy resins. In addition, other commonly known epoxy resins such as multifunctional epoxy resins and heterocyclic epoxy resins can also be used. These can be used alone, or two or more kinds can be used in combination. Furthermore, components other than epoxy resin may be included as impurities within the range of non-destructive properties.

Examples of the epoxy resin hardener include a phenol resin and a hardener such as a phenol resin that can be obtained by reacting a phenol compound and a xylylene compound as a divalent linking group in the absence of a catalyst or an acid catalyst. Examples of phenol compounds used in the manufacture of phenol resins include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-n-propylphenol, m-n-propylphenol, P-n-propylphenol, o-isopropylphenol, m-isopropylphenol, p-isopropylphenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isopropyl Butylphenol, p-isobutylphenol, octylphenol, nonylphenol, 2,4-xylenol, 2,6-xylenol, 3,5-xylenol, 2,4,6-trimethyl Phenol, resorcin, resorcinol, hydroquinone, 4-methoxyphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, p-cyclohexylphenol, o-ene Propylphenol, p-allylphenol, o-benzylphenol, p-benzylphenol, o-chlorophenol, p-chlorophenol, o-bromophenol, p-bromophenol, o-iodophenol, p-iodophenol, o-fluorophenol, m-fluoro Phenol, p-fluorophenol, etc. These phenol compounds may be used alone, or two or more kinds may be used in combination. As the xylylene compound as a divalent linking group used in the production of the phenol resin, the following xylylene dihalide, xylylene diethylene glycol and derivatives thereof can be used. That is, α,α'-dichloro-p-xylene, α,α'-dichloro-m-xylene, α,α'-dichloro-o-xylene, α,α'-dibromo-p Xylene, α,α'-dibromo-m-xylene, α,α'-dibromo-o-xylene, α,α'-diiodine-p-xylene, α,α'-diiodine-m-xylene , Α,α'-diiodo-o-xylene, α,α'-dihydroxy-p-xylene, α,α'-dihydroxy-m-xylene, α,α'-dihydroxy-o-xylene, α ,α'-dimethoxy-p-xylene, α,α'-dimethoxy-m-xylene, α,α'-dimethoxy-o-xylene, α,α'-diethoxy -P-xylene, α,α'-diethoxy-m-xylene, α,α'-diethoxy-o-xylene, α,α'-x-n-propoxy-p-xylene, α ,α'-n-propoxy-m-xylene, α,α'-di-n-propoxy-o-xylene, α,α'-di-isopropoxy-p-xylene, α,α'- Diisopropoxy-m-xylene, α,α'-di-isopropoxy-o-xylene, α,α'-di-n-butoxy-p-xylene, α,α'-x-x Butoxy-m-xylene, α,α'-di-n-butoxy-o-xylene, α,α'-diisobutoxy-p-xylene, α,α'-diisobutoxy- M-xylene, α,α'-diisobutoxy-o-xylene, α,α'-di-third butoxy-p-xylene, α,α'-di-third butoxy-m- Xylene, α,α'-di-third butoxy-o-xylene. These can be used alone or in combination of two or more.

When reacting the phenol compound with the xylylene compound, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, etc.; dimethyl sulfuric acid, diethyl sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, etc. can be used Organic carboxylic acids; super strong acids such as trifluoromethanesulfonic acid; strong acidic ion exchange resins such as alkane sulfonic acid type ion exchange resins; super strong acid ion exchange resins such as perfluoroalkane sulfonic acid type ion exchange resins (Trade name: Nafion, Nafion, DuPont (made by DuPont), "Nafion" is a registered trademark); natural and synthetic zeolites; activated clay (acid clay) and other acidic catalysts, at 50 ℃ ~ It is obtained by reacting at 250°C until the xylylene compound as a raw material disappears and the reaction composition becomes constant. The reaction time also depends on the raw materials and the reaction temperature, and is about 1 hour to 15 hours. In fact, it may be determined by tracking the reaction composition by gel permeation chromatography (GPC).

The epoxy group-containing acrylic copolymer is preferably a copolymer obtained by using glycidyl acrylate or glycidyl methacrylate as a raw material in an amount of 0.5% by mass to 6% by mass relative to the copolymer obtained. When the amount is 0.5% by mass or more, high adhesion is easily obtained. On the other hand, when it is 6% by mass or less, gelation can be suppressed. For the remainder, a mixture of alkyl acrylate, alkyl methacrylate, styrene, acrylonitrile, etc. having a C1-C8 alkyl group such as methyl acrylate and methyl methacrylate can be used. Among these, particularly preferred are ethyl (meth)acrylate and/or butyl (meth)acrylate. The mixing ratio is preferably adjusted in consideration of the Tg of the copolymer. If Tg is less than -10°C, there is a tendency that the viscosity of the adhesive layer 5 in the B-stage state becomes large, and the handleability tends to be deteriorated. Furthermore, the upper limit of the glass transition temperature (Tg) of the epoxy group-containing acrylic copolymer is, for example, 30°C. The polymerization method is not particularly limited, and examples thereof include bead polymerization and solution polymerization. Examples of commercially available epoxy-containing acrylic copolymers include HTR-860P-3 (trade name, manufactured by Nagase ChemteX Co., Ltd.).

The epoxy group-containing acrylic copolymer has a weight average molecular weight of 100,000 or more, and within this range, the adhesiveness and heat resistance are high, preferably 300,000 to 3 million, and more preferably 500,000 to 2 million. If the weight average molecular weight is 3 million or less, it is possible to suppress a decrease in the filling property between the semiconductor wafer and the substrate supporting it. The weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

The adhesive layer 5 may further contain hardening accelerators such as tertiary amines, imidazoles, and quaternary ammonium salts as needed. Specific examples of the hardening accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2- Phenylimidazolium trimellitate. These may be used alone or in combination of two or more.

The adhesive layer 5 may further contain an inorganic filler as needed. Specific examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, Boron nitride, crystalline silicon dioxide, amorphous silicon dioxide. These may be used alone or in combination of two or more.

The thickness of the adhesive layer 5 is, for example, 1 μm to 300 μm, preferably 5 μm to 150 μm, and more preferably 10 μm to 100 μm. If the thickness of the adhesive layer 5 is less than 1 μm, the adhesion tends to be insufficient, and on the other hand, if it exceeds 300 μm, the cut-off property and the pick-up property during expansion tend to become insufficient.

The embodiments of the present disclosure have been described in detail above, but the present invention is not limited to the above embodiments. For example, in the above embodiment, the slicing-sticking integrated film 10 including the substrate layer 1, the adhesive layer 3, and the adhesive layer 5 in sequence is exemplified, but the adhesive layer 5 may not be included Appearance. 2 is a cross-sectional view schematically showing an embodiment of the die-bonding adhesive film of the present disclosure. The die-cut adhesive film 20 shown in FIG. 2 includes a base material layer 1 and an adhesive layer 3 provided on the base material layer 1. In addition, the film 10 and the film 20 may further include a cover film (not shown) that protects the outermost layer on the opposite side to the base material layer 1. That is, the film 10 may further include a cover film covering the adhesive layer 5, and the film 20 may further include a cover film covering the adhesive layer 3. [Example]

Hereinafter, the present disclosure will be described more specifically based on examples, but the present invention is not limited to these examples. In addition, as long as there is no special description, all chemicals use reagents.

<Manufacture of polymer (A)> (Production Example A1) The polymer (A) of Production Example 1 was obtained by copolymerizing the following monomers (see Production Example 1 of Table 1). ·Quaternary ammonium salt monomer: [2-(methacryloyloxy)ethyl]trimethylammonium bis(trifluoromethylsulfonyl)imide 50 parts by mass ·Polymerizable monomer: 2-ethylhexyl acrylate 40 parts by mass 10 parts by mass of 2-hydroxyethyl acrylate

The acid value and hydroxyl value of the resin were determined according to Japanese Industrial Standards (JIS) K0070. The acid value was 0.0 mgKOH/g and the hydroxyl value was 48.4 mgKOH/g.

The obtained polymer (A) was vacuum-dried at 60° C. overnight, and the obtained solid component was subjected to elemental analysis using a full-automatic element analysis device vario EL manufactured by elementar company. The content of 2-methacryloxyethyl isocyanate introduced (the amount of functional groups capable of chain polymerization) was calculated from the nitrogen content.

SD-8022/DP-8020/RI-8020 manufactured by Tosoh Co., Ltd. was used, Gelpack GL-A150-S/GL-A160-S manufactured by Hitachi Chemical Co., Ltd. was used as the column, and tetrahydrofuran was used as the dissolution liquid. , GPC measurement was carried out, and the weight average molecular weight in terms of polystyrene was 20,000. The results are shown in Table 1.

(Production Example A2, Production Example A3) Except for using the monomers described in Production Example A2 and Production Example A3 in Table 1, the polymers (A) of Production Example A2 and Production Example A3 were obtained in the same manner as in Production Example A1, and the weight average molecular weight and the like were measured. . The results are shown in Table 1.

[Table 1]

<Synthesis of Sticky Ingredient (B)> (Production Example B1) The polymer is obtained by copolymerizing the following components. 20-mass parts of 2-hydroxyethyl acrylate (copolymerization component with hydroxyl groups) ·79 parts by mass of 2-ethylhexyl acrylate • 1 part by mass of methacrylic acid is copolymerized. To the obtained polymer, p-methoxyphenol (methoquinone) as a polymerization inhibitor and dioctyltin dilaurate as an urethane catalyst were added, and then 16.2 parts by mass of 2-methacrylic acid was added Acetyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko Co., Ltd.) obtained an acrylic resin solution (a solution containing an adhesive component (B)) having a functional group capable of chain polymerization.

The acid value and hydroxyl value were determined. The acid value was 6.5 mgKOH/g and the hydroxyl value was 32.8 mgKOH/g. In addition, the obtained acrylic resin was vacuum-dried at 60° C. overnight, and the obtained solid component was subjected to elemental analysis using a full-automatic elemental analysis device vario EL manufactured by elementar. And the content of 2-methacryloxyethyl isocyanate introduced (the amount of functional groups capable of chain polymerization) calculated from the nitrogen content was 0.9 mmol/g.

SD-8022/DP-8020/RI-8020 manufactured by Tosoh Co., Ltd. was used, Gelpack GL-A150-S/GL-A160-S manufactured by Hitachi Chemical Co., Ltd. was used as the column, and tetrahydrofuran was used as the dissolution liquid. , GPC measurement was performed, and the polystyrene-equivalent weight average molecular weight was 300,000. The results are shown in Table 2.

(Production Example B2) Except for using the monomers described in Production Example B2 in Table 2, the acrylic resin solution (solution containing the adhesive component (B)) of Production Example B2 was obtained in the same manner as in Production Example B1, and the weight average molecular weight and the like were measured. . The results are shown in Table 2.

[Table 2]

＜Fabrication of crystal cutting film＞ (Example 1) The mixture of the following components (A) to (D) and ethyl acetate in an amount of 25% by mass in total solid content of these components was stirred for 10 minutes to obtain a crystallite film (for adhesive layer) Varnish. (A) Production Example A1 polymer 10 g (solid content) (B) Acrylic resin of Production Example B1 100 g (solid content) (C) Thermal crosslinking agent: polyfunctional isocyanate (made by Japan Polyurethane Industry Co., Ltd., Coronate L, solid content 75%) 8.0 g (solid content) (D) Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba specialty chemicals) Co., Ltd., Irgacure 184, "Irgacure" is registered Trademark) 1.0 g

On a polyethylene terephthalate film with a width of 450 mm, a length of 500 mm, and a thickness of 38 μm that has undergone release treatment on one side, use an applicator to apply the adhesive while adjusting the gap to a thickness of 10 μm The varnish was then dried at 80°C for 5 minutes. In addition, a single-sided corona-treated polyolefin film with a width of 450 mm, a length of 500 mm, and a thickness of 100 μm was used, and the corona-treated surface of the polyolefin film and the polyterephthalate with the adhesive layer The adhesive layer of the ethylene glycol film is attached at room temperature, and is adhered by a rubber roller, thereby transferring the adhesive layer to the polyolefin film. Thereafter, a step of leaving at room temperature for 3 days (aging step) to obtain a crystal-cut film with a cover film.

＜Fabrication of Adhesive Monolayer Film＞ In the same manner as described above, a varnish for an adhesive layer for a dicing film was prepared, and a single-sided polyethylene terephthalate film with a width of 450 mm, a length of 500 mm, and a thickness of 38 μm subjected to release treatment on one side, Using an applicator, the adhesive varnish was applied while adjusting the gap so that the thickness of the adhesive layer was 10 μm, and then dried at 80° C. for 5 minutes. In addition, a polyethylene terephthalate film with a width of 450 mm, a length of 500 mm, and a thickness of 25 μm, which has been subjected to release treatment on one side, is used, and the release surface of the polyethylene terephthalate film is removed, and The adhesive layer of the polyethylene terephthalate film with an adhesive layer is bonded at room temperature to produce an adhesive layer single-layer film.

＜Fabrication of sticky crystal film＞ To the composition containing the following components, cyclohexanone was added and stirred and mixed, and further kneaded for 90 minutes using a bead mill. ·Epoxy resin: YDCN-703 (trade name made by Dongdu Chemical Co., Ltd., cresol novolac epoxy resin, epoxy equivalent 210, molecular weight 1200, softening point 80°C) 55 parts by mass Phenol resin: Milex XLC-LL (trade name manufactured by Mitsui Chemicals Co., Ltd., phenol resin, hydroxyl equivalent 175, water absorption rate 1.8%, heating weight reduction rate at 350°C 4%) 45 parts by mass ·Silane coupling agent: NUC A-189 (trade name made by NUC Co., Ltd., γ-mercaptopropyltrimethoxysilane) 1.7 parts by mass, and NUC A-1160 (trade name made by NUC Co., Ltd., γ- Ureidopropyltriethoxysilane) 3.2 parts by mass ·Filling material: Aerosil R972 (Filling dimethyl dichlorosilane on the surface of silicon dioxide and hydrolyzing it in a reactor at 400℃ with organic groups such as methyl groups on the surface, Aerosil in Japan (Aerosil) Trade name made by Co., Ltd., silica, average particle diameter 0.016 μm) 32 parts by mass

To the mixture obtained as described above, 280 parts by mass of acrylic rubber (Acrylic rubber) HTR-860P-3 (Nagase ChemteX) limited by shares containing 3% by mass of glycidyl acrylate or glycidyl methacrylate was added. The company's trade name, with a weight average molecular weight of 800,000), and 0.5 parts by mass of Curazol (Purezol) 2PZ-CN (trade name made by Shikoku Chemical Industry Co., Ltd.) as a hardening accelerator, 1-cyanoethyl Yl-2-phenylimidazole, "Curezol (Curezol)" is a registered trademark), stirred and mixed, and vacuum degassed to obtain a varnish.

After applying a varnish to a 35 μm-thick release polyethylene terephthalate film, it was heated and dried at 140°C for 5 minutes to form a B-stage coating film with a film thickness of 10 μm. Viscous crystal film of the carrier film.

＜Fabrication of integrated crystal cutting and crystal bonding＞ Together with the carrier film, the sticky crystal film was cut into a circle with a diameter of 318 mm. The crystal-cut film from which the cover film was peeled was attached to it at room temperature, and then it was left at room temperature for 1 day. Thereafter, the crystal-cut film was cut into a circle with a diameter of 370 mm, and the crystal-cut crystal-bonded integrated film of Example 1 was obtained. In addition, in order to perform the following evaluation, a plurality of slicing-crystal bonding integrated films were produced.

(Measurement of storage elastic coefficient of adhesive layer at 23°C) The storage elasticity coefficient of the adhesive layer at 23° C. was measured using an autograph (registered trademark), a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd. The adhesive single-layer film was used as a measurement sample. The two polyethylene terephthalate films cut into an adhesive layer with a width of 50 mm and a length of 30 mm were peeled off, and the adhesive was collected in a single layer. The elastic coefficient of the adhesive layer (without UV irradiation) at 23°C was measured with a distance between fixtures of 20 mm and a frequency of 1 Hz.

(Measurement of Surface Resistivity of Adhesive Layer) The die-cut crystal-bonded integrated film of Example 1 was cut to 150 mm×150 mm, and used as a measurement sample. Under the environment of 23±2°C and 50±2%RH, peel off the peeling sheet from the measurement sample, and measure the adhesive according to JIS K6911 using a high resistivity meter (manufactured by Mitsubishi Chemical Corporation, HIRESTA-UP MCP-HT450) The surface resistivity of the exposed surface of the layer. The value 30 seconds after the start of the measurement was read and set as the surface resistivity (Ω/□) of the adhesive layer (before UV irradiation). The crystal-bonded integrated film of Example 1 was irradiated with ultraviolet rays under the conditions of 70 mW and 200 mJ/cm ² , and then the surface resistivity (Ω/□) was measured in the same manner as described above. Let this be the surface resistivity (Ω/□) of the adhesive layer (after UV irradiation).

(30° peeling after UV curing) The crystal-bonded crystal integrated film of Example 1 was irradiated with ultraviolet light under the conditions of 70 mW and 200 mJ/cm ² . The film after ultraviolet irradiation was cut to a width of 25 mm. Use this as a measurement sample. Attach it to a silicon mirror wafer placed on a hot plate at 40°C. Leave it for about 30 minutes and use a tensile tester to measure the peel adhesion. The measurement conditions were set as the peeling angle: 30°, and the stretching speed: 60 mm/min. In addition, the storage of the measurement sample and the measurement of the peeling adhesive force were performed under the environment of a temperature of 23°C and a relative humidity of 50%.

(Pickup) After the die-bonding integrated film of Example 1 was attached to an 8-inch wafer (thickness 50 μm) at 80° C. for 10 seconds, the die-cutting was 10 mm×10 mm. The pick-up property of the semiconductor wafer obtained in the above step was evaluated using a flexible die bonder "DB-730" manufactured by Renesas Eastern Japan Semiconductor. The chuck for pickup uses "rubber tip (RUBBER TIP) 13-087E-33 (size: 10 mm × 10 mm)" manufactured by Micromechanics. The upper pin used "EJECTOR NEEDLE" SEN2-83-05 (diameter: 0.7 mm, tip shape: semi-circle with a diameter of 350 μm) manufactured by Micromechanics. The upper push pin is arranged with 9 pins at a pin center interval of 4.2 mm. The pick-up property was evaluated under the conditions of the push-up speed of the pin at the time of pickup: 10 mm/s and the push-up height: 200 μm. Pick up 100 wafers in succession, and determine that there are no errors such as chip breakage or pick-up errors as "A", and that even if one wafer has an error, it is determined as "B", and it will be from 2 wafers to 5 wafers. The case where an error occurs is judged as "C", and the case where an error occurs at a higher rate is judged as "D".

(Grain shear strength) Set the wafer crimped to the lead frame on the platform, hook and pull the wafer using a universal bond tester series 4000 (manufactured by Dage), thereby measuring the interface adhesion between the wafer and the lead frame (Before UV irradiation). The measurement conditions were carried out with the platform temperature at room temperature.

(Example 2 to Example 7 and Comparative Example 1, Comparative Example 2) Except for the composition shown in Table 3 and Table 4, the adhesive composition prepared in the same manner as in Example 1 was used to prepare a slicing-crystal bonding integrated film and the like, and the evaluation was performed.

[table 3]

[Table 4]

As shown in Table 3, the die-bonded integrated films of Examples 1 to 7 have low surface resistivity and therefore have excellent antistatic properties. In the die bonding step, even if the amount of protrusion height is low Can be picked up, the adhesive layer also has excellent crystal bonding properties.

On the other hand, in Comparative Example 1 shown in Table 4, the surface resistivity is high. In Comparative Example 2, although the surface resistivity decreased, the peel strength of the adhesive layer and the adhesive layer increased, the pick-up property decreased, and the shear strength of the crystal grain decreased. Therefore, contamination by the antistatic agent was confirmed. [Industry availability]

An aspect of the disclosed die-cut crystal integrated film has excellent antistatic properties, and suppresses contamination of the adhesive layer and increase in peeling strength during peeling, so that it can exhibit excellent pickup characteristics and crystal bonding characteristics Therefore, by using it in the semiconductor manufacturing process, excellent productivity can be obtained.

1‧‧‧ Base layer 3‧‧‧Adhesive layer 5‧‧‧ Adhesive layer 10‧‧‧Crystal-stick crystal integrated film 20‧‧‧Crystal-stick crystal integrated film adhesive film (adhesive film for crystal cutting)

FIG. 1 is a cross-sectional view schematically showing an embodiment of the integrated die-bonding crystal film of the present disclosure. 2 is a cross-sectional view schematically showing an embodiment of the adhesive film of the present disclosure.

1‧‧‧ Base layer

3‧‧‧Adhesive layer

5‧‧‧ Adhesive layer

10‧‧‧Crystal-stick crystal integrated film

Claims (7)

An adhesive film, which is an adhesive film for slicing-sticking integrated film, and includes at least: Substrate layer, and An adhesive layer provided on the substrate layer, The adhesive layer contains: A photopolymerizable component comprising structural units derived from a polymer (A), an energy-hardenable adhesive component (B) having a hydroxyl group, and a thermal crosslinking agent (C), the polymer (A) having a quaternary ammonium salt Group and hydroxyl group; and Photopolymerization initiator (D), The structural unit is at least a structural unit in which the polymer (A) and the adhesive component (B) are connected via the thermal crosslinking agent (C), and the structural component in which the adhesive component (B) is connected to each other via the thermal crosslinking agent (C) One. The adhesive film as described in item 1 of the patent application range, wherein the storage elastic coefficient of the adhesive layer at 23° C. is 10 MPa to 60 MPa. The adhesive film according to item 1 or 2 of the patent application scope, wherein the weight average molecular weight of the polymer (A) is 10,000 to 200,000. The adhesive film according to any one of claims 1 to 3, wherein the adhesive component (B) contains a resin having a functional group capable of chain polymerization, The functional group is at least one selected from the group consisting of acryloyl and methacryloyl. The adhesive film as described in any one of patent application items 1 to 4, wherein the thermal crosslinking agent (C) is a multifunctional isocyanate having more than two isocyanate groups in one molecule, and A reactant of a polyol having more than three OH groups in one molecule. The adhesive film according to any one of items 1 to 5 of the patent application range, wherein the photopolymerization initiator (D) is a photoradical polymerization initiator. A die-cut crystal-bonded crystal integrated film, comprising: the adhesive film as described in any one of the patent application items 1 to 6; and An adhesive layer provided on the adhesive layer of the adhesive film.

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