JP5175085B2 - Dicing substrate film and dicing film - Google Patents

Description

  The present invention relates to a dicing film for fixing a semiconductor wafer or the like when the semiconductor wafer or the like is diced into chips.

  A semiconductor wafer is made in advance in a large area, then diced (cut and separated) into chips and transferred to an expanding process. In the dicing, a dicing film is used for fixing the semiconductor wafer.

  The dicing film is basically composed of an adhesive layer for fixing a semiconductor wafer and a resin layer (a substrate film for dicing) that receives the cutting of a dicing blade. The semiconductor wafer fixed to the dicing film is diced into chips, and is picked up after being uniformly expanded in the surface direction on the expanding ring in order to separate the chips.

  In the semiconductor wafer dicing process, the adhesive layer or a part of the substrate film for dicing is also cut together with the wafer, so that the resin becomes a molten state due to frictional heat of the resin, and resin-derived cutting waste (dicing waste) is generated. Since this cutting waste contaminates the wafer and lowers the yield of chips, it is necessary to reduce it as much as possible.

  For example, the following dicing film has been reported mainly for the purpose of eliminating cutting waste in the dicing process.

  Patent Document 1 describes a polyolefin film such as polyethylene irradiated with 1 to 80 Mrad of an electron beam or γ-ray as a base film. However, since this film crosslinks the entire crosslinkable resin with an electron beam or the like, it becomes hard and sufficient expandability cannot be obtained.

  Patent Document 2 describes an ethylene / methyl methacrylate copolymer film as a base film. However, although this film can reduce a certain amount of cutting waste, it is not always sufficient.

  Patent Document 3 mainly discloses a resin layer B mainly composed of an ionomer resin obtained by crosslinking a terpolymer of ethylene, (meth) acrylic acid, and (meth) acrylic acid alkyl ester with metal ions, and an adhesive layer. A semiconductor wafer fixing adhesive tape laminated with A is described. However, since this film contains metal ions, contamination of the wafer becomes a problem.

  In Patent Document 4, a pressure-sensitive adhesive coated layer, a thermoplastic elastomer layer, and a resin layer are laminated in this order, and the thermoplastic elastomer layer contains 70% by mass or more of a hydrogenated styrene-butadiene copolymer. An adhesive tape base material comprising a composition and having a layer thickness of 30% or more with respect to the base material thickness is described. However, this film does not always have a sufficient cutting scrap reduction effect.

  In Patent Document 5, in a base film comprising at least two layers, polypropylene is used as a resin for the adhesive layer side, and a hydrogenated styrene-butadiene copolymer is used as a layer other than the resin layer on the adhesive layer side. The use is described.

By the way, the substrate film for dicing is usually rolled, manufactured, stored, transported and the like. For this reason, when the blocking between films occurs, the quality deteriorates. That is, even if the substrate film for dicing has an excellent quality, it is difficult to provide a high-quality dicing film unless the problem due to blocking is solved.
Japanese Patent Laid-Open No. 5-21234 JP-A-5-156214 Japanese Patent Laid-Open No. 9-8111 JP 2005-272724 A JP 2005-174963 A

  The main object of the present invention is to provide a dicing substrate film and a dicing film in which cutting waste (thread-like or whisker-like waste generated from a film after dicing) is hardly generated in a dicing process of a semiconductor wafer and blocking does not occur. With a purpose.

  As a result of intensive studies in order to solve the above problems, the present inventor has found that 90 to 30% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene- (meth) acrylic acid. A substrate film for dicing having an A layer containing 10 to 70% by weight of a copolymer is also a substrate film for dicing comprising A layer / B layer, and vinyl aromatic hydrocarbon-conjugated diene carbonization is formed in the A layer. A substrate film for dicing comprising 90 to 30% by weight of a hydrogenated product of a hydrogen copolymer and 10 to 70% by weight of an ethylene- (meth) acrylic acid copolymer, and containing a thermoplastic resin having rubber elasticity in the B layer. It has been found that almost no cutting waste is generated during dicing, and that the blocking resistance is excellent. Based on this knowledge, further studies have been made and the present invention has been completed.

  That is, the present invention provides the following dicing substrate film and dicing film.

  Item 1 A substrate for dicing having an A layer containing 90 to 30% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and 10 to 70% by weight of an ethylene- (meth) acrylic acid copolymer Film.

  Item 2. The substrate film for dicing according to Item 1, wherein the content of vinyl aromatic hydrocarbon units in the hydrogenated product of the vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is 5 to 20% by weight.

  Item 3 A substrate film for dicing comprising A layer / B layer, wherein the A layer comprises 90-30% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene- (meth) acrylic acid. Item 2. The substrate film for dicing according to Item 1, comprising 10 to 70% by weight of a copolymer, and the B layer contains a thermoplastic resin having rubber elasticity.

  Item 4. The substrate film for dicing according to Item 3, wherein the B layer further comprises 10 to 45 parts by weight of an antistatic agent with respect to 100 parts by weight of the thermoplastic resin having rubber elasticity.

  Item 5. The dicing substrate film according to Item 1, 2, 3 or 4, wherein the dicing substrate film has a total thickness of 50 to 300 μm.

  Item 6. The substrate film for dicing according to Item 3 or 4, wherein the total thickness of the substrate film for dicing is 50 to 300 μm, and the ratio of the thicknesses of the A layer and the B layer is 20/1 to 1/1.

  Item 7 A dicing film further comprising an adhesive layer on the A layer of the substrate film for dicing according to any one of Items 1 to 6.

  Item 8. A method for producing a substrate film for dicing consisting of a single layer, wherein 90-30% by weight of a hydrogenated vinyl aromatic hydrogen-conjugated diene hydrocarbon copolymer and an ethylene- (meth) acrylic acid copolymer A production method comprising extruding a resin containing 10 to 70% by weight.

  Item 9 A method for producing a substrate film for dicing comprising A layer / B layer, comprising 90-30% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene- (meth) acrylic acid A production method comprising co-extrusion molding a layer A resin containing 10 to 70% by weight of a copolymer and a layer B resin containing a thermoplastic resin having rubber elasticity.

  Since the substrate film for dicing according to the present invention hardly generates cutting waste in the dicing process, there is no concern about contamination of the wafer. In addition, even if the dicing film is wound into a roll, blocking between the films does not occur, so that high quality can be maintained.

I. Dicing Substrate Film The dicing substrate film of the present invention has a vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer hydrogenated product of 90 to 30% by weight and an ethylene- (meth) acrylic acid copolymer of 10 to 70% by weight. % (Layer A) containing at least%. Therefore, it includes a substrate film for dicing having a single layer or two or more layers having the A layer.
(1) Single-layer film When the substrate film for dicing of the present invention is a single layer, 90-30% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene- (meth) acrylic acid copolymer 10 to 70% by weight of polymer.

  Here, the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is a compound obtained by hydrogenating a copolymer of vinyl aromatic hydrocarbon and conjugated diene hydrocarbon. The compound is commercially available or can be easily produced by a known method. The vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer may be either random or block, but is preferably a block.

  Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl- Examples thereof include p-aminoethylstyrene, and these may be used alone or in combination of two or more. Styrene is particularly preferred.

  The conjugated diene hydrocarbon is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3. -Butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like, and particularly common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more. In particular, butadiene is preferred.

  The content of vinyl aromatic hydrocarbon (for example, styrene) units in the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is 5 to 20% by weight, preferably 5 to 15% by weight. In addition, the content of the conjugated diene hydrocarbon (eg, butadiene) unit is 80 to 95% by weight, preferably 85 to 95% by weight. When the content of vinyl aromatic hydrocarbon (for example, styrene) units exceeds 20% by weight, cutting scraps are likely to be generated, so the above range is preferably selected. The content of styrene monomer units is measured using an ultraviolet spectrophotometer or a nuclear magnetic resonance apparatus (NMR), and the content of diene monomer units is measured using a nuclear magnetic resonance apparatus (NMR). be able to.

  The hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer can be obtained by hydrogenating the vinyl aromatic hydrocarbon / conjugated diene hydrocarbon copolymer.

  The hydrogenation reaction is generally performed in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 7 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.

  In the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer used in the present invention, the hydrogenation rate of unsaturated double bonds based on the conjugated diene hydrocarbon in the block copolymer before hydrogenation (water The addition ratio is 60% or more, preferably 75% or more, more preferably 85% or more, particularly preferably 90% or more of the unsaturated double bond based on the conjugated diene hydrocarbon in the copolymer. It is desirable that The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR).

  The weight average molecular weight (Mw) of the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer may be, for example, about 100,000 to 500,000, preferably about 150,000 to 300,000. The weight average molecular weight can be measured using commercially available standard gel permeation chromatography (GPC).

  Examples of the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer include “Clayton G” manufactured by Kraton Polymer Japan Co., Ltd., “Hyblar” manufactured by Kuraray Co., Ltd., and “Dynalon” manufactured by JSR Co., Ltd. Can be mentioned.

  Preferred examples of the ethylene- (meth) acrylic acid copolymer include a binary copolymer composed of a structural unit derived from ethylene and a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid means acrylic acid or methacrylic acid. Therefore, specific examples of the ethylene- (meth) acrylic acid copolymer include an ethylene-acrylic acid binary copolymer or an ethylene-methacrylic acid binary copolymer. Preferably, it is an ethylene-methacrylic acid copolymer.

  The ethylene content of ethylene- (meth) acrylic acid copolymer (content of structural units derived from ethylene) is preferably 96 to 85% by weight, more preferably 95 to 88% by weight, particularly preferably 93 to 91% by weight. The (meth) acrylic acid content (constituent unit content derived from (meth) acrylic acid) is preferably 4 to 15% by weight, more preferably 5 to 12% by weight, and particularly preferably 7 to 9%. % By weight. Examples of the ethylene- (meth) acrylic acid copolymer include “Nucrel” manufactured by Mitsui DuPont Polychemical Co., Ltd.

  The content of hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer in the single layer film is 90 to 30% by weight, and the content of ethylene- (meth) acrylic acid copolymer is 10 to 70% by weight. %. In particular, since a single layer film does not include a separate blocking layer, if the content of hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is increased (for example, exceeding 50% by weight), blocking is performed. It becomes easy. Therefore, the hydrogenated content of the vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is 30 to 50% by weight, preferably 30 to 40% by weight, and the ethylene- (meth) acrylic acid copolymer The content is 50 to 70% by weight, preferably 60 to 70% by weight.

  When the single layer film of the present invention has the above composition, generation of cutting chips can be suppressed in the dicing process of the semiconductor wafer. Further, even when the film is rolled, blocking between the films can be effectively suppressed.

The thickness of the single layer film may be thicker than the cutting depth of the dicing blade and can be easily wound in a roll shape, and is, for example, 50 to 300 μm, preferably 60 to 250 μm, more Preferably it is 70-200 micrometers.
(2) Multilayer film When the substrate film for dicing of the present invention is a multilayer, a substrate film for two-layer dicing comprising the following A layer / B layer is exemplified, but the present invention is not limited thereto.

As the base film for two-layer dicing, for example, a base film for dicing consisting of A layer / B layer, wherein the A layer is a hydrogenated 90-30 wt% vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer. % And ethylene- (meth) acrylic acid copolymer 10 to 70% by weight, and the B layer includes a substrate film for dicing containing a thermoplastic resin having rubber elasticity.
A layer:
Examples of the hydrogenated styrene-conjugated diene block copolymer and the ethylene- (meth) acrylic acid copolymer used in the A layer include those described in the above single-layer film.

  The hydrogenated content of the vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is 90 to 30% by weight, preferably 80 to 30% by weight, and the ethylene- (meth) acrylic acid copolymer The content can be selected from the range of 10 to 70% by weight, preferably 20 to 70% by weight. In particular, in the case of a two-layer film, the layer B (antiblocking layer) can be laminated unlike a single-layer film, so that the content of hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is high. A wide range of the above can be selected.

  For example, the content of hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is more than 50% by weight and not more than 90% by weight, and the content of ethylene- (meth) acrylic acid copolymer is 10% by weight. In the case of% or more and less than 50% by weight, blocking is likely to occur in a single layer, but blocking does not occur because a blocking prevention layer is provided as the B layer.

B layer:
The thermoplastic resin having rubber elasticity used in the B layer is uniformly expanded in contact with the expanding ring. Examples of the thermoplastic resin having rubber elasticity include low-density polyethylene, medium-density polyethylene, linear low-density polyethylene which is an ethylene-α-olefin copolymer, or ultra-low-density polyethylene, and α-olefin is Propylene, butene-1, octene-1, 4methylpentene-1, hexene-1, octene-1 resin, styrene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer Polymer (EMA), ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer (EMMA), ethylene-methacrylic acid copolymer (EMAA), ethylene -Ethyl methacrylate copolymer, a mixture of these resins, and the like. Of these, EMA, EMAA or EMMA is preferable, and EMA is particularly preferable.

The B layer contains the above-described thermoplastic resin having rubber elasticity as an essential component, but may further contain an antistatic agent as necessary. Antistatic agents include anionic,
Known surfactants such as cationic and nonionic surfactants can be selected. In particular, from the viewpoint of durability and durability, polyether ester amide resins (hereinafter referred to as “PEEA resins”), hydrophilic polyolefin resins (hereinafter referred to as “ Nonionic surfactants such as “hydrophilic PO resin” are preferred.

The PEEA resin is a polymer composed of a polyether ester, which is a main unit component for imparting hydrophilicity, and a polyamide unit, and is commercially available or can be easily produced by a known method. Examples of the PEEA resin include Pelestat NC6321 from Sanyo Chemical Industries, Ltd. In addition, the production method is described in JP-A-64-45429, JP-A-6-287547, etc. According to this, for example, a polydiol component having an ether group in the main chain is added to a dicarboxylic acid. It can be produced by reacting the components into a terminal ester and reacting this with an aminocarboxylic acid or lactam. The PEEA resin has good compatibility with any of the above-mentioned layers of resin, and there is no phenomenon of bleeding out.

  Examples of the hydrophilic PO resin include hydrophilic polyethylene (hereinafter referred to as “hydrophilic PE resin”) or hydrophilic polypropylene (hereinafter referred to as “hydrophilic PP resin”).

  The hydrophilic PE resin or the hydrophilic PP resin is basically a block in which a polyethylene chain or a polypropylene chain and a polyoxyalkylene chain are bonded to each other, exhibiting a high static elimination action and eliminating the accumulation of static electricity. This bonding is performed by an ester group, an amide group, an ether group, a urethane group or the like. From the viewpoint of compatibility with the film resin, this bond is preferably an ester group or an ether group. As the hydrophilic PP resin, for example, Pelestat 230 manufactured by Sanyo Chemical Industries, Ltd. is exemplified.

  The molecular weight of the polyethylene chain or the polypropylene chain in the hydrophilic PE resin or the hydrophilic PP resin is, for example, about 1200 to 6000. This is because, within this molecular weight range, it is easy to acid-modify polyethylene or polypropylene at the stage before block bonding polyethylene or polypropylene to the polyoxyalkylene chain.

  The molecular weight of the polyoxyalkylene chain in the hydrophilic PE resin or hydrophilic PP resin is preferably about 1000 to 15000 from the viewpoint of heat resistance and reactivity with polyethylene or polypropylene after acid modification. The molecular weight described above is a value measured using GPC.

  The hydrophilic PE resin or the hydrophilic PP resin can be produced by, for example, acid-modifying polyethylene or polypropylene having the above-described molecular weight and reacting this with polyalkylene glycol. More details are described in, for example, Japanese Patent Application Laid-Open Nos. 2001-278985 and 2003-48990.

When B layer contains an antistatic agent, content of an antistatic agent is 10-45 weight part with respect to 100 weight part of thermoplastic resins which have the said rubber elasticity, Preferably it is 20-30 weight part. Within such a range, the semi-conductivity is effectively imparted without impairing the slipperiness of the B layer when uniformly expanded in contact with the expand ring, so that the generated static electricity can be quickly eliminated. . For example, the film of the present invention containing the antistatic agent in the above-described range is preferable because the surface resistivity of the back surface is about 10 ⁷ to 10 ¹² Ω / □.

  An anti-blocking agent and the like may be further added to the B layer as long as the effects of the present invention are not adversely affected. By adding an anti-blocking agent, blocking such as when the substrate film for dicing is rolled up is preferably suppressed. Examples of the anti-blocking agent include inorganic or organic fine particles.

Thickness of each layer The thickness of the base film for two-layer dicing composed of the A layer and the B layer is sufficient as long as it is thicker than the cutting depth of the dicing blade and can be easily wound into a roll. For example, it is 50-300 micrometers, Preferably it is 60-250 micrometers, More preferably, it is 70-200 micrometers.

  The ratio of the thickness of the A layer is 95 to 50%, preferably 90 to 65%, and the ratio of the thickness of the B layer is 5 to 50%, preferably with respect to the total thickness of the two-layer dicing substrate film. Is 10 to 35%. The ratio of the thicknesses of the A layer and the B layer is 20/1 to 1/1, preferably 10/1 to 10 / 5.5, more preferably 10/1 to 10/3.

  As a specific example of the substrate film for dicing, when the total thickness of the substrate film for dicing is 120 to 180 μm, the thickness of the A layer is 60 to 171 μm, preferably 78 to 162 μm. The thickness of B layer is 6-90 micrometers, Preferably it is 12-63 micrometers.

It is preferable that the thickness of the A layer is thicker than the depth of the deepest part of the dicing blade, so that the cutting of the dicing blade does not reach the B layer. By providing the A layer having such a thickness, cutting scraps as a base film are hardly generated.
II. Manufacturing method of substrate film for dicing The substrate film for dicing of the present invention is manufactured by coextrusion molding of a resin. Specifically, the substrate film for dicing consisting of a single layer (A layer) is composed of 90-30% by weight of a hydrogenated vinyl aromatic hydrogen-conjugated diene hydrocarbon copolymer and ethylene- (meth) acrylic acid copolymer. A resin (A layer resin) containing 10 to 70% by weight of a polymer can be produced by extrusion molding.

  The substrate film for dicing consisting of two layers of A layer / B layer is composed of 90-30% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene- (meth) acrylic acid copolymer. A layer A resin containing 10 to 70% by weight of the coalescence and B layer resin containing a thermoplastic resin having rubber elasticity can be produced by coextrusion molding.

  The resin for the A layer is prepared by dry blending or melt-kneading a predetermined proportion of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and an ethylene- (meth) acrylic acid copolymer. The B layer resin is prepared from a thermoplastic resin having rubber elasticity. In addition, you may add additives, such as an antistatic agent, to the resin which comprises B layer as needed.

  In the case of a single-layer film, the above-mentioned single-layer (A layer) resin is supplied to a screw type extruder and extruded from a single-layer T die at 180 to 225 ° C., and this is cooled at 50 to 70 ° C. It is cooled while passing through the glass and taken up substantially unstretched. Alternatively, the resin may be once obtained as pellets and then extruded as described above.

  In the case of a multilayer film, the above-mentioned resins for each layer are supplied to the screw type extruder in this order, extruded from a multilayer T die at 180 to 225 ° C, and passed through a cooling roll at 50 to 70 ° C. While cooling, it is taken up substantially unstretched. Alternatively, the resin for each layer may be once obtained as pellets and then extruded as described above.

The reason why the film is substantially unstretched at the time of taking is to effectively extend the film after dicing. This substantially non-stretching includes non-stretching or slight stretching that does not adversely affect the expansion of the dicing film. In general, the film may be pulled to such an extent that no sagging occurs during film take-up.
III. Dicing film The substrate film for dicing obtained as described above is coated with a known acrylic pressure-sensitive adhesive on the film to form a pressure-sensitive adhesive layer, and if necessary, on the acrylic pressure-sensitive adhesive layer (pressure-sensitive adhesive layer). A release film is provided to produce a dicing film. That is, an acrylic pressure-sensitive adhesive layer and a release film are formed on the A layer of the substrate film for dicing.

  As the pressure-sensitive adhesive component used in the acrylic pressure-sensitive adhesive layer, known ones can be used. For example, the pressure-sensitive adhesive component described in JP-A No. 5-21234 can be used. A known release film is also used.

Specific examples of acrylic pressure-sensitive adhesives include acrylic polymers selected from homopolymers and copolymers having (meth) acrylic acid ester as the main constituent monomer unit, and other functional monomers And a mixture of these polymers. For example, (meth) acrylic acid ester includes ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Glycidyl acrylate, 2-hydroxyethyl acrylate and the like can be preferably used. The molecular weight of the acrylic polymer is 1.0 × 10 ^{5 to} 10.0 × 10 ⁵ , and preferably 4.0 × 10 ^{5 to} 8.0 × 10 ⁵ .

  In addition, by including a radiation polymerizable compound in the pressure-sensitive adhesive layer as described above, the adhesive strength can be reduced by irradiating the pressure-sensitive adhesive layer with radiation after the wafer is cut and separated. As such a radiation polymerizable compound, for example, a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule that can be three-dimensionally reticulated by light irradiation is widely used (for example, JP JP-A-60-196,956, JP-A-60-223,139, etc.).

  Specifically, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and the like are used.

  Furthermore, in addition to the acrylate compounds as described above, urethane acrylate oligomers can also be used as the radiation polymerizable compound. The urethane acrylate oligomer is obtained by reacting an acrylate or methacrylate having a hydroxyl group with a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound such as a polyester type or a polyether type with a polyvalent isocyanate compound. This urethane acrylate oligomer is a radiation polymerizable compound having at least one carbon-carbon double bond.

  Further, in the pressure-sensitive adhesive layer, in addition to the pressure-sensitive adhesive and the radiation-polymerizable compound as described above, a compound (such as a leuco dye) that is colored by radiation irradiation, a light-scattering inorganic compound powder, and abrasive grains, as necessary. (A particle size of about 0.5 to 100 μm), an isocyanate curing agent, a UV initiator, and the like can also be contained.

  The dicing film is usually obtained in a rolled state cut into a tape shape.

  In the dicing film of the present invention, adhesion to the acrylic pressure-sensitive adhesive is improved by adding an acrylic resin to the surface layer of the substrate film for dicing (the layer on which the pressure-sensitive adhesive layer is formed, that is, the A layer). Yes. Therefore, when the semiconductor chip is picked up, no adhesive remains on the chip side, and contamination of the semiconductor chip can be prevented.

  Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to these Examples.

In the examples and comparative examples, the following raw materials were used.
-Styrene-butadiene block copolymer hydrogenated product: MD6945 (styrene content 15% by weight) manufactured by Kraton Polymer Japan Co., Ltd.
・ Hydrogen 7311 made by Kuraray Co., Ltd.
-Ethylene-methacrylic acid copolymer: Nucleel N1207C manufactured by Mitsui DuPont Polychemical Co., Ltd.
・ Ethylene-methyl acrylate copolymer: Rotolyl 9MA, manufactured by Atofina Japan
-Hydrophilic PO resin-based antistatic agent: Pelestat 230 manufactured by Sanyo Chemical Co., Ltd.
Example 1 (single layer)
A styrene-butadiene block copolymer hydrogenated product (styrene content 15% by weight) 35% by weight and an ethylene-methacrylic acid copolymer 65% by weight were blended to obtain a raw material resin. The raw material resin was put into an extruder having a barrel temperature of 180 to 220 ° C., extruded from a T die at 230 ° C., cooled and solidified with a take-up roll having a set temperature of 40 ° C., and wound up in an unstretched state. The thickness of the obtained film was 150 μm.

Comparative Example 1 (single layer)
A raw material resin was prepared by blending 95% by weight of a hydrogenated styrene-butadiene block copolymer (styrene content: 15% by weight) and 5% by weight of an ethylene-methacrylic acid copolymer. The raw material resin was put into an extruder having a barrel temperature of 180 to 220 ° C., extruded from a T die at 230 ° C., cooled and solidified with a take-up roll having a set temperature of 40 ° C., and wound up in an unstretched state. The thickness of the obtained film was 150 μm.

Example 2 (Multilayer)
A layer A resin was prepared by blending 25% by weight of a hydrogenated styrene-butadiene block copolymer (styrene content: 15% by weight) and 75% by weight of an ethylene-methacrylic acid copolymer. 100% by weight of ethylene-methyl acrylate copolymer was used as the resin for the B layer. A layer resin and B layer resin are respectively put into an extruder having a barrel temperature of 180 to 220 ° C., extruded from a 230 ° C. multilayer T die, cooled and solidified by a take-up roll having a set temperature of 40 ° C., and unstretched. It wound up in the state. The thickness of the obtained multilayer film was A layer 120 μm, B layer 30 μm, and overall thickness 150 μm.

Example 3 (Multilayer)
Example 2 except that 75% by weight of a styrene-butadiene block copolymer hydrogenated product (styrene content 15% by weight) and 25% by weight of an ethylene-methacrylic acid copolymer were blended to obtain a resin for layer A. A multilayer film was obtained in the same manner.

Example 4 (Multilayer)
A layer A resin was prepared by blending 25% by weight of a hydrogenated styrene-butadiene block copolymer (styrene content: 15% by weight) and 75% by weight of an ethylene-methacrylic acid copolymer. A resin for layer B was prepared by blending 25 parts by weight of a hydrophilic PO resin-based antistatic agent with 100 parts by weight of an ethylene-methyl acrylate copolymer. A layer resin and B layer resin are respectively put into an extruder having a barrel temperature of 180 to 220 ° C, extruded from a 230 ° C multilayer T die, cooled and solidified by a take-up roll having a set temperature of 40 ° C, and unstretched. It wound up in the state. The thickness of the obtained multilayer film was A layer 120 μm, B layer 30 μm, and overall thickness 150 μm.

Example 5 (Multilayer)
A multilayer film was obtained in the same manner as in Example 4 except that a hydrogenated styrene-isoprene block copolymer was used instead of the hydrogenated styrene-butadiene block copolymer. The thickness of the obtained multilayer film was A layer 120 μm, B layer 30 μm, and overall thickness 150 μm.

Comparative Example 2 (Multilayer)
100 weight% of ethylene- (meth) acrylic acid copolymer was used as A layer resin. 100% by weight of ethylene-methyl acrylate copolymer was used as the resin for the B layer. A layer resin and B layer resin are respectively put into an extruder having a barrel temperature of 180 to 220 ° C., extruded from a 230 ° C. multilayer T die, cooled and solidified by a take-up roll having a set temperature of 40 ° C., and unstretched. It wound up in the state. The thickness of the obtained multilayer film was A layer 120 μm, B layer 30 μm, and overall thickness 150 μm.

Comparative Example 3 (Multilayer)
100% by weight of a hydrogenated styrene-butadiene block copolymer (styrene content 15% by weight) was used as the resin for the A layer. 100% by weight of ethylene-methyl acrylate copolymer was used as the resin for the B layer. A layer resin and B layer resin are respectively put into an extruder having a barrel temperature of 180 to 220 ° C., extruded from a 230 ° C. multilayer T die, cooled and solidified by a take-up roll having a set temperature of 40 ° C., and unstretched. It wound up in the state. The thickness of the obtained multilayer film was A layer 120 μm, B layer 30 μm, and overall thickness 150 μm.

Test Example 1 (Evaluation method for cutting waste)
A part of the multilayer film obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was cut into a circular shape having a diameter of 180 mm to obtain a measurement sample, and a grinding apparatus (AUTOMATIC DICING SAW DAD- manufactured by DISCO Corporation) was used. 2H / 6), cut into the base film under the following conditions, then remove the sample from the grinding machine and let it dry at room temperature in a clean booth for 24 hours, then digital microscope manufactured by Keyence Corporation (VHX) -100), the presence or absence of cutting waste was evaluated at a magnification of 150 times.

The surface of the sample was arbitrarily observed at 10 locations, and “◯” was given when there was no cutting waste, and “X” was given when it was recognized that there was even a small amount of cutting waste. The results are summarized in Table 1.
(Cutting conditions)
Rotation speed: 30000rpm
Speed: 80mm / sec
Cut mode: Full-auto dicing of 10mm □ Cut depth: 100μm
Blade: Disco B1A801 SDC 400N50M51 (outer diameter 56mm x thickness 0.2mm x inner diameter 40mm)
Water volume: 1.2L / min
Test Example 2 (Blocking resistance)
A part of the multilayer film obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was cut into a size of 30 × 100 mm to obtain a sample. As shown in FIG. 1, two samples are overlapped at the positions of both end portions of 40 mm, and a weight of 50 g / cm ² is placed on the overlapped area of 30 × 40 mm and pressed. This is left in a room at 40 ° C. for 24 hours. Next, the pressurized state is released, both ends are gripped, and pulled at a speed of 200 mm / min with a tensile tester (type AGS100A manufactured by Shimadzu Corporation). The intensity (kg / 30 mm) at the moment when the overlapped part is separated is measured. If it is 6 kg / 30 mm or less, it is judged as “◯” as blocking with no practical problem, and if it exceeds 6 kg / 30 mm, it is judged as “x” as problematic blocking. The results are summarized in Table 1.

It is a schematic diagram of the evaluation method of blocking resistance.

Claims (9)

Vinyl aromatic hydrocarbon - conjugated diene hydrocarbon copolymer hydrogenated product 90 to 30% by weight of ethylene - metaphosphorous dicing substrate film having an A layer containing an acrylic acid copolymer 10 to 70 wt%. 2. The substrate film for dicing according to claim 1, wherein the vinyl aromatic hydrocarbon unit content of the hydrogenated product of the vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is 5 to 20% by weight. A dicing substrate film consisting of A layer / B layer, A layer of vinyl aromatic hydrocarbon - conjugated diene hydrocarbon copolymer hydrogenated product 90 to 30% by weight of ethylene - metaphosphorous acrylic acid copolymer 10 The substrate film for dicing according to claim 1, wherein the B layer contains a thermoplastic resin having rubber elasticity. The substrate film for dicing according to claim 3, wherein the B layer further contains 10 to 45 parts by weight of an antistatic agent with respect to 100 parts by weight of the thermoplastic resin having rubber elasticity. 5. The dicing substrate film according to claim 1, 2, 3, or 4, wherein the total thickness of the dicing substrate film is 50 to 300 [mu] m. 5. The dicing substrate film according to claim 3, wherein the total thickness of the dicing substrate film is 50 to 300 μm, and the ratio of the thicknesses of the A layer and the B layer is 20/1 to 1/1. A dicing film further comprising an adhesive layer on the A layer of the substrate film for dicing according to any one of claims 1 to 6. A method of manufacturing a dicing substrate film consisting of a single layer, the vinyl aromatization Hydrogen - hydrogenated product of conjugated diene hydrocarbon copolymer 90 to 30 wt% ethylene - metaphosphorous acrylic acid copolymer 10-70wt %, A manufacturing method comprising extrusion-molding a resin comprising A method of manufacturing A layer / dicing substrate film consisting of B layer, the vinyl aromatic hydrocarbon - conjugated diene hydrocarbon copolymer hydrogenated product 90 to 30% by weight of ethylene - metaphosphorous acrylic acid copolymer 10 A production method comprising coextruding a resin for an A layer containing ˜70% by weight and a resin for a B layer containing a thermoplastic resin having rubber elasticity.

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