JP5213462B2 - 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.
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 present invention has almost no generation of cutting waste (thread-like or whisker-like waste generated from the film after dicing) in the dicing process of the semiconductor wafer, and has excellent adhesion between the film surface layer and the acrylic adhesive. The purpose is to provide. Another object of the present invention is to provide a substrate film for dicing used for the dicing film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor is a substrate film for dicing laminated in the order of A layer / B layer / C layer, and vinyl aromatic hydrocarbons are formed on the A layer. -Hydrogenated product of conjugated diene hydrocarbon copolymer 60 to 10% by weight and ethylene- (meth) acrylic acid copolymer 40 to 90% by weight, and vinyl aromatic hydrocarbon-conjugated diene hydrocarbon in layer B A substrate film for dicing comprising 90-30% by weight of a hydrogenated copolymer and 10-70% by weight of an ethylene- (meth) acrylic acid copolymer, and comprising a thermoplastic resin having rubber elasticity in the C layer, It was found that all the above problems can be solved. 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 film for dicing laminated in the order of A layer / B layer / C layer, wherein the A layer is composed of 60 to 10% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene (Meth) acrylic acid copolymer 40 to 90% by weight, and B layer is a vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer hydrogenated 90 to 30% by weight and ethylene- (meth) acrylic acid. A substrate film for dicing comprising 10 to 70% by weight of a copolymer, wherein the C layer contains a thermoplastic resin having rubber elasticity.

  Item 2. The total thickness of the substrate film for dicing is 50 to 300 μm, the thickness of the A layer is 5 to 40%, and the thickness of the B layer is 20 to 90% with respect to the total thickness of the substrate film for dicing. Item 2. The substrate film for dicing according to Item 1, wherein

  Item 3. 3. A dicing film further comprising an adhesive layer on the A layer of the substrate film for dicing according to item 1 or 2.

  Item 4. A method for producing a substrate film for dicing which is laminated in the order of A layer / B layer / C layer, comprising 60 to 10% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene Resin for layer A containing (meth) acrylic acid copolymer 40 to 90 wt%, hydrogenated 90 to 30 wt% of vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and ethylene- (meth) acryl B layer resin containing 10 to 70% by weight of acid copolymer and C layer resin containing thermoplastic resin having rubber elasticity are coextruded in the order of A layer / B layer / C layer. Manufacturing method.

  Since the substrate film for dicing according to the present invention hardly generates cutting waste in the dicing process, there is no fear of wafer contamination or IC (integrated circuit) destruction. The dicing film in which the acrylic pressure-sensitive adhesive layer is provided on the substrate film for dicing according to the present invention is excellent in adhesiveness between the surface layer of the film and the acrylic pressure-sensitive adhesive.

I. Dicing Substrate Film The dicing substrate film of the present invention is a dicing substrate film that is laminated in the order of A layer / B layer / C layer, and the A layer is a vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer. The layer B contains a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer containing 60 to 10% by weight of the combined hydrogenated product and 40 to 90% by weight of the ethylene- (meth) acrylic acid copolymer. 90 to 30% by weight and 10 to 70% by weight of an ethylene- (meth) acrylic acid copolymer, and the C layer includes a thermoplastic resin having rubber elasticity.

  Hereinafter, each layer will be described.

A layer:
The A layer contains 60 to 10% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and 40 to 90% by weight of an ethylene- (meth) acrylic acid copolymer. If it is this composition, the cutting waste in the case of dicing can be suppressed.

  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 (eg, styrene) units in the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer is usually 5 to 40% by weight, preferably 5 to 15% by weight. Moreover, content of a conjugated diene hydrocarbon unit is 60 to 90 weight% normally, Preferably it is 85 to 95 weight%. The content of vinyl aromatic hydrocarbon (for example, styrene) 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). Can be measured.

  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.

  In layer A, a vinyl aromatic hydrocarbon-conjugated diene hydrocarbon in a resin composition comprising a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and an ethylene- (meth) acrylic acid copolymer. The content of the hydrogenated product of the copolymer is 60 to 10% by weight, preferably 50 to 20% by weight, more preferably 40 to 30% by weight, and the content of the ethylene- (meth) acrylic acid copolymer is It is 40 to 90% by weight, preferably 50 to 80% by weight, more preferably 60 to 70% by weight.

  By setting the A layer to the above composition, generation of cutting chips can be suppressed in the dicing process of the semiconductor wafer. Furthermore, when the content of the ethylene- (meth) acrylic acid copolymer (for example, EMA) is less than 40% by weight, the adhesiveness with the pressure-sensitive adhesive layer provided thereon tends to deteriorate. Moreover, when it exceeds 90 weight%, cutting waste will generate | occur | produce and it is not preferable. However, when the content is 40% by weight or more and 90% by weight or less, the adhesiveness between the surface of the layer A and the pressure-sensitive adhesive layer becomes excellent, and cutting waste can be suppressed.

B layer:
The layer B contains 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.

  Examples of the hydrogenated styrene-conjugated diene block copolymer and the ethylene- (meth) acrylic acid copolymer used in the B layer include those described in the A layer. The types of the hydrogenated styrene-conjugated diene block copolymer and / or ethylene- (meth) acrylic acid copolymer of the A layer and the B layer may be the same or different between the A layer and the B layer.

  In layer B, a vinyl aromatic hydrocarbon-conjugated diene hydrocarbon in a resin composition comprising a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and an ethylene- (meth) acrylic acid copolymer. The content of the hydrogenated product of the copolymer is 30 to 90% by weight, preferably 40 to 80% by weight, more preferably 50 to 80% by weight, and the content of the ethylene- (meth) acrylic acid copolymer is It is 10 to 70% by weight, preferably 20 to 60% by weight, and more preferably 20 to 50% by weight.

  Such a range is preferable because generation of resin-derived cutting waste (dicing waste) by the dicing blade in the B layer can be effectively suppressed.

C layer:
The thermoplastic resin having rubber elasticity used in the C 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 Copolymer (EMA), ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer (EMMA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl methacrylate copolymer And a mixture of these resins. Of these, EMA, EMAA or EMMA is preferable, and EMA is particularly preferable.

  The C layer may further contain an antistatic agent as necessary. As the antistatic agent used in the C layer, known surfactants such as anionic, cationic, and nonionic surfactants can be selected. In particular, from the viewpoint of durability and durability, polyether ester amide resin (hereinafter referred to as “PEEA”). Nonionic surfactants such as hydrophilic resin (hereinafter referred to as “hydrophilic PO resin”) and the like are preferable.

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 layer C contains an antistatic agent, the content of the antistatic agent is the sum of the hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and the ethylene- (meth) acrylic acid copolymer. It is 10-45 weight part with respect to 100 weight part, Preferably it is 20-30 weight part. Within such a range, the semi-conductivity is effectively imparted without impairing the slipperiness of the C 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 antiblocking agent or the like may be further added to the C layer as long as the effect of the present invention is 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 substrate film for dicing should be thicker than the cutting depth of the dicing blade and can be easily wound into a roll, for example, 50 to 300 μm, preferably It is 60-250 micrometers, More preferably, it is 70-200 micrometers.

  Further, the ratio of the thickness of the A layer to the total thickness of the substrate film for dicing is 5 to 40%, preferably 5 to 30%, and the ratio of the thickness of the B layer is 20 to 90%, preferably Is 40 to 90%, and the ratio of the thickness of the C layer is usually 5 to 40%, preferably 5 to 30%.

  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 layer A is 6 to 72 μm, preferably 6 to 54 μm. The thickness of the B layer is 24-162 μm, preferably 48-162 μm. The thickness of the C layer is 6 to 72 μm, preferably 6 to 54 μm.

The total thickness of the A layer and the B layer needs to be thicker than the depth of the deepest part of the dicing blade incision, so that the incision of the dicing blade does not reach the C layer. By providing the A layer and the B layer having such a thickness, cutting scraps as a base film are hardly generated.
II. Production Method of Dicing Substrate Film The three-layer dicing substrate film of the present invention is produced by multi-layer coextrusion molding of the resin for the A layer, the B layer and the C layer. Specifically, a resin for layer A containing 60 to 10% by weight of a hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and 40 to 90% by weight of an ethylene- (meth) acrylic acid copolymer B layer resin containing 90-30% by weight of hydrogenated vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer and 10-70% by weight of ethylene- (meth) acrylic acid copolymer, and rubber elasticity The resin for C layer containing the thermoplastic resin which has can be manufactured by coextrusion molding in order of A layer / B layer / C layer.

  The resins for the A layer, the B layer, and the C layer can be prepared by dry blending or melt-kneading a predetermined ratio of resin. In addition, you may add additives, such as an antistatic agent, to the resin which comprises C layer as needed.

  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 cooled while passing through a cooling roll at 50 to 70 ° C. It is taken out without stretching. 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 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 Co., Ltd.
-Hydrophilic PO resin-based antistatic agent: Pelestat 230 manufactured by Sanyo Chemical Co., Ltd.
Example 1
A layer A resin was prepared by blending 50% by weight of a hydrogenated styrene-butadiene block copolymer and 50% by weight of an ethylene-methacrylic acid copolymer. 80% by weight of a styrene-butadiene block copolymer hydrogenated product and 20% by weight of an ethylene-methacrylic acid copolymer were blended to obtain a resin for B layer. 100% by weight of ethylene-methyl acrylate copolymer was used as the resin for the C layer.

  A layer resin, B layer resin and C 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, and cooled and solidified by a take-up roll having a set temperature of 40 ° C. And wound up in an unstretched state. The thickness of the obtained multilayer film was A layer 20 μm, B layer 100 μm, C layer 30 μm, and overall thickness 150 μm.

Reference example 2
A multilayer film was obtained in the same manner as in Example 1 except that 20% by weight of a styrene-butadiene block copolymer hydrogenated product and 80% by weight of an ethylene-methacrylic acid copolymer were blended to obtain a resin for layer A. . The thickness of the obtained multilayer film was A layer 20 μm, B layer 100 μm, C layer 30 μm, and overall thickness 150 μm.

Example 3
A layer A resin was prepared by blending 40% by weight of hydrogenated styrene-butadiene block copolymer and 60% by weight of ethylene-methacrylic acid copolymer. A B layer resin was prepared by blending 40% by weight of a hydrogenated styrene-butadiene block copolymer and 60% by weight of an ethylene-methacrylic acid copolymer. 100% by weight of ethylene-methyl acrylate copolymer was used as the resin for the C layer.

  A layer resin, B layer resin and C 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, and cooled and solidified by a take-up roll having a set temperature of 40 ° C. And wound up in an unstretched state. The thickness of the obtained multilayer film was A layer 20 μm, B layer 100 μm, C layer 30 μm, and overall thickness 150 μm.

Example 4
A multilayer film was obtained in the same manner as in Example 1 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 20 μm, B layer 100 μm, C layer 30 μm, and overall thickness 150 μm.

Comparative Example 1
A multilayer film was obtained in the same manner as in Example 1 except that 100% by weight of ethylene-methacrylic acid copolymer was blended to obtain a resin for layer A. The thickness of the obtained multilayer film was A layer 20 μm, B layer 100 μm, C layer 30 μm, and overall thickness 150 μm.

Comparative Example 2
A layer A resin was prepared by blending 70% by weight of hydrogenated styrene-butadiene block copolymer and 30% by weight of ethylene-methacrylic acid copolymer. B layer resin was prepared by blending 60% by weight of a styrene-butadiene block copolymer hydrogenated product and 40% by weight of an ethylene-methacrylic acid copolymer. 100% by weight of ethylene-methyl acrylate copolymer was used as the resin for the C layer.

  A layer resin, B layer resin and C 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, and cooled and solidified by a take-up roll having a set temperature of 40 ° C. And wound up in an unstretched state. The thickness of the obtained multilayer film was A layer 20 μm, B layer 100 μm, C 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 4 and Comparative Examples 1 and 2 was cut into a circular shape with a diameter of 180 mm to obtain a measurement sample, and a grinding device (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 (Adhesiveness)
Acrylic adhesive was applied to a thickness of 10 μm on the surface of layer A of the multilayer films obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and a polyimide sheet having a thickness of 100 μm was pasted. A sample for measurement was cut into a circle. This sample was set in a grinding machine (AUTOMATIC DICING SAW DAD-2H / 6 manufactured by DISCO Corporation), and cut from the polyimide sheet side under the following conditions.
(Cutting conditions)
Rotation speed: 30000rpm
Speed: 80mm / sec
Cut mode: Full auto dicing of 3mm □ Cut depth: 150μm
Blade: Disco B1A801 SDC 400N50M51 (outer diameter 56mm x thickness 0.2mm x inner diameter 40mm)
Water volume: 1.2L / min
Next, the sample was removed from the grinding apparatus, and the polyimide sheets cut to 3 mm × 3 mm were peeled one by one, and it was visually confirmed whether or not the acrylic adhesive was attached to the 900 polyimide sheet side. Among the 900 pieces of polyimide sheets, those having an acrylic adhesive on the polyimide sheet side were designated as “◯” for 29 pieces or less, and “x” for 30 pieces or more. The results are summarized in Table 1.

  Good adhesiveness was obtained for the layer A containing an ethylene-methacrylic acid copolymer in the range of 40 to 90% by weight.

Claims (4)

A dicing substrate film obtained by laminating in this order A layer / B layer / C layer, the A layer is a vinyl aromatic hydrocarbon - conjugated diene hydrocarbon copolymer hydrogenated product 60 to 30% by weight of an ethylene - (Meth) acrylic acid copolymer 40 to 70 % by weight, and layer B is a vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer hydrogenated 90 to 30% by weight and ethylene- (meth) acrylic acid. A substrate film for dicing comprising 10 to 70% by weight of a copolymer, wherein the C layer contains a thermoplastic resin having rubber elasticity. The total thickness of the substrate film for dicing is 50 to 300 μm, the thickness of the A layer is 5 to 40%, and the thickness of the B layer is 20 to 90% with respect to the total thickness of the substrate film for dicing. The substrate film for dicing according to claim 1, wherein A dicing film further comprising an adhesive layer on the A layer of the substrate film for dicing according to claim 1 or 2. A manufacturing method of the A layer / B layer / C layer for dicing a substrate film obtained by laminating in this order, the vinyl aromatic hydrocarbon - conjugated diene hydrocarbon copolymer hydrogenated product 60 to 30% by weight of an ethylene - Resin for layer A containing (meth) acrylic acid copolymer 40 to 70 % by weight, hydrogenated product of vinyl aromatic hydrocarbon-conjugated diene hydrocarbon copolymer 90 to 30% by weight and ethylene- (meth) acrylic B layer resin containing 10 to 70% by weight of acid copolymer and C layer resin containing thermoplastic resin having rubber elasticity are coextruded in the order of A layer / B layer / C layer. Manufacturing method.