JP2008066496A - Substrate film for dicing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate film for dicing which is excellent in antistatic property, without generating dicing waste. <P>SOLUTION: The substrate film etc. for dicing includes: (i) 80-10 wt.% of styrene system elastomer resin and 20-90 wt.% of ternary copolymerization of (meta)acrylic acid alkyl ester system monomer, diene system monomer, and styrene system elastomer resin composition resin with styrene system monomer; (ii) a layer (A) composed of antistatic agent of 10-30 pts.wt. with regard to the 100 pts.wt. of the styrene system resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dicing film for fixing a semiconductor wafer or the like when dicing (cutting and separating) the semiconductor wafer or the like into chips.

  The semiconductor wafer is made in advance with a large area, then diced into chips (cut and separated), and transferred to the mounting 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 the semiconductor wafer and a resin layer (a substrate film for dicing) that receives the cutting of the dicing cutter. As the substrate film for dicing, a polyolefin film or a polyvinyl chloride film is generally used. However, the polyvinyl chloride film is in decline due to environmental problems.

  When dicing a semiconductor wafer, it is important to reduce the generation of chips (dicing waste) from the adhesive layer or the substrate film for dicing. In order to solve this, for example, 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, and Patent Document 2 describes In addition, it is described that an ethylene / methyl methacrylate copolymer film is used as a base film. However, although these substrate films can reduce dicing waste to some extent, further improvements are required.

  In addition, after the semiconductor wafer attached to the adhesive layer of the dicing film is diced into chips, the dicing film is uniformly expanded (expanded) in the vertical and horizontal directions in order to facilitate the pick-up process. A process of spreading the film uniformly is required. Therefore, a dicing film that can be expanded uniformly has been desired.

  For example, Patent Documents 3 and 4 report dicing films with improved uniform expandability. Patent Document 3 describes that a polyolefin film having a certain surface roughness and having an in-plane retardation before and after stretching in a predetermined range is used as a dicing tape for a semiconductor wafer. Specifically, a layer (A) containing crystalline polyethylene as a main component and a layer containing amorphous polyolefin containing 40% by weight or more of at least one component selected from the group consisting of ethylene, propylene and butene-1 (B ) Is a polyolefin film laminated with (A) / (B) / (A).

  In Patent Document 4, a terpolymer resin having elasticity obtained by copolymerizing ethylene, methacrylic acid, and (meth) acrylic acid alkyl ester (C3 to C8 alkyl group) is used as a substrate film for dicing. A dicing tape composed of two layers by providing an adhesive layer is described.

  However, the demand for uniform expandability is high, and Patent Documents 3 and 4 have room for further improvement. Further, even in the films of Patent Documents 3 and 4, the generation of dicing waste has been a problem.

  By the way, a dicing film is usually rolled, manufactured, stored and transported. For this reason, when the blocking between films occurs, the quality deteriorates. That is, even if it has excellent quality as a dicing film, it is difficult to provide a high-quality dicing film unless the problem due to blocking is solved.

  In addition, if static electricity is charged on the dicing film that fixes the semiconductor wafer, the semiconductor wafer itself is contaminated by adsorbing dust and cutting powder generated at the time of dicing. There is a problem that an IC (integrated circuit) formed on the wafer is destroyed by static electricity.

  As a means to solve this problem, a semiconductor wafer fixing sheet in which an antistatic agent layer containing a surfactant is formed between a base sheet and an adhesive layer or between a base sheet and an overcoat agent layer has been reported. (For example, Patent Document 5).

Further, in order to improve the water resistance of the antistatic agent layer, 100 parts by weight of a base polymer, light is applied between the base sheet and the pressure-sensitive adhesive layer and / or on the non-layered surface of the base-material sheet. The photocurable antistatic agent layer containing 10 to 200 parts by weight of the curable compound, 0.055 to 25 parts by weight of the antistatic agent and 0.1 to 10 parts by weight of the photoinitiator is 0.1 to 20 g / m ² . It has been reported that the photocurable antistatic agent layer is formed into a three-dimensional network structure by laminating at a lamination amount and photopolymerizing (for example, Patent Document 6).
Japanese Patent Laid-Open No. 5-21234 JP-A-5-156214 JP 2001-232683 A Japanese Patent Laid-Open No. 7-230972 Japanese Patent Laid-Open No. 9-190990 JP 2000-183140 A

  An object of the present invention is to provide a substrate film for dicing that has excellent antistatic properties and does not generate dicing waste (thread-like waste generated from the film after dicing).

  As a result of intensive studies to solve the above problems, the present inventors have found that 80 to 10% by weight of a styrene elastomer resin (hereinafter referred to as SE resin) and a (meth) acrylic acid alkyl ester monomer. A predetermined amount of an antistatic agent is added to a blend resin comprising 20 to 90% by weight of a terpolymer resin (hereinafter referred to as MBS ternary resin) of a diene monomer (particularly butadiene) and a styrene monomer. It has been found that when the film comprising it is used as a substrate film for dicing, it has excellent antistatic properties, does not generate thread-like dicing waste, has uniform expandability, and is excellent in blocking resistance. . Based on this knowledge, further studies have been made and the present invention has been completed.

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

  Item 1. (1) It comprises 80 to 10% by weight of a styrene elastomer resin and 20 to 90% by weight of a terpolymer resin of a (meth) acrylic acid alkyl ester monomer, a diene monomer and a styrene monomer. A substrate film for dicing comprising a styrene resin composition and (2) a layer (A) comprising 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the styrene resin composition.

Item 2. The layer (A);
(I) 100 to 80% by weight of styrene elastomer resin and 0 to 20% by weight of terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer A layer (B) comprising a styrene resin composition and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the styrene resin composition;
Item 2. The substrate film for dicing according to Item 1, wherein the layers are laminated in the order of (A) / (B) / (A).

Item 3. The layer (A);
A layer (C) comprising (i) a polyethylene resin and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the polyethylene resin;
Item 8. The substrate film for dicing according to Item 1, wherein the substrate film is laminated by (A) / (C).

Item 4. The layer (A);
(I) 100 to 80% by weight of styrene elastomer resin and 0 to 20% by weight of terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer A layer (B) comprising a styrene-based resin composition, and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the styrene-based resin composition;
A layer (C) comprising (i) a polyethylene resin and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the polyethylene resin;
Item 2. The substrate film for dicing according to Item 1, wherein the films are laminated in the order of (A) / (B) / (C).

  Item 5. The substrate film for dicing according to any one of claims 1 to 4, wherein the antistatic agent is a polyether ester amide resin and / or a hydrophilic polyolefin resin.

  Item 6. The styrene elastomer resin is a hydrogenated resin of a random copolymer resin of a styrene monomer and a diene monomer, and / or a block copolymer resin of a styrene monomer and a diene monomer. Item 6. The substrate film for dicing according to any one of Items 1 to 5, which is a hydrogenated resin.

  Item 7. The polyethylene resin constituting the polyethylene resin layer (C) is an ethylene homopolymer, a copolymer of ethylene and an olefin monomer having 3 to 8 carbon atoms, or ethylene and an alkyl (meth) acrylate ester. Item 5. The substrate film for dicing according to Item 3 or 4, which is a copolymer with a monomer.

  Item 8. The pressure-sensitive adhesive layer (D) is provided on the layer (A) of the substrate film for dicing according to any one of Items 1 to 7, and the release layer (E) is further provided on the pressure-sensitive adhesive layer (D). Dicing film.

  The substrate film for dicing according to the present invention has excellent antistatic properties and does not generate dicing waste. Therefore, highly accurate dicing is possible, and even a smaller semiconductor wafer or the like can be picked up easily and reliably.

Hereinafter, the present invention will be described in detail.
I. Dicing Substrate Film The dicing substrate film of the present invention comprises (i) 80 to 10% by weight of a styrene elastomer resin, a (meth) acrylic acid alkyl ester monomer, a diene monomer (particularly butadiene), and styrene. A blend resin (styrene-based resin composition) composed of 20 to 90% by weight of a terpolymer resin with a monomer, and (ii) 10 to 30 parts by weight with respect to 100 parts by weight of the styrene-based resin composition A film comprising a layer (A) comprising an antistatic agent. That is, the substrate film for dicing of the present invention is a single layer film or two or more layers film containing a predetermined amount of an antistatic agent in the styrene resin composition.

The (meth) acrylic acid alkyl ester monomer means a methacrylic acid alkyl ester monomer or an acrylic acid alkyl ester monomer.
(1) Single layer film: (A)
As an embodiment of the substrate film for dicing of the present invention, there is a single layer film (A) comprising 80 to 10% by weight of SE resin and 20 to 90% by weight of MBS ternary resin and an antistatic agent.

SE resin The SE resin used in the present invention mainly has a function of imparting the expandability (elasticity) necessary for the substrate film for dicing. The SE resin is a copolymer composed of a styrene monomer and a diene monomer, or a hydrogenated product thereof. The SE resin is a soft thermoplastic resin (thermoplastic elastomer) having elasticity, and can be film-formed by itself.

  Examples of the styrene monomer constituting the SE resin include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N , N-diethyl-p-aminoethylstyrene, and the like. These may be used alone or in combination of two or more. Styrene is particularly preferred.

  The diene monomer constituting the SE resin 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, with 1,3-butadiene and isoprene being particularly common Is mentioned. These may be used alone or in combination of two or more. In particular, butadiene is preferred.

  The content of the styrene monomer unit in the SE resin is usually 8 to 75% by weight, preferably 10 to 70% by weight, and the content of the diene monomer unit is usually 25 to 92% by weight. It is preferably 20 to 90% by weight. 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 SE resin has a hardness (JIS K6253 durometer type A) of about 40 to 90, preferably about 50 to 80. Its specific gravity (ASTM D297) is about 0.85 to 1.0, MFR (ASTM D1238: 230 ° C., 21.2 N) is about 3 to 6 g / 10 min, and glass transition temperature (Tg) is differential scanning. The value measured by the calorimetric method (DSC method) is about -50 to 30 ° C, preferably about -40 to 20 ° C.

  The SE resin has a weight average molecular weight (Mw) of, 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).

  The SE resin used in the present invention may be a copolymer comprising a styrene monomer and a diene monomer, but since a double bond derived from a diene monomer remains, it is known. It is good to saturate by hydrogenation (for example, nickel catalyst etc.) by the method. This is because it becomes a more stable resin excellent in heat resistance, chemical resistance, durability and the like. The hydrogenation rate of the SE resin is 85% or more, preferably 90% or more, more preferably 95% or more of the double bond based on the conjugated diene compound in the copolymer. This hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).

  Examples of the SE resin used in the present invention include a hydrogenated random copolymer composed of a styrene monomer and a diene monomer (hereinafter also referred to as “hydrogenated random copolymer”), a styrene monomer And a hydrogenated product of a block copolymer composed of a monomer and a diene monomer (hereinafter also referred to as “hydrogenated block copolymer”), or a blend thereof.

Specific examples of the hydrogenated random copolymer include a styrene monomer unit represented by the formula: —CH (C ₆ H ₅ ) CH ₂ — and a formula: —CH ₂ CH ₂ CH ₂ CH ₂ —. And a hydrogenated random copolymer in which an ethylene unit and a butylene unit represented by the formula: —CH (C ₂ H ₅ ) CH ₂ — are randomly bonded.

  In the hydrogenated random copolymer, the content of the styrene monomer unit is about 60 to 75% by weight, preferably about 65 to 70% by weight. The glass transition temperature (Tg) is about 0 to 30 ° C, preferably about 10 to 20 ° C. The weight average molecular weight is about 100,000 to 500,000, preferably about 150,000 to 300,000.

  A hydrogenated random copolymer having such characteristics can be produced, for example, by the method described in JP-A No. 2004-59741 or in accordance therewith.

  On the other hand, as a hydrogenated block copolymer, one having a block segment derived from a styrene monomer at one end or both ends of the copolymer and further having a block segment derived from a diene monomer, or these Blended ones are listed.

The hydrogenated block copolymer has, for example, a block segment derived from a styrenic monomer represented by the formula: —CH (C ₆ H ₅ ) CH ₂ — at one end of the copolymer, The block segment includes an ethylene unit represented by the formula: —CH ₂ CH ₂ CH ₂ CH ₂ — and / or a butylene unit represented by the formula: —CH (C ₂ H ₅ ) CH ₂ —. And a hydrogenated block copolymer having a segment containing an ethylene unit represented by the formula: —CH ₂ CH ₂ CH ₂ CH ₂ — at the other end of the copolymer.

  In the hydrogenated block copolymer, the content of the styrenic monomer unit is about 8 to 50% by weight, preferably about 10 to 40% by weight. The glass transition temperature (Tg) is about −50 to 0 ° C., preferably about −40 to −10 ° C. The weight average molecular weight is about 100,000 to 500,000, preferably about 150,000 to 300,000. SEBC is exemplified as a specific example of the hydrogenated block copolymer having the above-described characteristics.

Alternatively, as a hydrogenated block copolymer, for example, at both ends of the copolymer, it has a block segment derived from a styrenic monomer represented by the formula: —CH (C ₆ H ₅ ) CH ₂ —, In the middle, a block segment containing an ethylene unit represented by the formula: —CH ₂ CH ₂ CH ₂ CH ₂ — and / or a butylene unit represented by the formula: —CH (C ₂ H ₅ ) CH ₂ — Examples thereof include a hydrogenated block copolymer.

  In the hydrogenated block copolymer, the content of the styrenic monomer unit is about 8 to 50% by weight, preferably about 10 to 40% by weight. The glass transition temperature (Tg) is about −50 to 0 ° C., preferably about −40 to −10 ° C. The weight average molecular weight is about 100,000 to 500,000, preferably about 150,000 to 300,000. SEBS is exemplified as a specific example of the hydrogenated block copolymer having the above characteristics.

  Among SE resins, a hydrogenated random copolymer is not as elastic as a hydrogenated block copolymer, but has an advantage that dicing with a dicer is easy to cut. On the other hand, the degree of blocking between films tends to be stronger in hydrogenated random copolymers than in hydrogenated block copolymers. Therefore, in order to have both the ease of cutting and the blocking resistance, a blended SE resin comprising a hydrogenated random copolymer as a main component and blended with a hydrogenated block copolymer is suitable. Can be used for

  The weight ratio of the hydrogenated random copolymer to the hydrogenated block copolymer in the blended SE resin is, for example, about 55 to 80% by weight for the hydrogenated random copolymer and 45 to 20% by weight for the hydrogenated block copolymer. % Is preferred.

MBS ternary resin The MBS ternary resin used in the present invention suppresses blocking of the film, suppresses dicing waste (filamentous waste), and plays a role of imparting appropriate waist hardness to the film.

  The MBS ternary resin is a copolymer of a (meth) acrylic acid alkyl ester monomer, a diene monomer (particularly butadiene), and a styrene monomer as described above. Specifically, the MBS ternary resin comprises (meth) acrylic acid alkyl ester (MAA) monomer units of 30 to 62% by weight, diene monomer units of 3 to 35% by weight, and styrene monomers. It is a copolymer composed of 35 to 67% by weight of units. Here, the alkyl of the alkyl ester of the MAA monomer unit is generally an alkyl having 1 to 5 carbon atoms (particularly methyl, ethyl, etc.), and the hardness tends to decrease as the carbon number increases. Specific examples of the MAA monomer unit include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and the like. In addition, what was described as a raw material of said SE resin can be used for a diene monomer and a styrene monomer.

  The MBS ternary resin is a hard resin, and its hardness (JIS K6253 durometer type D) is about 20 to 50, preferably 30 to 40. Its specific gravity (ASTM D297) is about 1.09 to 1.11, MFR (ASTM D1238: 230 ° C., 21.2 N) is about 2.0 to 6.0 g / 10 min, and glass transition temperature (Tg) Is a value measured by a differential scanning calorimetry (DSC method) of about 80 to 95 ° C, preferably about 85 to 90 ° C. The weight average molecular weight (Mw) of the MBS ternary resin is about 100,000 to 400,000, preferably about 100,000 to 200,000. The measurement is based on the GPC method.

A substrate film for dicing according to the present invention includes a resin (styrene-based resin composition) in which the soft SE resin and the hard MBS ternary resin are blended at a predetermined ratio, and the blend ratio is SE. The resin is 80 to 10% by weight, preferably 70 to 45% by weight, and the MBS ternary resin is 20 to 90% by weight, preferably 30 to 55% by weight. Thereby, dicing waste does not generate | occur | produce, it has a uniform and moderate expansibility, and the outstanding effect of being excellent in the blocking resistance of films is exhibited. When the SE resin exceeds 80% by weight and the MBS ternary resin is less than 20% by weight, the effect of inhibiting blocking is particularly lowered, and the appropriate waist hardness tends to be lowered. On the other hand, when the SE resin is less than 10% by weight and the MBS ternary resin is more than 90% by weight, it is difficult to uniformly expand the film and the hardness of the waist tends to be hard.

Antistatic Agent The dicing substrate film of the present invention contains an antistatic agent. The content of the antistatic agent is 10 to 30 parts by weight, preferably about 15 to 25% by weight, based on 100 parts by weight of the blend resin (styrene resin composition).

  As the antistatic agent, known surfactants such as anionic, cationic, and nonionic surfactants can be selected. In particular, polyether ester amide resin (hereinafter referred to as PEEA resin) from the viewpoint of durability and durability. Nonionic surfactants such as hydrophilic polyolefin resins (hereinafter referred to as hydrophilic PO resins) are suitable.

  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.

Content of antistatic agents, such as PEEA resin or hydrophilic PO resin, is 10-30 weight part with respect to 100 weight part of said styrenic resin compositions, Preferably it is 15-25 weight part. Within such a range, semi-conductivity is effectively imparted without impairing the properties of the film of the present invention, so that the generated static electricity can be quickly eliminated. For example, the film of the present invention containing an antistatic agent in the above-described range has a surface resistivity of about 10 ⁷ to 10 ¹² Ω / □.

  The layer thickness of the single-layer dicing substrate film (A) of the present invention may be at least thicker than the cut depth of the dicer and can be easily wound in a roll shape. It may be about 200 μm, preferably about 80 to 250 μm.

  Next, the manufacturing method of the substrate film for single-layer dicing according to the present invention will be described. 80 to 10% by weight of SE resin and 20 to 90% by weight of MBS ternary resin are dry blended or melt-kneaded and uniformly mixed and dispersed to obtain a styrenic resin composition. 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of this styrenic resin composition, and the resulting mixture is supplied to a screw-type extruder, and a film is formed from a single-layer T die at 200 to 225 ° C. And is cooled while passing through a cooling roll at 50 to 70 ° C. and taken up substantially unstretched.

Here, the reason why the film is substantially unstretched 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.
(2) Three-layer film: (A) / (B) / (A)
As another embodiment of the substrate film for dicing of the present invention, the layer (A), (i) 100 to 80% by weight of a styrene elastomer resin, and a (meth) acrylic acid alkyl ester monomer and a diene monomer A styrene resin composition comprising 0 to 20% by weight of a terpolymer resin of styrene and a styrene monomer, and (ii) 10 to 30 parts by weight of an antistatic agent per 100 parts by weight of the styrene resin composition Examples include a substrate film for dicing comprising at least three layers including a layer (B) composed of an agent and laminated in the order of (A) / (B) / (A).

  First, the resin composition and antistatic agent constituting the layer (A) are the same as described above.

  The layer (B) corresponding to the intermediate layer contains SE resin in an amount of 80% by weight or more, preferably 85% by weight or more, and contains MBS ternary resin in an amount of 20% by weight or less, preferably 15% by weight or less. Further, the antistatic agent is contained in an amount of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 100 parts by weight of the styrene resin composition. In addition, about SE resin, MBS ternary resin, and antistatic agent in a layer (B), the same thing as the single layer film (A) of said (1) can be used.

  The layer (B) imparts expandability (elasticity) to the substrate film for dicing, but the co-extrusion molding described later is not performed smoothly due to the softness of the SE resin itself, or the thickness of the intermediate layer When the thickness is increased, the hardness of the entire film waist may become softer. Blending the MBS ternary resin up to 20% by weight solves these problems.

  The substrate film for dicing according to the present invention has the layer (B) containing SE resin as a main component between two layers (A) having high blocking resistance. And generation of dicing waste can be further suppressed.

  The layer thickness of the substrate film for dicing comprising the three layers (A) / (B) / (A) of the present invention is 80 to 300 μm, preferably 80 to 250 μm, for the same reason as in the case of the single layer. Among them, the thickness of each layer (A) is 4 to 135 μm, preferably 8 to 115 μm, and the layer (B) is 30 to 290 μm, preferably 65 to 240 μm.

  Next, a method for producing a three-layer dicing substrate film of the present invention will be described. In this case, a three-layer coextrusion molding method is preferably employed.

  Specifically, 80 to 10% by weight of SE resin and 20 to 90% by weight of MBS ternary resin are dry blended or melt-kneaded and uniformly mixed and dispersed to obtain a styrenic resin composition. 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the styrene resin composition to obtain a resin mixture for the layer (A).

  Further, 100 to 80% by weight of SE resin and 0 to 20% by weight of MBS ternary resin are dry blended or melt-kneaded and uniformly mixed and dispersed to obtain a styrenic resin composition. 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the styrene resin composition to obtain a resin mixture for the layer (B).

Next, using three screen type extruders, the resin for the layer (A) is supplied to two units, and the resin for the layer (A) is supplied to one unit at 200 to 225 ° C. (A ) / (B) / (A) are co-extruded from a three-layer T-die in the form of a film, cooled while passing through a cooling roll at 50 to 70 ° C., and taken substantially unstretched. Substantially non-stretching is synonymous with the above (1).
(3) Two-layer film: (A) / (C)
As another embodiment of the substrate film for dicing of the present invention, the layer (A), (i) a polyethylene resin, and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the polyethylene resin. And a substrate film for dicing comprising at least two layers laminated with (A) / (C).

  First, the resin composition and antistatic agent constituting the layer (A) are the same as described above.

  The polyethylene-based resin constituting the polyethylene-based resin layer (C) may be a polymer having a polyethylene unit as a main component, for example, an ethylene homopolymer (ethylene homopolymer), ethylene and an olefin having 3 to 8 carbon atoms. A copolymer with a monomer or a copolymer of ethylene and a (meth) acrylic acid alkyl ester monomer is preferred. The copolymer preferably contains a polyethylene unit of 80% by weight or more, preferably 90% by weight or more.

  Among polyethylene resins, copolymers are preferred, but copolymers of ethylene and (meth) acrylic acid alkyl ester monomers are more preferred. This is because the interlayer adhesion with the layer (A) is excellent. Specifically, ethylene-methyl acrylate copolymer (EMA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer ( EEA) and the like are exemplified. Of these, EMA is particularly preferable.

  The MFR (ASTM D1238: 230 ° C., 21.2 N) of the polyethylene resin is about 0.5 to 10.0 g / 10 min, and the glass transition temperature (Tg) was measured by a differential scanning calorimetry method (DSC method). The value is about -130 to 0 ° C, preferably about -120 to -10 ° C.

  The weight average molecular weight (Mw) of the polyethylene resin is about 100,000 to 300,000, preferably about 150,000 to 200,000. The measurement is based on the GPC method.

  The layer (B) contains 10 to 30 parts by weight, preferably 15 to 25 parts by weight of the antistatic agent with respect to 100 parts by weight of the polyethylene resin. In addition, about the antistatic agent in a layer (B), the same thing as the single-layer film (A) of said (1) can be used.

  The layer thickness of the substrate film for dicing comprising the two layers (A) / (C) of the present invention is determined taking into consideration that it is at least thicker than the cutting depth of the dicer and is easily wound in a roll shape. Can do. In particular, when the dicer reaches the film C layer, it leads to generation of dicing debris. Therefore, in order to suppress this, it is preferable to make the thickness of the layer (A) larger than the cutting depth of the dicer. The total thickness of the substrate film for dicing is usually about 80 to 300 μm, preferably about 80 to 250 μm. Among them, the thickness of the layer (A) may be about 40 to 97% of the total thickness, and the thickness of the layer (C) may be about 3 to 60% of the total thickness. Specifically, the layer (A) Is about 30 to 295 m, preferably about 40 to 240 μm, and the thickness of the layer (C) is about 5 to 180 μm, preferably about 10 to 80 μm.

  Since the substrate film for dicing consisting of two layers of the present invention is formed by laminating a polyethylene-based resin layer (C) having high blocking resistance, the substrate film for single-layer dicing described in (1) above and (2 The blocking resistance is remarkably improved as compared with the substrate film for three-layer dicing described in (1). Accordingly, whether the film is rolled in a tightened state, or rolled in a larger diameter, or the storage location becomes hot, the problem of blocking which is a problem is completely eliminated.

  Next, a method for producing a two-layer dicing substrate film of the present invention will be described. In this case, a two-layer coextrusion method is preferably employed.

  Specifically, 80 to 10% by weight of SE resin and 20 to 90% by weight of MBS ternary resin are dry blended or melt-kneaded and uniformly mixed and dispersed to obtain a styrenic resin composition. 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the styrene resin composition to obtain a resin mixture for the layer (A).

  Further, the polyethylene resin is dry blended or melt-kneaded, and 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the polyethylene resin to obtain a resin mixture for the layer (C).

Next, each resin mixture is supplied to two screen-type extruders, and co-extruded in a film form from a two-layer T die at 200 to 225 ° C., and this is put into a cooling roll at 50 to 70 ° C. Cool while passing and take up substantially unstretched. Substantially non-stretching is synonymous with the above (1).
(4) Three-layer film: (A) / (B) / (C)
As another embodiment of the substrate film for dicing according to the present invention, the layer (A), the layer (B) and the layer (C) are laminated in the order of (A) / (B) / (C). A substrate film for dicing consisting of at least three layers can be mentioned.

  The resin composition and antistatic agent constituting the layer (A), the layer (B) and the layer (C) are the same as described above.

  The layer thickness of the substrate film for dicing comprising the three layers (A) / (B) / (C) of the present invention is considered to be at least thicker than the cutting depth of the dicer and is easily wound in a roll shape. Can be decided. In particular, when the dicer reaches the film C layer, it leads to generation of dicing debris. Therefore, in order to suppress this, the total thickness of the layer (A) and the layer (B) is made thicker than the cutting depth of the dicer. Is preferred. The total thickness of the substrate film for dicing is usually 70 to 300 μm, preferably 80 to 250 μm.

  In this case, the total thickness of the layer (A) and the layer (B) is preferably set to about 40 to 97% of the total thickness, and the layer (C) is set to about 3 to 60% of the total thickness. For example, the total thickness of the layer (A) and the layer (B) is about 30 to 295 μm, preferably about 40 to 240 μm, and the thickness of the layer (C) is set to 5 to 180 μm, preferably 10 to 150 μm. Is good.

  Since the substrate film for dicing consisting of three layers of the present invention is formed by laminating a polyethylene resin layer (C) having high blocking resistance, the substrate film for single-layer dicing described in (1) above and (2 The blocking resistance is remarkably improved as compared with the substrate film for three-layer dicing described in (1). Accordingly, whether the film is rolled in a tightened state, or rolled in a larger diameter, or the storage location becomes hot, the problem of blocking which is a problem is completely eliminated.

  Next, a method for producing a three-layer dicing substrate film of the present invention will be described. In this case, a three-layer coextrusion molding method is preferably employed.

  Specifically, 80 to 10% by weight of SE resin and 20 to 90% by weight of MBS ternary resin are dry blended or melt-kneaded and uniformly mixed and dispersed to obtain a styrenic resin composition. 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the styrene resin composition to obtain a resin mixture for the layer (A).

  Further, 100 to 80% by weight of SE resin and 0 to 20% by weight of MBS ternary resin are dry blended or melt-kneaded and uniformly mixed and dispersed to obtain a styrenic resin composition. 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the styrene resin composition to obtain a resin mixture for the layer (B).

  Further, the polyethylene resin is dry blended or melt-kneaded, and 10 to 30 parts by weight of an antistatic agent is added to 100 parts by weight of the polyethylene resin to obtain a resin mixture for the layer (C).

Next, using three screw-type extruders, one unit is the layer (A) resin, the other unit is the layer (B) resin, and the other unit is the layer ( C) resin is supplied and coextruded in the form of a film from a three-layer T die in the order of (A) / (B) / (C) at 200 to 225 ° C., and this is cooled at 50 to 70 ° C. -Cool while passing through the rod and take up substantially unstretched. Substantially non-stretching is synonymous with the above (1).
II. Dicing film The substrate film for dicing obtained as described above has a pressure-sensitive adhesive layer (D) formed by coating a known pressure-sensitive adhesive on the layer (A), and a release layer on the pressure-sensitive adhesive layer (D). (E) is formed, and the dicing film of the present invention is manufactured. This film is usually obtained in a rolled state cut into a tape shape.

  As the pressure-sensitive adhesive component used in the pressure-sensitive adhesive layer (D), known ones can be used. For example, the pressure-sensitive adhesive component described in Patent Document 1 (Japanese Patent Laid-Open No. 5-21234) can be used. A known release layer (E) is also used.

  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.

Evaluation of dicing waste and semiconductivity of the substrate films for dicing obtained in the examples and comparative examples was performed as follows.
<Dicing waste>
Each sample was diced under the following conditions. Of the grinding scraps generated in the grinding line 100 mm, the number of filamentous scraps having a size exceeding 100 μm is counted. If there is grinding scraps of a size exceeding 100 μm, it is rejected and the number is counted as “x”. If the grinding scrap is 100 μm or less, it will be accepted and marked “◯”.

Type 27HEDG made by Blade Disco Co., Ltd.
Blade ・ 40000rpm
Cutting speed: 100mm / sec Cut size: 5mm square Cut depth: 50μm
<Semiconductive>
First, a voltage of 10 kv is applied to the sample using Honest Meter 2H0110 manufactured by Sicid Electrostatic Co., Ltd. The sample is charged and becomes saturated. When the saturation voltage state is reached, leave for 30 seconds. The saturation voltage (kv) that decays during the 30 seconds is measured, and if the time for which the measured voltage is halved (half-life) is 5 seconds or less, it indicates that it has excellent semiconductivity. If it exceeds 5 seconds, it will be rejected and marked as “x”.
(Example 1)
SE resin (hydrogenated resin of styrene / butadiene random elastomer) (manufactured by Asahi Kasei Chemicals Corporation, product type SS9000, hardness JIS K6253 durometer type A: 80, Tg: 20 ° C., weight average molecular weight: 180,000) , MBS ternary resin (MMA / styrene / butadiene) (manufactured by Denki Kagaku Kogyo Co., Ltd., variety TH-23T, hardness JIS K6253 durometer type D: 34, Tg: 83 ° C., weight average molecular weight: 130,000) 30% by weight Dry blended. To 100 parts by weight of this blend resin, 16 parts by weight of a polyether ester amide resin (variety Perestat NC6321 melting point 203 ° C. manufactured by Sanyo Chemical Co., Ltd.) is added, and this is supplied to a screw type extruder having a barrel temperature of 180 to 220 ° C. Then, it was extruded from a single layer T die at 220 ° C., cooled and solidified while passing through a 60 ° C. cooling roll, and wound up in an unstretched state.

The thickness of the obtained film was 150 μm.
(Example 2)
40% by weight of the same SE resin as in Example 1 and another SE resin (hydrogenated resin of styrene block at one end, ethylene block at the other end and intermediate butadiene block) (manufactured by JSR Corporation, varieties Dynalon 4630P, hardness JIS K6253 durometer type A: 78, Tg: −45 ° C., weight average molecular weight: 150,000) 15% by weight was dry blended to 45% by weight of the same MBS ternary resin as in Example 1. To 100 parts by weight of this blend resin, 16 parts by weight of a polyether ester amide resin (variety Perestat NC6321 melting point 203 ° C. manufactured by Sanyo Chemical Co., Ltd.) is added, and this is supplied to a screw type extruder having a barrel temperature of 180 to 220 ° C. Then, it was extruded from a single layer T die at 220 ° C., cooled and solidified while passing through a 60 ° C. cooling roll, and wound up in an unstretched state.

The thickness of the obtained film A was 150 μm.
(Example 3)
16 weight of polyetheresteramide resin (manufactured by Sanyo Kasei Co., Ltd., Perestat NC6321 melting point 203 ° C.) with respect to 100 weight parts of resin obtained by dry blending 50 weight% of SE resin and 50 weight% of MBS ternary resin as in Example 1. The resin added in part was used as the resin for the layer (A).

  Further, a resin obtained by adding 16 parts by weight of a polyetheresteramide resin (manufactured by Sanyo Chemical Co., Ltd., Pelestat NC6321 melting point 203 ° C.) to 100 parts by weight of the SE resin as in Example 1 was used as a resin for the layer (B). .

  Three-layer coextrusion molding was performed using each of the above resins. That is, the resin for layer (A) is supplied to two screw extruders, and the resin for layer (B) is supplied to one screw extruder, respectively, from a three-layer T die (A) / (B) / (A) was coextruded, cooled and taken off without stretching. At this time, the barrel temperature, T-die temperature, and cooling roll temperature of the extruder were the same as those in Example 1.

The total thickness of the obtained three-layer dicing substrate film was 150 μm, each outer layer (A) was 15 μm, and the middle layer (B) was 120 μm.
Example 4
16 weight of polyetheresteramide resin (variety Perestat NC6321 melting point 203 ° C., manufactured by Sanyo Chemical Co., Ltd.) with respect to 100 weight parts of resin obtained by dry blending 52 weight% of SE resin and 48 weight% of MBS ternary resin as in Example 1. The resin added in part was used as the resin for the layer (A).

  Further, it is hydrophilic with respect to 100 parts by weight of polyethylene resin having a bond of about 9.5% by weight of methylmethacrylate (manufactured by Atofina Japan Co., Ltd., variety Rotril 9MA02, melting point 99 ° C., weight average molecular weight: 150,000). Resin to which 16 parts by weight of a functional PP resin (variety Perestat 300, melting point 135 ° C., manufactured by Sanyo Chemical Co., Ltd.) was added was used as the resin for the layer (C).

  Using the above two types of resins, co-extrusion was performed with two screw extruders. One of them supplies the resin for the layer (A) to the screw type extruder having a barrel temperature of 180 to 220 ° C., and the other one supplies the resin for the layer (C) to the screw type extruder of the same temperature, This was coextruded from a two-layer T die at 220 ° C., cooled and solidified while passing through a 60 ° C. cooling roll, and wound up in an unstretched state.

The thickness of the obtained base film for two-layer dicing was 150 μm, and the layer (A) was 140 μm.
(Example 5)
16 weights of polyetheresteramide resin (manufactured by Sanyo Chemical Co., Ltd., Pereztat NC6321, melting point 203 ° C.) with respect to 100 parts by weight of a resin obtained by dry blending 70% by weight of SE resin and 30% by weight of MBS ternary resin as in Example 1. The resin added in part was used as the resin for the layer (A).

  The resin for layer (B) was obtained by adding 16 parts by weight of a polyetheresteramide resin (product type Perestat NC6321 melting point 203 ° C., manufactured by Sanyo Chemical Co., Ltd.) to 100 parts by weight of the same SE resin as in Example 1.

  A polyethylene resin to which the same hydrophilic PP resin as in Example 4 was added was used as a resin for the layer (C).

  Three-layer coextrusion molding was performed using the above three types of resins. That is, the resin for each layer is supplied to three screw-type extruders, co-extruded from a three-layer T die so as to be (A) / (B) / (C), cooled and taken out without stretching. It was. At this time, the barrel temperature of each extruder was 180 to 220 ° C., the three-layer T die temperature was 220 ° C., and the cooling roll temperature was 60 ° C.

The total thickness of the obtained three-layer dicing substrate film was 150 μm, the layer (A) was 60 μm, the layer (B) was 80 μm, and the layer (C) was 10 μm.
(Comparative Example 1)
SE resin (hydrogenated resin of styrene / butadiene random elastomer) (manufactured by Asahi Kasei Chemicals Corporation, product type SS9000, hardness JIS K6253 durometer type A: 80, Tg: 20 ° C., weight average molecular weight: 180,000) , MBS ternary resin (MMA / styrene / butadiene) (manufactured by Denki Kagaku Kogyo Co., Ltd., variety TH-23T, hardness JIS K6253 durometer type D: 34, Tg: 83 ° C., weight average molecular weight: 130,000) 30% by weight Dry blended resin, supplied to a screw type extruder with a barrel temperature of 180-220 ° C, extruded from a single layer T die at 220 ° C, cooled and solidified through a 60 ° C cooling roll, and unstretched I wound up with.

The thickness of the obtained substrate film for dicing was 150 μm, and there was no difference from Example 1 in appearance.
(Comparative Example 2)
SE resin (hydrogenated resin of styrene / butadiene random elastomer) (manufactured by Asahi Kasei Chemicals Corporation, product type SS9000, hardness JIS K6253 durometer type A: 80, Tg: 20 ° C., weight average molecular weight: 180,000) , MBS ternary resin (MMA / styrene / butadiene) (manufactured by Denki Kagaku Kogyo Co., Ltd., variety TH-23T, hardness JIS K6253 durometer type D: 34, Tg: 83 ° C., weight average molecular weight: 130,000) 30% by weight 5 parts by weight of a polyether ester amide resin (variety Perestat NC6321 melting point 203 ° C., manufactured by Sanyo Chemical Co., Ltd.) is added to 100 parts by weight of the dry blended resin, and this is supplied to a screw type extruder having a barrel temperature of 180 to 220 ° Then, extrude from a single layer T die at 220 ° C and cool while passing through a 60 ° C cooling roll. It was solidified and wound up in an unstretched state.

The thickness of the obtained substrate film for dicing was 150 μm, and there was no difference from Example 1 in appearance.
(Comparative Example 3)
SE resin (hydrogenated resin of styrene / butadiene random elastomer) (manufactured by Asahi Kasei Chemicals Corporation, product type SS9000, hardness JIS K6253 durometer type A: 80, Tg: 20 ° C., weight average molecular weight: 180,000) , MBS ternary resin (MMA / styrene / butadiene) (manufactured by Denki Kagaku Kogyo Co., Ltd., variety TH-23T, hardness JIS K6253 durometer type D: 34, Tg: 83 ° C., weight average molecular weight: 130,000) 30% by weight Forty parts by weight of the dry blended resin, 40 parts by weight of hydrophilic PP resin (manufactured by Sanyo Chemical Co., Ltd., Pelestat 300 melting point 135 ° C.) is added and supplied to a screw type extruder having a barrel temperature of 180 to 220 ° C. Extruded from a single layer T die at 220 ° C, cooled and solidified through a 60 ° C cooling roll, unstretched Winded up in a state.

  The thickness of the obtained substrate film for dicing was not stable, and a resin flow pattern was generated in appearance and a good film could not be obtained.

  A part of the film obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was cut to obtain a measurement sample, and the semiconductivity, dicing waste and film-forming properties were measured and summarized in Table 1.

  As described above, in Examples 1 to 5, good results were obtained in any of the semiconductivity, the dicing waste, and the film forming property.

Claims (8)

  (I) 80 to 10% by weight of a styrene elastomer resin and 20 to 90% by weight of a terpolymer of a (meth) acrylic acid alkyl ester monomer, a diene monomer, and a styrene monomer. A substrate film for dicing comprising a styrenic resin composition and (ii) a layer (A) comprising 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the styrenic resin composition. The layer (A);
(I) 100 to 80% by weight of styrene elastomer resin and 0 to 20% by weight of terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer A layer (B) comprising a styrene resin composition and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the styrene resin composition;
The substrate film for dicing according to claim 1, wherein the substrate film is laminated in the order of (A) / (B) / (A). The layer (A);
A layer (C) comprising (i) a polyethylene resin and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the polyethylene resin;
The substrate film for dicing according to claim 1, wherein the substrate film is laminated with (A) / (C). The layer (A);
(I) 100 to 80% by weight of styrene elastomer resin and 0 to 20% by weight of terpolymer resin of (meth) acrylic acid alkyl ester monomer, diene monomer and styrene monomer A layer (B) comprising a styrene-based resin composition, and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the styrene-based resin composition;
A layer (C) comprising (i) a polyethylene resin and (ii) 10 to 30 parts by weight of an antistatic agent with respect to 100 parts by weight of the polyethylene resin;
The substrate film for dicing according to claim 1, wherein the substrate film is laminated in the order of (A) / (B) / (C).   The substrate film for dicing according to any one of claims 1 to 4, wherein the antistatic agent is a polyether ester amide resin and / or a hydrophilic polyolefin resin.   The styrene elastomer resin is a hydrogenated resin of a random copolymer resin of a styrene monomer and a diene monomer, and / or a block copolymer resin of a styrene monomer and a diene monomer. The substrate film for dicing according to claim 1, which is a hydrogenated resin.   The polyethylene resin constituting the polyethylene resin layer (C) is an ethylene homopolymer, a copolymer of ethylene and an olefin monomer having 3 to 8 carbon atoms, or ethylene and an alkyl (meth) acrylate ester. 5. The substrate film for dicing according to claim 3, which is a copolymer with a monomer.   It has an adhesive layer (D) on the layer (A) of the substrate film for dicing according to any one of claims 1 to 7, and further has a release layer (E) on the adhesive layer (D). Having dicing film.