JP6554708B2 - Resin composition for dicing film substrate, dicing film substrate and dicing film - Google Patents

Description

  The present invention relates to a resin composition for a dicing film substrate, a dicing film substrate, and a dicing film.

  In the manufacturing process of a semiconductor device such as an IC, it is common to perform a dicing process for dividing the semiconductor wafer into chips after thinning the semiconductor wafer on which the circuit pattern is formed. In the dicing process, a stretchable wafer processing film (called a dicing film or dicing tape) is attached to the back surface of the semiconductor wafer, and the semiconductor wafer is divided into chips by a dicing blade while using cooling water and cleaning water. . In the next expansion step, the dicing tape corresponding to the cut wafer is expanded to make chips smaller. At this time, the semiconductor wafer is fixed with a dicing film to prevent chips from scattering.

  Since the dicing film may stick to a semiconductor wafer under heating conditions, heat resistance is required. If the heat resistance of the dicing film is low, it may be difficult to peel off due to softening due to heat, or may adhere to the work table (die). Furthermore, if the dicing film is deformed by warping or warping, the thinned semiconductor wafer may be deformed. For this reason, the dicing film is required to have heat resistance as well as expandability for fixing the semiconductor wafer as the dicing film.

  In the dicing process, a method of cutting the inside of the dicing film holding the wafer in order to completely cut the semiconductor wafer is the mainstream. Therefore, the balance between the splitting property and expandability of the dicing film is also important.

  As a material for forming a dicing film, an ionomer obtained by crosslinking an ethylene / (meth) acrylic acid copolymer with a metal ion is used. For example, radiation curing type wafer processing pressure-sensitive adhesive tape (Patent Document 1) made of a resin composition containing an ionomer and an antistatic resin containing a polyether component, and together with an ionomer, ethylene, (meth) acrylic acid, and (meta ) A resin composition for a dicing film base material containing a polymer containing an alkyl acrylate ester as a constituent (Patent Document 2) and the like.

  Further, as a resin composition containing an ionomer as described above, an ionomer / polyamide blend containing polyamide and a copolymer ionomer containing ethylene and an α, β-ethylenically unsaturated carboxylic acid (Patent Document 3). ) Is also known.

JP 2011-210887 A JP 2012-89732 A JP 2000-516984 A

  Although the wafer processing pressure-sensitive adhesive tape described in Citation 1, which combines an ionomer and an antistatic resin, is excellent in antistatic properties, there is no description regarding heat resistance. Moreover, about the resin composition for dicing film base materials of the patent document 2 which combined the ionomer and the polymer which uses ethylene, (meth) acrylic acid, and the (meth) acrylic-acid alkylester as a structural component, heat resistance is good. Although it is described as improved, the results of the heat resistance test in the examples are ○ (all the samples including the comparative example) are ○ (not fully extended), and a marked improvement in heat resistance is recognized over the conventional technology. I don't think it was done. Furthermore, the ionomer composition described in Patent Document 3 is for the production of molded parts and the like, and there is no description relating to applications related to semiconductors such as dicing films. Further, since this blend contains a large amount of polyamide of 40 to 60% by mass, it can be pelletized but cannot be formed into a film.

  The present invention has been made in view of the above-described problems of the prior art, and the object is to provide a dicing film substrate that is excellent in heat resistance and has a good balance between severability and expandability. It is another object of the present invention to provide a resin composition for a dicing film substrate that can be suitably used for forming a dicing film, and to provide a dicing film substrate and a dicing film having the above characteristics.

  That is, according to the present invention, the following resin composition for a dicing film substrate, a dicing film substrate, and a dicing film are provided.

[1] At least one resin (A) selected from the group consisting of an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer is 30 parts by mass or more and 95 parts by mass or less. ,
At least one resin (B) selected from the group consisting of polyamide and polyurethane and not less than 5 parts by weight and less than 40 parts by weight;
Antistatic agents other than the polyamide (C) 0 parts by mass or more and 30 parts by mass or less,
(However, the resin (A), the resin (B), and the antistatic agent (C) are 100 parts by mass in total) A resin composition for a dicing film substrate.
[2] The resin composition for a dicing film substrate according to [1], wherein the content of the antistatic agent (C) is 5 parts by mass or more and 30 parts by mass or less.
[3] The resin composition for a dicing film substrate according to [1] or [2], wherein the polyurethane is a thermoplastic polyurethane elastomer.
[4] A dicing film substrate including at least one layer formed of the resin composition for a dicing film substrate according to any one of [1] to [3].
[5] A dicing film substrate according to [4];
A dicing film having an adhesive layer laminated on at least one surface of the dicing film substrate.

  The present invention provides a resin composition for a dicing film substrate, which is a resin composition having excellent heat resistance, and exhibits a well-balanced severability and expandability suitable as a dicing film when a film is formed. provide.

Hereinafter, the dicing film substrate resin composition of the present invention will be described in detail, and the dicing film substrate and the dicing film will be described in detail.
In addition, in this specification, the notation of "-" showing a numerical range is the meaning containing the value of the lower limit and upper limit of a numerical range.
In addition, “(meth) acrylic acid” is a notation that includes both “acrylic acid” and “methacrylic acid”, and “(meth) acrylate” refers to both “acrylate” and “methacrylate”. It is a notation used inclusive.

1. Resin composition for dicing film base material The 1st aspect of this invention is the resin composition for dicing film base materials containing the following components.
30 parts by mass or more and 95 parts by mass or less of at least one resin (A) selected from the group consisting of an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer;
5 parts by mass or more and less than 40 parts by mass of at least one resin (B) selected from the group consisting of polyamide and polyurethane;
Antistatic agents other than the polyamide (C) 0 parts by mass or more and 30 parts by mass or less (provided that the total of the component (A), the component (B) and the component (C) is 100 parts by mass).

<Resin (A)>
The resin (A) in the present invention is composed of an ethylene / unsaturated carboxylic acid copolymer (hereinafter also simply referred to as “copolymer (A)”) and an ionomer (hereinafter referred to as an ethylene / unsaturated carboxylic acid copolymer). And at least one selected from the group consisting of “ionomer (A)”. In the present invention, the ionomer of the ethylene / unsaturated carboxylic acid copolymer used as the resin (A) is a part of or all of the carboxyl groups of the ethylene / unsaturated carboxylic acid copolymer. It has been neutralized. In the present invention, an ionomer in which at least a part of the acid groups of the ethylene / unsaturated carboxylic acid copolymer is neutralized with a metal (ion) is an acid of the ethylene / unsaturated carboxylic acid copolymer. A group in which the group is not neutralized by a metal (ion) is referred to as a “copolymer”.

  The ethylene / unsaturated carboxylic acid copolymer constituting the copolymer (A) or its ionomer (A) is at least a binary copolymer obtained by copolymerizing ethylene and an unsaturated carboxylic acid, Further, it may be a ternary or multi-component copolymer in which the third copolymer component is copolymerized. The ethylene / unsaturated carboxylic acid copolymer may be used alone or in combination of two or more ethylene / unsaturated carboxylic acid copolymers.

  Examples of the unsaturated carboxylic acid constituting the ethylene / unsaturated carboxylic acid binary copolymer include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic anhydride, and maleic anhydride. Examples thereof include unsaturated carboxylic acids having 4 to 8 carbon atoms such as acids. In particular, acrylic acid or methacrylic acid is preferable.

  When the ethylene / unsaturated carboxylic acid copolymer (A) is a ternary or higher multi-component copolymer, it may contain a monomer (third copolymer component) that forms the multi-component copolymer. As the third copolymer component, unsaturated carboxylic acid ester (for example, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate) (Meth) acrylic acid alkyl esters such as dimethyl maleate and diethyl maleate), unsaturated hydrocarbons (eg, propylene, butene, 1,3-butadiene, pentene, 1,3-pentadiene, 1-hexene, etc.), Vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), oxides such as vinyl sulfate and vinyl nitrate, halogen compounds (eg, vinyl chloride, vinyl fluoride, etc.), vinyl group-containing primary and secondary amine compounds, monoxide Carbon, sulfur dioxide, etc. are mentioned, and as these copolymerization components, Saturated carboxylic acid esters are preferred.

  For example, when the ethylene / unsaturated carboxylic acid copolymer (A) is a terpolymer, a terpolymer of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester, ethylene, Preferable examples include terpolymers of unsaturated carboxylic acids and unsaturated hydrocarbons.

  As unsaturated carboxylic acid ester, unsaturated carboxylic acid alkyl ester is preferable, As for carbon number of the alkyl part of alkyl ester, 1-12 are preferable, 1-8 are more preferable, and 1-4 are still more preferable. Examples of the alkyl moiety include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, 2-ethylhexyl, isooctyl and the like.

Specific examples of unsaturated carboxylic acid esters include unsaturated carboxylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl moiety (for example, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, acrylic acid). Alkyl acrylates such as isooctyl, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isobutyl methacrylate, and maleic acid alkyl esters such as dimethyl maleate and diethyl maleate).
Among unsaturated carboxylic acid alkyl esters, (meth) acrylic acid alkyl esters having 1 to 4 carbon atoms in the alkyl moiety are more preferred.

  The form of the copolymer may be any of a block copolymer, a random copolymer, and a graft copolymer, and may be any of a binary copolymer and a ternary copolymer. Among them, a binary random copolymer, a ternary random copolymer, a binary random copolymer graft copolymer, or a ternary random copolymer graft copolymer is preferable in terms of industrial availability. More preferably, it is a binary random copolymer or a ternary random copolymer.

  Specific examples of ethylene / unsaturated carboxylic acid copolymers include ethylene / acrylic acid copolymers, binary copolymers such as ethylene / methacrylic acid copolymers, and ethylene / methacrylic acid / isobutyl acrylate copolymers. And terpolymers such as Commercially available products that are marketed as ethylene / unsaturated carboxylic acid copolymers may also be used. For example, the Nuclel series (registered trademark) manufactured by Mitsui DuPont Polychemical Co., Ltd. may be used.

  The copolymerization ratio (mass ratio) of the unsaturated carboxylic acid ester in the ethylene / unsaturated carboxylic acid copolymer is preferably 1% by mass to 20% by mass, more preferably 5% by mass to 15% by mass. . The content ratio of the structural unit derived from the unsaturated carboxylic acid ester is 1% by mass or more, preferably 5% by mass or more from the viewpoint of expandability. In addition, the content ratio of the structural unit derived from the unsaturated carboxylic acid ester is preferably 20% by mass or less, and more preferably 15% by mass or less from the viewpoint of preventing blocking and fusion.

  The ionomer (A) used as the resin (A) in the present invention is preferably one in which the carboxyl group contained in the ethylene / unsaturated carboxylic acid copolymer is crosslinked (neutralized) with a metal ion at an arbitrary ratio. Examples of metal ions used for neutralizing acid groups include metal ions such as lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, zinc ions, magnesium ions, and manganese ions. Among these metal ions, magnesium ions, sodium ions and zinc ions are preferable, and sodium ions and zinc ions are more preferable because of the availability of industrialized products.

The degree of neutralization of the ethylene / unsaturated carboxylic acid copolymer in the ionomer (A) is preferably 10% to 85%, more preferably 15% to 82%. When the degree of neutralization is 10% or more, scratch resistance can be further improved, and when it is 85% or less, processability and moldability are excellent.
The degree of neutralization is the compounding ratio (mol%) of metal ions with respect to the number of moles of acid groups, particularly carboxyl groups, in the ethylene / unsaturated carboxylic acid copolymer.

The melt flow rate (MFR) of the ethylene / unsaturated carboxylic acid copolymer and its ionomer is preferably in the range of 0.2 g / 10 min to 20.0 g / 10 min, preferably 0.5 g / 10 min to 20.0 g. / 10 min is more preferable, and 0.5 g / 10 min to 18.0 g / 10 min is still more preferable. When the melt flow rate is within the above range, it is advantageous in molding.
In addition, MFR is a value measured by 190 degreeC and the load of 2160g by the method based on JISK7210-1999.

Content of resin (A) in the resin composition for dicing film base materials of this invention is 30 mass with respect to the total amount of resin (A), resin (B) mentioned later, and antistatic agent (C) mentioned later. Part by mass to 95 parts by mass, preferably 40 parts by mass to 90 parts by mass, and more preferably 50 parts by mass to 90 parts by mass.
When the content of the resin (A) is within the above range, the film processability is excellent.

<Resin (B)>
The resin (B) in the present invention is at least one selected from the group consisting of polyamide and polyurethane. In general, the melting point of the ethylene / unsaturated carboxylic acid copolymer and its ionomer used as the resin (A) is as low as 100 ° C. or less, and the heat resistance of the resin composition mixed with the resin having a high melting point is somewhat Rising is within the scope of the estimation. However, in the present invention, among resins having a relatively high melting point, polyamide and / or polyurethane are combined with an ethylene / unsaturated carboxylic acid copolymer or its ionomer (resin (A)) to obtain polyamide or polyurethane. It was found that a resin composition having higher heat resistance than expected from the melting point of the resin was obtained. Furthermore, it has been found that a film produced using such a resin composition has not only excellent heat resistance but also a well-balanced dividing property and expandability suitable as a dicing film.

  Examples of polyamides include carboxylic acids such as oxalic acid, adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine. Polycondensates with diamines such as decamethylenediamine, 1,4-cyclohexyldiamine and m-xylylenediamine, cyclic lactam ring-opening polymers such as ε-caprolactam and ω-laurolactam, 6-aminocaproic acid, 9- Examples thereof include polycondensates of aminocarboxylic acids such as aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, or the copolymerization of the above-mentioned cyclic lactam, dicarboxylic acid and diamine.

The polyamide may be commercially available. Specifically, nylon 4, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 11, nylon 12, copolymer nylon (for example, nylon 6/66, nylon 6/12, nylon 6/610, nylon 66/12, nylon 6/66/610, etc.), nylon MXD6, nylon 46, and the like.
Among these polyamides, nylon 6 and nylon 6/12 are preferable.

  As the polyurethane, a thermoplastic polyurethane elastomer is preferably used. Thermoplastic polyurethane elastomers include polyisocyanates (eg, aliphatic, alicyclic or aromatic diisocyanates), polymeric polyols (eg, polyether polyols, polycarbonate polyols, acrylic polyols) and chain extenders (eg, ethylene glycol). Diols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, bisphenol A, p-xylylene glycol) The thing obtained by superposition | polymerization is mentioned.

Content of resin (B) in the resin composition for dicing film base materials of this invention is 5 mass parts or more with respect to the total amount of resin (A), resin (B), and the antistatic agent (C) mentioned later. It is less than 40 parts by mass, preferably 5 parts by mass or more and 35 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less.
If the content of the resin (B) is less than 5 parts by mass, the effect of improving the heat resistance by the resin (B) is not exhibited, and if it is 40 parts by mass or more, film processing cannot be performed.

<Antistatic agent (C)>
It is preferable that the resin composition for dicing film base materials of this invention contains an antistatic agent (C) in addition to resin (A) and resin (B). The antistatic agent (C) not only imparts antistatic properties to the resin composition, but further improves the heat resistance of the resin composition by interaction with the resin (A) and the resin (B).

  Examples of the antistatic agent (C) include a high molecular weight antistatic agent and a low molecular weight antistatic agent such as a surfactant. Among these antistatic agents, polymer antistatic agents are preferred because surface contamination due to bleed-out is suppressed.

The polymer type antistatic agent is a conductive part (for example, a structural part derived from polyether, a quaternary ammonium base part or the like) and a non-conductive part (for example, a structural part derived from polyamide or a structure derived from polyolefin such as polyethylene). And a structural part derived from acrylate, a structural part derived from methacrylate, a structural part derived from styrene, and the like, and a molecular weight of 300 or more (preferably 1000 to 10,000). The molecular weight is a weight average molecular weight in terms of polystyrene measured by GPC.
In addition, electroconductivity means that the surface resistivity measured based on ASTM D257 is 10 ¹⁰ Ω / □ or less.

  Examples of the polymer type antistatic agent include nonionic polymer type antistatic agents such as polyethylene oxide, polypropylene oxide, polyethylene glycol, polyether ester amide, polyether ester, polyether polyolefin, and ethylene oxide / epichlorohydrin copolymer. Agents, anionic polymer type antistatic agents such as polystyrene sulfonic acid, cationic polymers such as quaternary ammonium salt-containing acrylate polymer, quaternary ammonium salt-containing styrene polymer, quaternary ammonium salt-containing polyethylene glycol methacrylate polymer Type antistatic agent and the like.

  More specifically, for example, a polyether ester amide described in JP-A-1-163234, a polyolefin block described in JP-A-2001-278985, and a hydrophilic polymer block include , A block copolymer having a structure in which the olefinic monomer is polymerized and a block copolymer having a structure in which the olefinic block obtained by polymerizing the olefinic monomer and the hydrophilic block obtained by polymerizing the hydrophilic monomer are alternately coupled. Coalescence is mentioned.

  Among these antistatic agents, polyether ester amide is preferable from the viewpoints of compatibility with the resin (A) and the resin (B), heat resistance, and antistatic properties. The polyether ester amide refers to a copolymer having a structural part derived from polyamide and a structural part derived from polyether, and these structural parts are ester-bonded.

Examples of polyamides that form structural sites derived from polyamides in polyether ester amides include dicarboxylic acids (eg, succinic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexane. Dicarboxylic acids) and diamines (eg, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, methylenebis (4-aminocyclohexane), m-xylylenediamine, p-xylylenediamine, etc.), ε- Caprolactam Ring-opening polymerization of lactams such as ω-dodecalactam, polycondensation of aminocarboxylic acids such as 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or the aforementioned lactam, dicarboxylic acid and diamine It can be obtained by copolymerization or the like. Such polyamide segments are nylon 4, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T, nylon 11, nylon 12, nylon 6/66, nylon 6/12, nylon 6/610, nylon 66/12, nylon 6/66/610, and nylon 11 and nylon 12 are particularly preferable. The molecular weight of the polyamide block is, for example, about 400 to 5000.
When polyamide is used as the resin (B), the antistatic agent (C) is a compound other than the polyamide used in (B).

  Examples of the polyether block include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyalkylene glycols such as polyoxyethylene / polyoxypropylene glycol, and mixtures thereof. These molecular weights are, for example, about 400 to 6000, and more preferably about 600 to 5000.

  As the polyether ester amide, the structural site derived from polyoxyalkylene glycol (preferably polyethylene glycol or polypropylene glycol) is 5% by mass to 80% by mass (more preferably 15% by mass) based on the total mass of the polyether ester amide. -70 mass%) is preferable. Furthermore, the polyether ester amide having a melting point of less than 190 ° C. has a melt flow rate (MFR) measured at 190 ° C. under a load of 2160 g of 0.1 to 1000 g / 10 minutes (more preferably 1 to 100 g / 10 minutes). Preferably, the polyether ester amide having a melting point of 190 ° C. or higher has a melt flow rate measured at 230 ° C. and a load of 2160 g of 0.1 to 1000 g / 10 minutes (more preferably 1 to 100 g / 10 minutes). ) Is preferred. The polyether ester amide preferably has a melting point (temperature indicating the maximum endotherm) measured by a suggestive scanning calorimeter (DSC) of 130 ° C. to 175 ° C. Such a polyether ester amide can be obtained by reacting a polyamide having a molecular weight of 600 to 5000, a polyoxyalkylene glycol and, if necessary, a carboxylic acid.

  Examples of the low molecular weight antistatic agent include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, phosphorus Anionic antistatic agent having an anionic group such as acid ester base, amino acid antistatic agent, amphoteric antistatic agent such as aminosulfate antistatic agent, amino alcohol antistatic agent, glycerin antistatic agent, polyethylene glycol antistatic agent Nonionic antistatic agents such as

  As the antistatic agent, a commercially available product may be used. Specific examples include Pelestat 230, Pelestat HC250, Pelestat 300, Pelestat 2450, Peletron PVL, and Irgastat P-16 manufactured by BASF Japan, manufactured by Sanyo Chemical Industries, Ltd. P-18FCA, P-20, P-22 and the like.

  The antistatic agent preferably has a melting point of 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, from the viewpoint of enhancing the effect of improving the heat resistance of the resin composition. In addition, the melting temperature measured with the suggestion scanning calorimeter (DSC) can be used for melting | fusing point based on JIS-K7121 (1987).

  The content of the antistatic agent (C) in the resin composition for a dicing film substrate of the present invention is 0 part by mass or more based on the total amount of the resin (A), the resin (B), and the antistatic agent (C). 30 parts by mass or less, preferably 5 parts by mass or more and less than 30 parts by mass, and more preferably 5 parts by mass or more and less than 25 parts by mass. When the content of the antistatic agent (C) is less than 5 parts by mass, the effect of improving the heat resistance by the antistatic agent is hardly exhibited, and when it exceeds 30% by mass, the extensibility of the film deteriorates.

<Other polymers and additives>
Other polymers and various additives may be added to the resin composition for a dicing film substrate of the present invention as necessary within a range not impairing the effects of the present invention. Examples of the other polymer include polyolefins such as polyethylene and polypropylene. Such other polymers can be blended in a proportion of, for example, 20 parts by mass or less with respect to 100 parts by mass in total of the (A), (B), and (C). Examples of the additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, dyes, lubricants, antiblocking agents, antistatic agents, antifungal agents, antibacterial agents, flame retardants, and flame retardant aids. Examples thereof include an agent, a crosslinking agent, a crosslinking aid, a foaming agent, a foaming aid, an inorganic filler, and a fiber reinforcing material. A small amount of the additive may be added from the viewpoint of preventing heat fusion. Specific examples of ultraviolet absorbers include benzophenone, benzoate, benzotriazole, cyanoacrylate, hindered amine, etc .; specific examples of fillers include silica, clay, calcium carbonate, barium sulfate, glass beads, talc, etc. Can be mentioned.

<Manufacturing method>
The resin composition for a dicing film substrate of the present invention is obtained by mixing the resin (A), the resin (B), and optionally an antistatic agent (C), and, if necessary, other polymers and additives. be able to. Although there is no limitation in particular in the manufacturing method of a resin composition, it can obtain by melt-kneading, after dry-blending all the components, for example.

  The resin composition for a dicing film substrate of the present invention preferably has a melt flow rate (MFR) measured at 230 ° C. under a load of 2160 g of 1 g / 10 minutes to 50 g / 10 minutes. In particular, when ethylene / (meth) acrylic acid copolymer or ionomer (A) is used as the resin (A), the MFR at 230 ° C. is preferably 20 g / 10 min or less. When the MFR at 230 ° C. is 20 g / 10 min or less, a film having an excellent balance between heat resistance at 140 ° C. and expandability can be obtained.

2. Dicing film base material The 2nd aspect of this invention is a dicing film base material which contains at least one layer which consists of a resin composition for dicing film base materials of this invention mentioned above.

  Since the dicing film base material of the present invention is obtained by molding the resin composition for a dicing film base material of the present invention, the dicing film base material is excellent in severability and expandability suitable as a dicing film.

  The structure of the dicing film substrate is not particularly limited, and may be a single layer structure or a multilayer structure having two or more layers. When the dicing film substrate has a multilayer structure, for example, a structure in which a plurality of sheets formed using the resin composition for a dicing film substrate of the present invention are laminated may be used, or the dicing film substrate of the present invention may be used. The structure which laminated | stacked the other resin layer on the sheet | seat shape | molded using the resin composition for water may be sufficient.

  Resins constituting the other resin layer laminated on the dicing film substrate of the present invention are linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-α olefin copolymer, polypropylene, ethylene Saturated carboxylic acid copolymer, ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid alkyl ester terpolymer, ethylene / unsaturated carboxylic acid alkyl ester copolymer, ethylene / vinyl ester copolymer, ethylene / unsaturated Representative examples include a carboxylic acid alkyl ester / carbon monoxide copolymer, or an unsaturated carboxylic acid grafted product thereof, or a single or arbitrary blended product.

  Examples of the layer structure include a dicing film substrate of the present invention / ethylene / unsaturated carboxylic acid copolymer or ionomer thereof, and a dicing film substrate / ethylene / unsaturated carboxylic acid copolymer of the present invention or ionomer / book thereof. The dicing film base material of invention, etc. are mentioned.

The other resin layer to be laminated may be a functional layer (for example, an adhesive sheet or the like), or a substrate such as a polyolefin film (or sheet) or a polyvinyl chloride film (or sheet). . The substrate may have either a single layer structure or a multilayer structure. In the present invention, these substrates are referred to as “dicing film substrates”.
In order to improve the adhesive force on the surface of the dicing film substrate, a known surface treatment such as a corona discharge treatment may be performed on the surface of the dicing film substrate.
Further, from the viewpoint of improving heat resistance, the resin for dicing film substrate or the dicing film substrate of the present invention may be irradiated with an electron beam as necessary.

  In order to obtain a dicing film substrate, the resin composition for a dicing film substrate of the present invention may be processed into a film by a known method. The processing method is not particularly limited. For example, the dicing film substrate of the present invention may be formed by various known molding methods such as a conventionally known T-die cast molding method, T-die nip molding method, inflation molding method, extrusion lamination method, and calendar molding method. Can be manufactured.

  In the case of a multilayer dicing film substrate, the other resin and the resin composition for a dicing film substrate of the present invention can be produced by, for example, a coextrusion laminating method.

  When laminating the resin composition for a dicing film substrate of the present invention on the surface of another resin layer by a T-die film molding machine, an extrusion coating molding machine or the like, in order to improve the adhesion to the other resin layer It may be formed through an adhesive resin layer by a coextrusion coating molding machine. As such an adhesive resin, a single substance or a blend of any plural kinds selected from the aforementioned various ethylene copolymers or an unsaturated carboxylic acid graft product thereof can be given as a representative example.

  Also, as a molding example of a multilayer dicing film substrate, a T-die film molding machine or an extrusion coating molding machine is used, and the resin composition for a dicing film substrate of the present invention is thermally bonded to the surface of another substrate. And a method of forming a multilayer body. At this time, a multilayer material in which another substrate and a layer made of the resin composition for a dicing film substrate of the present invention are laminated is obtained.

  The thickness of the sheet serving as the dicing film substrate is not particularly limited, but considering that it is used as a constituent member of the dicing film, it is preferably 65 μm or more from the viewpoint of holding the frame during dicing and 200 μm or less from the viewpoint of expandability. .

3. Dicing film The 3rd aspect of this invention is a dicing film provided with the dicing film base material of this invention mentioned above, and the adhesion layer laminated | stacked on the at least one surface.
When the dicing film substrate is a multilayer, it is preferable that the layer made of the resin composition for dicing film of the present invention is the outermost layer from the viewpoint of heat resistance, and further the adhesive layer is on the outermost layer. The formed structure is more preferable.
The dicing film of the present invention has the dicing film substrate of the present invention and further has an adhesive layer. The adhesive layer is disposed on the surface of the dicing film substrate. The semiconductor wafer can be diced by attaching a dicing film to the semiconductor wafer via the adhesive layer.

  As described above, since the resin composition for a dicing film substrate of the present invention has excellent heat resistance, the dicing film of the present invention also has excellent heat resistance. Therefore, if the dicing film of the present invention is used, a semiconductor wafer can be processed efficiently and with high accuracy.

(Adhesive layer)
The dicing film of the present invention comprises the dicing film base material of the present invention and an adhesive layer provided on one side of the dicing film base material, and a semiconductor wafer to be subjected to dicing processing is attached to the adhesive layer. Fixed. The thickness of the pressure-sensitive adhesive layer depends on the type of pressure-sensitive adhesive, but is preferably 3 to 100 μm, and more preferably 3 to 50 μm.

  A conventionally well-known adhesive can be used as an adhesive which comprises an adhesion layer. Examples of the pressure-sensitive adhesive include rubber-based, acrylic-based, silicone-based, and polyvinyl ether-based pressure-sensitive adhesives; radiation curable pressure-sensitive adhesives; Especially, when the peelability of the dicing film from the semiconductor wafer is taken into consideration, the adhesive layer preferably contains an ultraviolet curable adhesive.

  Examples of the acrylic pressure-sensitive adhesive that can constitute the pressure-sensitive adhesive layer include a homopolymer of (meth) acrylic acid ester and a copolymer of (meth) acrylic acid ester and a copolymerizable monomer. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as (meth) acrylic acid isononyl, (meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, ( Meth) acrylic acid glycidyl ester and the like.

  Specific examples of the copolymerizable monomer with (meth) acrylic acid ester include (meth) acrylic acid, itaconic acid, maleic anhydride, (meth) acrylic acid amide, (meth) acrylic acid N-hydroxymethylamide, ( Examples include meth) acrylic acid alkylaminoalkyl esters (for example, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, etc.), vinyl acetate, styrene, acrylonitrile and the like.

  Although the ultraviolet curable adhesive which can comprise an adhesion layer is not specifically limited, The said acrylic adhesive and ultraviolet curing component (component which can add a carbon-carbon double bond to the polymer side chain of an acrylic adhesive) And a photopolymerization initiator. Furthermore, you may add additives, such as a crosslinking agent, a tackifier, a filler, anti-aging agent, a coloring agent, etc. to an ultraviolet curable adhesive agent as needed.

  The ultraviolet curing component contained in the ultraviolet curing adhesive is, for example, a monomer, oligomer, or polymer that has a carbon-carbon double bond in the molecule and can be cured by radical polymerization. Specific examples of the UV effect component include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol Esters of (meth) acrylic acid and polyhydric alcohols such as di (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and oligomers thereof; 2-propenyl di-3-butenyl cyanurate, 2-hydroxyethylbis ( Examples include isocyanurates such as 2-acryloxyethyl) isocyanurate, tris (2-methacryloxyethyl) isocyanurate, and tris (2-methacryloxyethyl) isocyanurate.

  Specific examples of the photopolymerization initiator contained in the UV curable adhesive include benzoin alkyl ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, aromatic ketones such as α-hydroxycyclohexyl phenyl ketone, benzyl Aromatic ketals such as dimethyl ketal, thioxanthones such as polyvinylbenzophenone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, and diethylthioxanthone are included.

  Examples of the crosslinking agent contained in the ultraviolet curable adhesive include a polyisocyanate compound, a melamine resin, a urea resin, a polyamine, and a carboxyl group-containing polymer.

  It is preferable to affix a separator on the surface of the adhesive layer of the dicing film of the present invention. By sticking the separator, the surface of the adhesive layer can be kept smooth. In addition, the film for semiconductor production can be easily handled and transported, and label processing can be performed on the separator.

  The separator may be paper or a synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate, or the like. Moreover, in order to improve the peelability from an adhesion layer, the surface which touches the adhesion layer of a separator may be given mold release processes, such as a silicone process and a fluorine process, as needed. The thickness of a separator is 10-200 micrometers normally, Preferably it is about 25-100 micrometers.

(Manufacture of dicing film)
When the dicing film of the present invention is produced, the pressure-sensitive adhesive is a known method such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, etc. A method of directly applying to a base material, or a surface layer of a dicing film base material (a layer formed from the resin composition of the present invention) after applying an adhesive on the release sheet by the above-mentioned known method to provide an adhesive layer And the like, and a method of transferring the adhesive layer to the adhesive layer.
A dicing film can also be produced by coextrusion of a resin composition for a dicing film substrate and a material constituting the adhesive layer (coextrusion molding method).
Further, the pressure-sensitive adhesive composition layer may be subjected to heat crosslinking as necessary to form a pressure-sensitive adhesive layer.
Furthermore, you may affix a separator on the surface of an adhesion layer.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. Unless otherwise specified, “part” is based on mass.

1. Resin (A)
As resin (A), the following ethylene / unsaturated carboxylic acid copolymer (hereinafter referred to as “copolymer”) and ethylene / unsaturated carboxylic acid copolymer ionomer (hereinafter referred to as “ionomer”) Got ready. The melt flow rate (MFR) of the following resin is a value measured at 190 ° C. under a load of 2160 g in accordance with JIS K7210 (1999).
・ Ionomer 1 (IO1)
Ethylene content: 80% by weight, methacrylic acid content: 10% by weight, butyl acrylate content: 10% by weight, degree of neutralization: 70% zinc neutralization, MFR: 1 g / 10 minutes, ionomer 2 (IO2)
Ethylene content: 85% by mass, methacrylic acid content: 15% by mass, degree of neutralization: 59% zinc neutralization, MFR: 1 g / 10 min. Ionomer 3 (IO3)
Ethylene content: 85% by mass, methacrylic acid content: 15% by mass, degree of neutralization: 54% Na neutralization, MFR: 1 g / 10 min. Ionomer 4 (IO4)
Ethylene content: 88% by mass, methacrylic acid content: 12% by mass, degree of neutralization: 36% zinc neutralization, MFR: 2 g / 10 min. Copolymer (EMAA1)
Ethylene content: 91% by mass, methacrylic acid content: 9% by mass, MFR: 3 g / 10 min. Copolymer (EMAA2)
Ethylene content: 96% by mass, methacrylic acid content: 4% by mass, MFR: 7 g / 10 min. Copolymer (EMAA3)
Ethylene content: 91% by mass, methacrylic acid content: 9% by mass, MFR: 5 g / 10 min

2. Resin (B)
The following resins were prepared as the resin (B).
Polyamide 1 (PA1): Nylon 6 (Amilan CM1017 manufactured by Toray Industries, Inc.)
Polyamide 2 (PA2): Nylon 6-12 (UBE nylon 7024B manufactured by Ube Industries, Ltd.)
-Polyurethane (TPU): Thermoplastic polyurethane elastomer (Milactolan P485RSUI manufactured by Tosoh Corporation)
Polypropylene (PP): Prime Polypro (registered trademark) F219DA manufactured by Prime Polymer Co., Ltd.

3. Antistatic agent (C)
The following polyether ester amide was prepared as an antistatic agent (C). The MFR of the polyether ester amide is a value measured at 190 ° C. under a load of 2160 g in accordance with JIS K7210 (1999).
-Polyetheresteramide: Pelestat 230 manufactured by Sanyo Chemical Industries, Ltd.

Example 1
The resin (A) and resin (B) in the proportion (mass%) shown in Table 1 were dry blended. Next, a dry blended mixture was introduced into a resin inlet of a 30 mmφ twin screw extruder, and melt kneaded at a die temperature of 230 ° C. to obtain a resin composition 1 for a dicing film substrate.
About the obtained resin composition, MFR was measured by 230 degreeC and the 2160g load based on JISK7210 (1999), and was described in Table 1.

  The obtained resin composition 1 for dicing film base material was shape | molded on the conditions of the process temperature of 230 degreeC using the 40 mm diameter T die film molding machine, and produced 100-micrometer-thick T-die film. The obtained T-die film was used as a dicing film substrate and evaluated by the following method. The evaluation results are shown in Table 1.

(1) Heat resistance at 140 ° C. and 160 ° C. Each of the dicing film base materials was cut into an MD direction (Machine Direction) 10 cm × TD direction (Transverse Direction) 3 cm to obtain a film for evaluation. At the center of the evaluation film in the MD direction, a marked line having a length of 60 mm was written in the MD direction.
Each evaluation film was left at 140 ° C. or 160 ° C. under a load of 5 g for 2 minutes, and then the length of the marked line was measured. The length of the marked line after the heating test relative to the length of the marked line before the heating test. Was calculated.
Length of marked line after heating test [%] = (Length of marked line after heating test / 60 mm) × 100

A marked line length of 100 means that the film has not been changed by heating. If the marked line length exceeds 100, it means that the film has been stretched by heating. When the length is less than 100, it means that the film is shrunk by heating.
140 ° C. heat resistance or 160 ° C. heat resistance was evaluated according to the following criteria based on the length of the marked line after the heating test.
A: Mark length after heating test is 100.0
○: The length of the marked line after the heating test is 100.1 to 110.0, or 90.0 to 99.9
(Triangle | delta): The length of the marked line after a heating test is 110.1-115.0, or 86.0-89.9
X: The length of the marked line after the heating test is 115.1 or more, or 85.9 or less.

(2) Surface resistivity In accordance with JIS K6911, using Hiresta-UP manufactured by Mitsubishi Chemical Corporation, the applied voltage is 500 V and the measurement time is 30 seconds under an atmosphere of 23 ° C. and 50% relative humidity. It was measured.

(3) Expandability (expansion rate)
A square of 300 mm or more in the MD direction and 300 mm or more in the TD direction was cut out from the dicing film base material, and a 141 mm square was drawn using a square with a writing instrument such as an oil-based pen (hereinafter, measurement target). An object to be measured was set on a wafer expansion device for 8-inch wafers (a wafer expansion device TEX-218G GR-8 manufactured by Technovision). At this time, the center of the stage of the wafer expansion apparatus was set so that the center of the square drawn on the measurement object was aligned. Next, the stage was pulled up by 15 mm and the dicing film substrate was expanded, and then allowed to stand for 60 seconds, and the length (side length) of each side of the square drawn on the measurement object was measured. The elongation percentage (%) (= side length after extension / side length before extension × 100) was calculated for each of the two MD direction side lengths obtained, and the average value was defined as the extension rate [%].

(4) Tensile test (modulus)
The dicing film substrate was cut into a strip shape having a width of 10 mm to be a measurement target. Based on JIS K7127, 10% modulus, 25% modulus, and 50% modulus in each of the MD direction and TD direction of the measurement object were measured. The test speed was 500 mm / min.

(Examples 2-5, Comparative Examples 1-2)
A resin composition was prepared in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 1. Furthermore, T-die film was produced using the produced resin composition. The obtained T-die film was used as a dicing film substrate and evaluated by the above method. The evaluation results are shown in Table 1.

As is clear from the results shown in Table 1, the resin compositions of Examples 1 to 5 in which the resin (A) and the resin (B) are combined are compared with Comparative Example 1 in which the resin (A) is used alone. There was little change of the film after a 140 degreeC heat resistance test, and the more excellent heat resistance was shown. Such excellent heat resistance is obtained when either an ethylene / unsaturated carboxylic acid copolymer (EMAA) or an ethylene / unsaturated carboxylic acid copolymer ionomer (IO) is used as the resin (A). Was also recognized.
Further, when the content of the resin (B) was 40% by mass, the resin composition could not be processed into a film.

(Examples 6-20, Comparative Examples 3-5)
Similar to Example 1 except that the resin (A), the resin (B), and the antistatic agent (C) were used and the composition of the resin composition was changed to the ratio (mass%) shown in Table 2 or Table 3. A resin composition was prepared. Furthermore, T-die film was produced using the produced resin composition. The obtained T-die film was used as a dicing film substrate and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 2 and 3.

As is apparent from the results shown in Tables 2 and 3, the resin compositions of Examples 1 to 20 in which the resin (A), the resin (B), and the antistatic agent (C) are combined are the same as the resin (A) and the charge. Compared with the comparative example 3 which combined only the inhibitor (C), there was little change of the film after a 140 degreeC heat resistance test, and the outstanding heat resistance was shown. Such excellent heat resistance is obtained when either an ethylene / unsaturated carboxylic acid copolymer (EMAA) or an ethylene / unsaturated carboxylic acid copolymer ionomer (IO) is used as the resin (A). Was also recognized.
Moreover, when content of resin (B) became 40 mass% (comparative example 4), it became impossible to film-process a resin composition.

(Examples 21 and 22, Comparative Example 5)
Resin composition as in Example 1 except that resin (A), resin (B) and antistatic agent (C) were used and the composition of the resin composition was changed to the ratio (mass%) shown in Table 4. Was made. (The resin compositions of Examples 21 and 22 are the same as the resin compositions of Examples 6 and 16.) A T-die film was produced using the resin composition produced further. About the obtained T-die film, 160 degreeC heat resistance was tested. The 160 ° C. heat resistance test method and its evaluation criteria are substantially the same as the 140 ° C. heat resistance test except that the heating temperature is 160 ° C. The results are shown in Table 4.

As is clear from the results shown in Table 4, the film prepared with the resin composition of Comparative Example 6 using polypropylene instead of the resin (B) is composed of a resin (A), a resin (B), and an antistatic agent ( Unlike the films prepared with the resin compositions of Examples 21 and 22 containing C), the length of the film increased 2.5 times or more in the 160 ° C. heat resistance test.
From these results, heat resistance is improved by selecting polyamide or polyurethane, not simply selecting a resin having a melting point higher than that of the ethylene / unsaturated carboxylic acid copolymer or its ionomer.

  The resin composition for a dicing film substrate of the present invention is a resin composition that has excellent heat resistance and is effective for forming a film having an excellent balance between splitting properties and expandability. Therefore, by using the dicing film substrate and the dicing film using the resin composition for the dicing film substrate of the present invention, the dicing process and the subsequent expansion process at the time of manufacturing the semiconductor are smoothly performed, and there is no tape residue or deformation. Semiconductor manufacturing becomes possible.

Claims (8)

At least one resin (A) selected from the group consisting of an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer;
At least one resin (B) selected from the group consisting of polyamide and polyurethane and not less than 5 parts by weight and less than 40 parts by weight;
Antistatic agents other than the polyamide (C) 0 parts by mass or more and 30 parts by mass or less,
(However, the resin (A), the resin (B), and the antistatic agent (C) are 100 parts by mass in total) A resin composition for a dicing film substrate.   The resin composition for a dicing film substrate according to claim 1, wherein the content of the antistatic agent (C) is 5 parts by mass or more and 30 parts by mass or less.   The resin composition for a dicing film substrate according to claim 1 or 2, wherein the polyurethane is a thermoplastic polyurethane elastomer. The resin composition for a dicing film substrate according to claim 1 or 2, wherein the resin (B) is polyamide. The resin composition for dicing film base materials as described in any one of Claims 1-4 whose said resin (B) is 10 mass parts or more and less than 40 mass parts. The resin composition for a dicing film substrate according to any one of claims 1 to 5, wherein the resin (A) is an ionomer of the ethylene / unsaturated carboxylic acid copolymer. A dicing film substrate comprising at least one layer comprising the resin composition for a dicing film substrate according to any one of claims 1 to 6 . A dicing film substrate according to claim 7 ;
A dicing film comprising an adhesive layer laminated on at least one surface of the dicing film substrate.