KR102293749B1 - Dicing film substrate and dicing film - Google Patents

Abstract

Disclosed is a dicing film substrate having excellent heat resistance and excellent balance between chip breakability and expandability. 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 ethylene/unsaturated carboxylic acid-based copolymers and ionomers of the ethylene/unsaturated carboxylic acid-based copolymers, polyamide and polyurethane; 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, and 0 parts by mass or more and 30 parts by mass or less of an antistatic agent (C) other than the polyamide (provided that the resin (A), A first resin layer comprising a resin composition containing a resin (B) and an antistatic agent (C) in a total of 100 parts by mass), an ethylene/unsaturated carboxylic acid copolymer, and the ethylene/unsaturated carboxylic acid copolymer A dicing film substrate comprising a second resin layer comprising at least one resin (D) selected from the group consisting of ionomers.

Description

Dicing film substrate and dicing film

The present invention relates to a dicing film substrate and a dicing film.

In the manufacturing process of semiconductor devices, such as an IC, after thinning the semiconductor wafer in which the circuit pattern was formed, it is common to perform the dicing process for dividing a semiconductor wafer into chip unit. In the dicing process, a flexible wafer processing film (referred to as a dicing film or a dicing tape) is adhered to the back surface of a semiconductor wafer, and a semiconductor wafer is used with a dicing blade while using cooling water and washing water. is divided into chips. And in the next expansion process, the chip|tip is made small by expanding the dicing tape corresponding to the cut|disconnected wafer. At this time, the semiconductor wafer is fixed with a dicing film, and the scattering of a chip is prevented.

Since a dicing film may stick to a semiconductor wafer under heating conditions, heat resistance is calculated|required. When the heat resistance of a dicing film is low, it may become difficult to peel by softening by heat, etc., or it may stick on a work table (die). Moreover, when distortion, such as distortion or warping, etc. generate|occur|produces in a dicing film by heat, the thinned semiconductor wafer may deform|transform. For this reason, about the dicing film, heat resistance is calculated|required together with the expandability for fixing a semiconductor wafer as a dicing film.

Moreover, in the stealth dicing process, in order to form a cracking layer inside a semiconductor wafer by a laser, and to perform complete cutting of a semiconductor wafer, a semiconductor wafer is cut with the stress of the dicing film which holds the wafer. it is required to Therefore, in the dicing film, it is important to balance the chip breakability and expandability.

As a material for forming the dicing film, an ionomer obtained by crosslinking an ethylene/(meth)acrylic acid copolymer with a metal ion is used. For example, an ionomer and an adhesive tape for processing a radiation-curable wafer comprising a resin composition containing an antistatic resin containing a polyether component (Patent Document 1), along with the ionomer, ethylene, (meth)acrylic acid, and The resin composition for dicing film base materials containing the polymer which has (meth)acrylic-acid alkylester as a structural component (patent document 2) etc. are mentioned.

In addition, as a resin composition containing an ionomer as described above, an ionomer/polyamide formulation comprising a polyamide and an ionomer of a copolymer containing ethylene and α,β-ethylenically unsaturated carboxylic acid (patent Document 3) is also known.

Japanese Patent Laid-Open No. 2011-210887 Japanese Patent Laid-Open No. 2012-89732 Japanese Patent Publication No. 2000-516984

Although the adhesive tape for wafer processing described in patent document 1 which combined an ionomer and antistatic resin is excellent in antistatic property, there is no description regarding heat resistance. In addition, with respect to the resin composition for a dicing film base material of Patent Document 2 in which an ionomer and a polymer comprising ethylene, (meth)acrylic acid, and (meth)acrylic acid alkyl ester are combined as constituent components, it is described that heat resistance is improved. As for the result of the heat resistance test in , Example, all the samples including the comparative example were ○ (not elongated), and it is not considered that the remarkable improvement in heat resistance was recognized compared with the prior art. In addition, about the ionomer compound described in patent document 3, it is for manufacture of molded parts etc., and there is no description regarding the use related to semiconductors, such as a dicing film. In addition, since this formulation contains polyamide in a large amount at 40-60 mass %, pelletization is possible, but film-forming is impossible.

The present invention has been made in view of the problems of the prior art, and its object is to provide a dicing film base material and a dicing film that are excellent in heat resistance and have a balanced chip breakability and expandability. have.

That is, according to this invention, the dicing film base material and dicing film shown below are provided.

[1] 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;

0 parts by mass or more and 30 parts by mass or less of an antistatic agent (C) other than the polyamide (however, the total of component (A), component (B), and component (C) is referred to as 100 parts by mass)

A first resin layer made of a resin composition containing

A dicing film comprising a second resin layer comprising at least one resin (D) selected from the group consisting of an ethylene-unsaturated carboxylic acid-based copolymer and an ionomer of the ethylene-unsaturated carboxylic acid-based copolymer. write.

[2] The dicing film substrate according to [1], wherein the content of the antistatic agent (C) is 0 parts by mass.

[3] The 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.

[4] The dicing film substrate according to any one of [1] to [3], wherein the polyurethane is a thermoplastic polyurethane elastomer.

[5] The dicing film substrate according to any one of [1] to [4];

It has an adhesive layer laminated|stacked on at least one surface of the said dicing film base material, The dicing film characterized by the above-mentioned.

The present invention provides a dicing film substrate and a dicing film having excellent heat resistance and exhibiting a well-balanced chip breaking property and expandability suitable as a dicing film.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one Embodiment of the dicing film base material of this invention.
It is sectional drawing which shows one Embodiment of the dicing film of this invention.

Hereinafter, while the dicing film base material of this invention is demonstrated in detail, the dicing film is also demonstrated in detail.

In addition, in this specification, the description of "to" which shows a numerical range is meaning including the value of the lower limit and upper limit of a numerical range.

In addition, "(meth)acrylic acid" is a notation used including both "acrylic acid" and "methacrylic acid", and "(meth)acrylate" is both "acrylate" and "methacrylate" It is a notation used including .

1. Dicing film substrate

A first aspect of the present invention is a dicing film substrate. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one Embodiment of the dicing film base material of this invention. As shown in FIG. 1, the dicing film base material 10 of this embodiment has the structure in which the 1st resin layer 1 and the 2nd resin layer 2 were laminated|stacked. Next, each layer is demonstrated.

1-1. first resin layer

The first resin layer is 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. and 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, and 0 parts by mass or more and 30 parts by mass of an antistatic agent (C) other than the polyamide It is a layer which consists of the resin composition containing the following (however, the sum total of a component (A), a component (B), and a component (C) is called 100 mass parts). Such a resin composition layer is excellent in heat resistance, and is excellent in the balance of chip breakability and expandability.

<Resin (A)>

The resin (A) in the present invention is an ethylene/unsaturated carboxylic acid copolymer (hereinafter simply referred to as “copolymer (A)”) and an ionomer of the ethylene/unsaturated carboxylic acid copolymer (hereinafter simply referred to as “copolymer (A)”). It is at least 1 sort(s) selected from the group which consists of "ionomer (A)"). In the present invention, the ionomer of the ethylene/unsaturated carboxylic acid copolymer used as the resin (A) is one in which a part or all of the carboxyl groups of the ethylene/unsaturated carboxylic acid copolymer are neutralized with a metal (ion). In the present invention, an "ionomer" in which at least a part of the acid groups of the ethylene/unsaturated carboxylic acid-based copolymer are neutralized with a metal (ion), and the acid group of the ethylene/unsaturated carboxylic acid-based copolymer are neutralized with a metal (ion) What is not formed is called a "copolymer".

The ethylene/unsaturated carboxylic acid-based copolymer constituting the copolymer (A) or the ionomer (A) is at least a binary copolymer in which ethylene and unsaturated carboxylic acid are copolymerized, and a third copolymer It may be a ternary or more multicomponent copolymer in which the components are copolymerized. In addition, an ethylene/unsaturated carboxylic acid type copolymer may be used individually by 1 type, and may use 2 or more types of ethylene/unsaturated carboxylic acid type copolymer together.

As the unsaturated carboxylic acid constituting the ethylene/unsaturated carboxylic acid binary copolymer, for example, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic acid, maleic anhydride, etc. and unsaturated carboxylic acids having 4 to 8 carbon atoms. In particular, acrylic acid or methacrylic acid is preferable.

When the ethylene/unsaturated carboxylic acid-based copolymer (A) is a ternary or more multi-component copolymer, a monomer (third copolymerization component) that forms the multi-component copolymer may also be included. Examples of the third copolymerization component include unsaturated carboxylic acid esters (eg, 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 (for example, vinyl acetate, vinyl propionate, etc.), oxides such as vinyl sulfuric acid and vinyl nitric acid, halogen compounds (for example, vinyl chloride, vinyl fluoride, etc.), vinyl group-containing primary and secondary amine compounds, carbon monoxide , sulfur dioxide, and the like, and as these copolymerization components, unsaturated carboxylic acid esters are preferable.

For example, when the ethylene/unsaturated carboxylic acid copolymer (A) is a ternary copolymer, a ternary copolymer of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester, ethylene, and an unsaturated carboxylic acid; A terpolymer with an unsaturated hydrocarbon, etc. are mentioned suitably.

As unsaturated carboxylic acid ester, unsaturated carboxylic acid alkylester is preferable, 1-12 are preferable, as for carbon number of the alkyl part of alkylester, 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 the unsaturated carboxylic acid ester include unsaturated carboxylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl moiety (for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, and isooctyl acrylate) , methyl methacrylate, ethyl methacrylate, methacrylic acid alkyl esters such as isobutyl methacrylate, maleic acid alkyl esters such as dimethyl maleate and diethyl maleate); and the like.

Among the unsaturated carboxylic acid alkylesters, (meth)acrylic acid alkylesters having 1 to 4 carbon atoms in the alkyl moiety are more preferable.

Any of a block copolymer, a random copolymer, and a graft copolymer may be sufficient as the form of a copolymer, and any of a binary copolymer and a terpolymer may be sufficient. Among them, from the viewpoint of being industrially available, a binary random copolymer, a ternary random copolymer, a graft copolymer of a binary random copolymer, or a graft copolymer of a ternary random copolymer is preferable, and more preferably binary random copolymer or ternary random copolymer.

Specific examples of the ethylene/unsaturated carboxylic acid copolymer include binary copolymers such as ethylene/acrylic acid copolymer and ethylene/methacrylic acid copolymer, and terpolymers such as ethylene/methacrylic acid/isobutyl acrylate copolymer. can be heard Moreover, you may use the commercial item marketed as an ethylene-unsaturated carboxylic acid type copolymer, For example, the Nucrel series (trademark) manufactured by Mitsui DuPont Polychemicals, etc. can be used.

4 mass % - 20 mass % are preferable, as for the copolymerization ratio (mass ratio) of unsaturated carboxylic acid in an ethylene-unsaturated carboxylic acid type copolymer, More preferably, they are 5 mass % - 15 mass %. 1 mass % - 20 mass % are preferable, as for the copolymerization ratio (mass ratio) of the unsaturated carboxylic acid ester in an ethylene-unsaturated carboxylic acid type copolymer, More preferably, they are 5 mass % - 15 mass %. The content rate of the structural unit derived from unsaturated carboxylic acid ester is 1 mass % or more from a scalability viewpoint, It is preferable that it is preferably 5 mass % or more. Moreover, it is preferable that it is 20 mass % or less from a viewpoint of preventing blocking and fusion|fusion, and, as for the content rate of the structural unit derived from unsaturated carboxylic acid ester, it is more preferable that it is 15 mass % or less.

In the ionomer (A) used as the resin (A) in the present invention, it is preferable that the carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer are crosslinked (neutralized) in an arbitrary ratio with a metal ion. Metal ions, such as a lithium ion, a sodium ion, a potassium ion, a rubidium ion, a cesium ion, a zinc ion, a magnesium ion, and a manganese ion, are mentioned as a metal ion used for neutralization of an acidic radical. Among these metal ions, a magnesium ion, a sodium ion, and a zinc ion are preferable from the viewpoint of the availability of industrialized products, and a sodium ion and a zinc ion are more preferable.

10 % - 85 % are preferable and, as for the neutralization degree of the ethylene-unsaturated carboxylic acid type copolymer in an ionomer (A), 15 % - 82 % are more preferable. When the degree of neutralization is 10% or more, chip breakability can be further improved, and when it is 85% or less, workability and moldability are excellent.

In addition, the neutralization degree is the compounding ratio (mol%) of the metal ion with respect to the mole number of the acidic radical which an ethylene-unsaturated carboxylic acid type copolymer has, especially a carboxyl group.

The melt flow rate (MFR) of the ethylene/unsaturated carboxylic acid-based copolymer and its ionomer is preferably in the range of 0.2 g/10 min to 20.0 g/10 min, and more than 0.5 g/10 min to 20.0 g/10 min. Preferably, 0.5 g/10 min to 18.0 g/10 min is more preferable. When a melt flow rate is in the said range, it is advantageous at the time of shaping|molding.

In addition, MFR is a value measured by the method based on JISK7210-1999 at 190 degreeC and 2160 g of loads.

Content of resin (A) in the resin composition which comprises a 1st resin layer is 30 mass parts or more and 95 mass with respect to the total amount of resin (A), resin (B) mentioned later, and antistatic agent (C) mentioned later. It is a part or less, 40 mass parts or more and 90 mass parts or less are preferable, and 50 mass parts or more and 90 mass parts or less are more preferable.

When content of resin (A) is in the said range, it is excellent in film workability.

<Resin (B)>

Resin (B) in this invention is at least 1 sort(s) chosen from the group which consists of polyamide and polyurethane. Generally, the melting point of the ethylene/unsaturated carboxylic acid copolymer or its ionomer used as the resin (A) is as low as 100° C. or less, and accordingly, the heat resistance of the resin composition mixed with the high melting point resin increases to some extent, It is within the scope of the estimate. However, among resins having a relatively high melting point, by combining polyamide and/or polyurethane with an ethylene/unsaturated carboxylic acid-based copolymer or its ionomer (resin (A)), it is expected from the melting point of polyamide or polyurethane. A resin composition having higher heat resistance than that is obtained. In addition, the film produced using such a resin composition has not only excellent heat resistance but also the well-balanced chip breaking property and expandability suitable as a dicing film.

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

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 (eg, 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. As the thermoplastic polyurethane elastomer, polyisocyanates (eg, aliphatic, alicyclic or aromatic diisocyanates), high molecular polyols (eg, polyether polyols, polycarbonate polyols, acrylic polyols) and chain extenders ( For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, bisphenol A, p-xylylene those obtained by copolymerization of diols such as glycol).

Content of resin (B) in the resin composition which comprises 1st resin layer is 5 mass parts or more and less than 40 mass parts with respect to the total amount of resin (A), resin (B), and antistatic agent (C) mentioned later. and 5 mass parts or more and 35 mass parts or less are preferable, and 5 mass parts or more and 30 mass parts or less are more preferable.

When content of resin (B) is less than 5 mass parts, the heat resistance improvement effect by resin (B) is not exhibited. Moreover, if content of resin (B) is 40 mass parts or more, manufacture of the dicing film base material containing a 1st resin layer and a 2nd resin layer becomes difficult. Specifically, when the content of the resin (B) is 40 parts by mass or more and less than 60 parts by mass, film molding is possible, but the extrusion of the first layer becomes unstable, and the thickness precision of the film used as the first resin layer becomes insufficient. easy. Moreover, when content of resin (B) is 60 mass parts or more, although the thickness precision of a film is sufficient, there exists a tendency for interlayer adhesiveness with a 2nd resin layer to fall.

<Antistatic agent (C)>

It is preferable that the resin composition which comprises a 1st resin layer contains an antistatic agent (C) in addition to resin (A) and resin (B). An antistatic agent (C) not only provides antistatic property to a resin composition, but also improves the heat resistance of a resin composition by interaction with resin (A) and resin (B).

Examples of the antistatic agent (C) include high molecular weight antistatic agents and low molecular weight antistatic agents such as surfactants. Among these antistatic agents, a polymer type antistatic agent is preferable at the point that the surface contamination by bleed-out is suppressed.

The polymer-type antistatic agent refers to a conductive moiety (for example, a polyether-derived structural moiety, a quaternary ammonium base moiety, etc.) and a non-conductive moiety (e.g., a polyamide-derived structural moiety, a polyolefin-derived structure such as polyethylene) site, acrylate-derived structural moiety, methacrylate-derived structural moiety, styrene-derived structural moiety, etc.), and is a copolymer having a molecular weight of 300 or more (preferably 1000 to 10000). Molecular weight is the weight average molecular weight of polystyrene conversion measured by GPC.

In addition, electroconductivity means that the surface resistivity measured based on ASTMD257 is 10 ¹⁰ ohms/square or less.

Examples of the polymer-type antistatic agent include nonionic polymer-type antistatic agents such as polyethylene oxide, polypropylene oxide, polyethylene glycol, polyether esteramide, polyether ester, polyether polyolefin, and ethylene oxide/epichlorohydrin-based copolymer. Antistatic agents, anionic polymeric antistatic agents such as polystyrenesulfonic acid, quaternary ammonium salt-containing acrylate polymers, quaternary ammonium salt-containing styrene polymers, and cationic polymeric antistatic agents such as quaternary ammonium salt-containing polyethylene glycol methacrylate polymers can

More specifically, for example, polyether ester amide described in JP-A-H1-163234 or a block of polyolefin disclosed in JP-A 2001-278985, and a hydrophilic polymer block copolymers having a structure in which blocks are repeatedly bonded together, and copolymers having a structure in which olefinic blocks formed by polymerization of olefinic monomers and hydrophilic blocks formed by polymerization of hydrophilic monomers are repeatedly bonded to each other have.

Among these antistatic agents, from the viewpoint of compatibility with resin (A) and resin (B), heat resistance, and antistatic property, polyether esteramide is preferable. Polyetheresteramide refers to a copolymer having a structural moiety derived from polyamide and a structural moiety derived from polyether, and these structural moieties are ester-bonded.

As a polyamide forming a structural moiety derived from polyamide in polyether esteramide, for example, dicarboxylic acid (eg, oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid) , 1,4-cyclohexanedicarboxylic acid, etc.) 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, polycondensation with p-xylylenediamine, etc.), ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12- It is obtained by polycondensation of aminocarboxylic acids, such as aminododecanoic acid, or copolymerization of the said lactam, dicarboxylic acid, and diamine, etc. Such polyamide segments include 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, etc., especially nylon 11, nylon 12, etc. are preferable. The molecular weight of the polyamide block is, for example, about 400 to 5000.

In addition, when using polyamide as resin (B), let the structural site|part derived from polyamide of antistatic agent (C) be a compound other than polyamide used as resin (B).

Moreover, as a polyether block, polyoxyalkylene glycol, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, or these mixtures, etc. are illustrated. These molecular weights are, for example, about 400-6000, Furthermore, about 600-5000 is good.

As the polyether esteramide, the structural moiety derived from polyoxyalkylene glycol (preferably polyethylene glycol or polypropylene glycol) is 5% by mass to 80% by mass (more preferably 15% by mass) with respect to the total mass of the polyether esteramide. It is preferable that mass % - 70 mass %) is contained. In addition, the polyether esteramide having a melting point of less than 190°C preferably has a melt flow rate (MFR) of 0.1 to 1000 g/10 min (more preferably 1 to 100 g/10 min) measured at 190° C. and a load of 2160 g. Polyetheresteramide having a melting point of 190°C or higher preferably has a melt flow rate of 0.1 to 1000 g/10 min (more preferably 1 to 100 g/10 min) at 230°C and a load of 2160 g. Moreover, it is preferable that the melting|fusing point (the temperature which shows the maximum amount of heat absorption) of polyether esteramide measured with a differential scanning calorimeter (DSC) is 130 degreeC - 175 degreeC. Such polyether esteramide can be obtained by reacting a polyamide having a molecular weight of 600 to 5000, polyoxyalkylene glycol, and, if necessary, carboxylic acid.

Examples of the low-molecular antistatic agent include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfuric acid ester bases, phosphoric acid ester bases, and the like. and positive antistatic agents such as anionic antistatic agents having an anionic group, amino acid antistatic agents and amino sulfate ester antistatic agents, amino alcohol antistatic agents, glycerin antistatic agents, and nonionic antistatic agents such as polyethylene glycol antistatic agents.

As an antistatic agent, a commercial item may be used, As a specific example, Sanyo Chemical Industry Co., Ltd. PELESTAT 230, Pelestat HC250, Pelestat 300, Pelestat 2450, PELECTRON PVL, BASF Japan company make Irgastat P-16, the same P-18FCA, the same P-20, the same P-22, etc. are mentioned.

Moreover, from a viewpoint of improving the effect of improving the heat resistance of a resin composition, it is preferable that melting|fusing point is 100 degreeC or more and 200 degrees C or less, and, as for an antistatic agent, it is more preferable that they are 120 degreeC or more and 200 degrees C or less. In addition, as melting|fusing point, based on JIS-K7121 (1987), the melting|fusing temperature measured with a differential scanning calorimeter (DSC) can be used.

The content of the antistatic agent (C) in the resin composition constituting the first resin layer is 0 parts by mass or more and 30 parts by mass or less with respect to the total amount of the resin (A), the resin (B), and the antistatic agent (C). , 5 mass parts or more and less than 30 mass parts are preferable, and 5 mass parts or more and less than 25 mass parts are more preferable. When content of an antistatic agent (C) is less than 5 mass parts, the heat resistance improvement effect by an antistatic agent is hard to be exhibited, and when it exceeds 30 mass parts, the extensibility of a film may deteriorate. 80 mass % or more and 100 mass % or less are preferable, and, as for the total content of resin (A) in a 1st resin layer, resin (B), and antistatic agent (C), 90 mass % or more and 100 mass % or less are more preferable.

<Other Polymers and Additives>

Other polymers and various additives may be added to the resin composition constituting the first resin layer as needed within a range that does not impair the effects of the present invention. Examples of the other polymers include polyolefins such as polyethylene, polypropylene, and ethylene/α-olefin copolymer (the α-olefin includes propylene, butylene, octene, and the like). Such other polymers can be mix|blended in the ratio of 20 mass parts or less with respect to a total of 100 mass parts of said (A), (B), and (C). As an example of the additives, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, dyes, lubricants, antiblocking agents, antistatic agents, mildew inhibitors, antibacterial agents, flame retardants, flame retardant aids, crosslinking agents, crosslinking aids, foaming agents, foaming aids, An inorganic filler, a fiber reinforcement, etc. are mentioned. You may add a small amount of the said additive from a viewpoint of heat-sealing prevention. Specific examples of the ultraviolet absorber include benzophenone, benzoate, benzotriazole, cyanoacrylate, and hindered amine; Specific examples of the filler include silica, clay, calcium carbonate, barium sulfate, glass beads, and talc.

<Method for producing a resin composition>

The resin composition which comprises a 1st resin layer can be obtained by mixing resin (A), resin (B), and an antistatic agent (C) as needed, and another polymer and an additive as needed. Although there is no limitation in particular in the manufacturing method of a resin composition, For example, after dry blending all the components, it can obtain by melt-kneading.

As for the resin composition which comprises 1st resin layer, it is preferable that melt flow rate (MFR) measured by 230 degreeC and 2160 g load is 1 g/10min - 50 g/10min. When an ethylene/(meth)acrylic acid copolymer or an ionomer (A) is used especially as resin (A), it is preferable that MFR in 230 degreeC is 20 g/10min or less. If MFR in 230 degreeC is 20 g/10min or less, the film excellent in the balance of the heat resistance in 140 degreeC, and expandability will be obtained.

1-2. 2nd resin layer

The second resin layer is a layer containing the resin (D), and the resin (D) is at least selected from the group consisting of an ethylene/unsaturated carboxylic acid copolymer and an ionomer of the ethylene/unsaturated carboxylic acid copolymer. It is one kind of resin. Resin (D) is a material with high adhesiveness with the resin composition which comprises a 1st resin layer. Therefore, by laminating|stacking with the 1st resin layer, it becomes possible to raise the intensity|strength of a dicing film base material, and to maintain the balance between chip breakability and expandability required for a dicing film without generating the problem of delamination.

<Resin D>

The resin (D) in the present invention is an ethylene/unsaturated carboxylic acid copolymer (hereinafter simply referred to as “copolymer (D)”) and an ionomer of the ethylene/unsaturated carboxylic acid copolymer (hereinafter simply referred to as “copolymer (D)”). It is at least 1 sort(s) selected from the group which consists of "ionomer (D)"). In the present invention, the ionomer of the ethylene/unsaturated carboxylic acid copolymer used as the resin (D) is one in which a part or all of the carboxyl groups of the ethylene/unsaturated carboxylic acid copolymer are neutralized with a metal (ion). . In the present invention, an "ionomer" in which at least a part of the acid groups of the ethylene/unsaturated carboxylic acid-based copolymer is neutralized by a metal (ion), and the acid group of the ethylene/unsaturated carboxylic acid-based copolymer by a metal (ion) What is not neutralized is called a "copolymer."

In addition, as demonstrated in detail below, resin (D) is resin similar to resin (A) contained in the resin composition which comprises a 1st resin layer.

The ethylene/unsaturated carboxylic acid copolymer constituting the copolymer (D) or the ionomer (D) is at least a binary copolymer in which ethylene and unsaturated carboxylic acid are copolymerized, and the third copolymer component is copolymerized It may be a ternary or more multi-component copolymer. In addition, an ethylene/unsaturated carboxylic acid type copolymer may be used individually by 1 type, and may use 2 or more types of ethylene/unsaturated carboxylic acid type copolymer together.

As the unsaturated carboxylic acid constituting the ethylene/unsaturated carboxylic acid binary copolymer, for example, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic acid, maleic anhydride, etc. and unsaturated carboxylic acids having 4 to 8 carbon atoms. In particular, acrylic acid or methacrylic acid is preferable.

When the ethylene/unsaturated carboxylic acid-based copolymer (D) is a ternary or more multi-component copolymer, a monomer (third copolymerization component) that forms the multi-component copolymer may also be included. Examples of the third copolymerization component include unsaturated carboxylic acid esters (eg, 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 (for example, vinyl acetate, vinyl propionate, etc.), oxides such as vinyl sulfuric acid and vinyl nitric acid, halogen compounds (for example, vinyl chloride, vinyl fluoride, etc.), vinyl group-containing primary and secondary amine compounds, carbon monoxide , sulfur dioxide, and the like, and as these copolymerization components, unsaturated carboxylic acid esters are preferable.

For example, when the ethylene/unsaturated carboxylic acid copolymer (D) is a ternary copolymer, a ternary copolymer of ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester, ethylene, and an unsaturated carboxylic acid; A terpolymer with an unsaturated hydrocarbon, etc. are mentioned suitably.

As unsaturated carboxylic acid ester, unsaturated carboxylic acid alkylester is preferable, 1-12 are preferable, as for carbon number of the alkyl part of alkylester, 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 the unsaturated carboxylic acid ester include unsaturated carboxylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl moiety (for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, and isooctyl acrylate) , methyl methacrylate, ethyl methacrylate, methacrylic acid alkyl esters such as isobutyl methacrylate, maleic acid alkyl esters such as dimethyl maleate and diethyl maleate); and the like.

Among the unsaturated carboxylic acid alkylesters, (meth)acrylic acid alkylesters having 1 to 4 carbon atoms in the alkyl moiety are more preferable.

Any of a block copolymer, a random copolymer, and a graft copolymer may be sufficient as the form of a copolymer, and any of a binary copolymer and a terpolymer may be sufficient. Among them, from the viewpoint of being industrially available, a binary random copolymer, a ternary random copolymer, a graft copolymer of a binary random copolymer, or a graft copolymer of a ternary random copolymer is preferable, and more preferably binary random copolymer or ternary random copolymer.

Specific examples of the ethylene/unsaturated carboxylic acid copolymer include binary copolymers such as ethylene/acrylic acid copolymer and ethylene/methacrylic acid copolymer, and terpolymers such as ethylene/methacrylic acid/isobutyl acrylate copolymer. can be heard Moreover, you may use the commercial item marketed as an ethylene-unsaturated carboxylic acid type copolymer, For example, the Nucrel series (trademark) manufactured by Mitsui DuPont Polychemicals, etc. can be used.

4 mass % - 20 mass % are preferable, as for the copolymerization ratio (mass ratio) of unsaturated carboxylic acid in an ethylene-unsaturated carboxylic acid type copolymer, More preferably, they are 5 mass % - 15 mass %. 1 mass % - 20 mass % are preferable, as for the copolymerization ratio (mass ratio) of the unsaturated carboxylic acid ester in an ethylene-unsaturated carboxylic acid type copolymer, More preferably, they are 5 mass % - 15 mass %. The content rate of the structural unit derived from unsaturated carboxylic acid ester is 1 mass % or more from a scalability viewpoint, It is preferable that it is preferably 5 mass % or more. Moreover, it is preferable that it is 20 mass % or less from a viewpoint of preventing blocking and fusion|fusion, and, as for the content rate of the structural unit derived from unsaturated carboxylic acid ester, it is more preferable that it is 15 mass % or less.

In the ionomer (D) used as the resin (D) in the present invention, the carboxyl group contained in the ethylene/unsaturated carboxylic acid copolymer is preferably crosslinked (neutralized) in an arbitrary ratio with a metal ion. Metal ions, such as a lithium ion, a sodium ion, a potassium ion, a rubidium ion, a cesium ion, a zinc ion, a magnesium ion, and a manganese ion, are mentioned as a metal ion used for neutralization of an acidic radical. Among these metal ions, a magnesium ion, a sodium ion, and a zinc ion are preferable from the viewpoint of the availability of industrialized products, and a sodium ion and a zinc ion are more preferable.

10 % - 85 % are preferable and, as for the neutralization degree of the ethylene-unsaturated carboxylic acid type copolymer in an ionomer (D), 15 % - 82 % are more preferable. When the degree of neutralization is 10% or more, chip breakability can be further improved, and when it is 85% or less, workability and moldability are excellent.

In addition, the neutralization degree is the compounding ratio (mol%) of the metal ion with respect to the mole number of the acidic radical which an ethylene-unsaturated carboxylic acid type copolymer has, especially a carboxyl group.

The melt flow rate (MFR) of the ethylene/unsaturated carboxylic acid-based copolymer and its ionomer is preferably in the range of 0.2 g/10 min to 20.0 g/10 min, and more than 0.5 g/10 min to 20.0 g/10 min. Preferably, 0.5 g/10 min to 18.0 g/10 min is more preferable. When a melt flow rate is in the said range, it is advantageous at the time of shaping|molding.

In addition, MFR is a value measured by the method based on JISK7210-1999 at 190 degreeC and 2160 g of loads.

80 mass % or more and 100 mass % or less are preferable, and, as for content of resin (D) in a 2nd resin layer, 90 mass % or more and 100 mass % or less are more preferable.

<Additives>

Various additives and other resin may be added to resin (D) which comprises a 2nd resin layer as needed in the range which does not impair the effect of this invention. As an example of the additive, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, dyes, lubricants, antiblocking agents, antistatic agents, mildew inhibitors, antibacterial agents, flame retardants, flame retardant aids, crosslinking agents, crosslinking aids, foaming agents, foaming aids, An inorganic filler, a fiber reinforcement, etc. are mentioned. You may add a small amount of the said additive from a viewpoint of heat-sealing prevention. Specific examples of the ultraviolet absorber include benzophenone, benzoate, benzotriazole, cyanoacrylate, and hindered amine; Specific examples of the filler include silica, clay, calcium carbonate, barium sulfate, glass beads, and talc. Examples of other resins include polyethylene, polypropylene, and ethylene/α-olefin copolymer.

1-3. layer composition

The dicing film base material of this invention is a dicing film base material containing the said 1st resin layer and the said 2nd resin layer (refer FIG. 1). Although the layer structure is not specifically limited as long as a dicing film base material contains the said two layers, From a viewpoint of preventing delamination, it is preferable that the 1st resin layer and the 2nd resin layer are laminated|stacked directly.

Resin (A) contained in the resin composition which comprises a 1st resin layer, and resin (D) which comprises a 2nd resin layer may be the same resin, or may be different. As a preferable combination of the first resin layer and the second resin layer, the combination of the ionomer of the ethylene/unsaturated carboxylic acid copolymer and the ionomer of the ethylene/unsaturated carboxylic acid copolymer is preferable from the viewpoint of chip breakability and expandability. do.

The multilayer structure used as three or more layers may be sufficient as a dicing film base material. For example, a configuration in which a second resin layer is provided in a place in which a plurality of sheets to be molded using the resin composition constituting the first resin layer are laminated may be employed, or the second resin layer is sandwiched by two first resin layers. configuration may be sufficient. Moreover, in addition to the 1st resin layer and the 2nd resin layer, the structure which laminated|stacked the other resin layer may be sufficient.

The resin constituting the other resin layer laminated on the dicing film substrate of the present invention is linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), ethylene-α olefin copolymer, polypropylene, and ethylene/vinyl ester copolymer. A typical example is a blend product selected from, single-piece or an arbitrary plurality.

In addition, the other resin layer to be laminated|stacked may be a functional layer (for example, adhesive sheet etc.), and may be sufficient as a base material, such as a polyolefin film (or sheet), a polyvinyl chloride film (or a sheet|seat). The substrate may have either a single layer or a multilayer structure. In this invention, including these base materials, it is called "dicing film base material."

In order to improve the adhesive force of the dicing film base material surface, you may give well-known surface treatment, such as corona discharge treatment, to the dicing film base material surface, for example.

Moreover, you may irradiate an electron beam to a 1st resin layer, a 2nd resin layer, another resin layer, or a dicing film base material from a viewpoint of a heat resistance improvement as needed.

1-4. Manufacturing method

As a manufacturing method of the dicing film base material of this invention, the resin composition which comprises a 1st resin layer, and resin (D) which comprises a 2nd resin layer are processed into a film shape by a well-known method, respectively, and the method of laminating|stacking is mentioned. can Although there is no particular limitation on the method of processing the resin composition or resin into a film shape, for example, the conventionally known T die cast molding method, T die nip molding method, inflation molding method, extrusion lamination method, calender molding method, etc. Various molding methods, Films can be made.

Moreover, the dicing film base material of this invention can be manufactured by performing coextrusion lamination of the resin composition which comprises a 1st resin layer, and resin (D) which comprises a 2nd resin layer, for example.

For example, when laminating the resin composition constituting the first resin layer on the surface of the film of the resin (D) used as the second resin layer by a T-die film molding machine or an extrusion coating molding machine, the second resin layer and In order to improve the adhesiveness of , it may be formed through an adhesive resin layer by a co-extrusion coating molding machine. As such an adhesive resin, a single-piece|unit selected from the above-mentioned various ethylene copolymers, or these unsaturated carboxylic acid graft materials, or the blend which consists of arbitrary plurality is mentioned as a representative example.

In addition, as a molding example of the dicing film substrate of the present invention, a T-die film molding machine or an extrusion coating molding machine is used to form a first resin layer on the surface of the film of the resin (D) serving as the second resin layer The method of forming a laminated body by heat-bonding a resin composition is mentioned.

Moreover, although the method of forming the layer which consists of the resin composition used as a 1st resin layer on the film of resin (D) used as a 2nd resin layer was described, on the contrary, the film of the resin composition used as a 1st resin layer on the contrary. The dicing film base material of this invention can be manufactured also by the method of forming a layer with the resin (D) used as a 2nd resin layer, or providing a 1st resin or a 2nd resin layer on top of another resin layer. have.

Although the thickness of the dicing film base material is not particularly limited, considering its use as a constituent member of the dicing film, it is preferably 65 µm or more from the viewpoint of frame holding during dicing and 200 µm or less from the viewpoint of expandability. The thickness of each resin layer constituting the dicing film substrate is not particularly limited as long as their total does not exceed the thickness of the dicing film substrate, but both the first resin layer and the second resin layer are 30 µm or more and 100 µm It is preferable that it is the following, and it is preferable that ratio of the thickness of a 1st resin layer and a 2nd resin layer is 30/70-70/30.

2. Dicing Film

A 2nd 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 at least one surface of them. 2 : is sectional drawing which shows one Embodiment of the dicing film 20 of this invention. As shown in FIG. 2, the dicing film 20 of this invention is the dicing film base material 10 containing the 1st resin layer 1 and the 2nd resin layer 2, and the adhesive provided on the surface. It has a layer (11).

From a heat resistant viewpoint, it is preferable to be comprised so that a 1st resin layer may become an outermost layer, and the structure in which the adhesion layer was formed in the outermost layer is more preferable. The adhesion layer is arrange|positioned on the surface of a dicing film base material. A dicing film can be adhere|attached to a semiconductor wafer through this adhesion layer, and a semiconductor wafer can be diced.

As described above, since the dicing film substrate of the present invention has excellent heat resistance, the dicing film of the present invention is also a film having excellent heat resistance and excellent balance between chip breakability and expandability. For this reason, if the dicing film of this invention is used, a semiconductor wafer can be processed efficiently and with high precision.

<Adhesive layer>

The dicing film of this invention is equipped with the dicing film base material of this invention, and the adhesive layer provided on the single side|surface of the dicing film base material, The semiconductor wafer used as the object of dicing is stuck and fixed to the adhesive layer. Although the thickness of an adhesion layer also depends on the kind of adhesive, it is preferable that it is 3-100 micrometers, and it is more preferable that it is 3-50 micrometers.

As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, a conventionally known pressure-sensitive adhesive can be used. Examples of the pressure-sensitive adhesive include a rubber-based, acrylic-based, silicone-based, and polyvinyl ether-based pressure-sensitive adhesive; radiation curing adhesive; Heat-foaming type adhesive, etc. are included. Especially, when the peelability of the dicing film from a semiconductor wafer, etc. are considered, it is preferable that an adhesive layer contains an ultraviolet curable adhesive.

Examples of the acrylic pressure-sensitive adhesive capable of constituting 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 the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isononyl (meth)acrylate, etc. (meth)acrylic acid alkyl ester, (meth)acrylic acid hydroxyethyl, (meth)acrylic acid hydroxybutyl, (meth)acrylic acid hydroxyalkyl ester, such as (meth)acrylic acid hydroxyhexyl, (meth)acrylic acid glycidyl ester etc. are included.

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

The UV-curable pressure-sensitive adhesive capable of constituting the pressure-sensitive adhesive layer is not particularly limited, but contains the acrylic pressure-sensitive adhesive, an ultraviolet curing component (a component capable of adding a carbon-carbon double bond to the polymer side chain of the acrylic pressure-sensitive adhesive), and a photopolymerization initiator. do. Moreover, you may add additives, such as a crosslinking agent, a tackifier, a filler, an antioxidant, a coloring agent, to an ultraviolet curing adhesive agent as needed.

The ultraviolet curable component contained in the ultraviolet curable pressure-sensitive 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 ultraviolet curing component include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, neo esters of (meth)acrylic acid and polyhydric alcohols such as pentyl glycol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate, and oligomers thereof; 2-propenyldi-3-butenylcyanurate, 2-hydroxyethylbis(2-acryloxyethyl)isocyanurate, tris(2-methacryloxyethyl)isocyanurate, tris(2- isocyanurates, such as methacryloxyethyl) isocyanurate, etc. are contained.

Specific examples of the photopolymerization initiator contained in the UV-curable pressure-sensitive adhesive include benzoin alkyl ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; aromatic ketones such as α-hydroxycyclohexylphenyl ketone; Aromatic ketals, such as benzyl dimethyl ketal, thioxanthone, such as polyvinyl benzophenone, chloro thioxanthone, dodecyl thioxanthone, dimethyl thioxanthone, and diethyl thioxanthone, etc. are contained.

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

It is preferable to attach a separator to the surface of the adhesion layer of the dicing film of this invention. By affixing a separator, the surface of an adhesion layer can be kept smooth. Moreover, while handling and conveyance of the film for semiconductor manufacture become easy, it also becomes possible to label-process on a separator.

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

<Method for producing dicing film>

When manufacturing the dicing film of the present invention, the pressure-sensitive adhesive is diced using a known method, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, etc. A method of applying directly to a film substrate, or a method of applying an adhesive on a release sheet by the above-known method to provide an adhesive layer, and then attaching it to the surface layer of a dicing film substrate to transfer the adhesive layer, etc. can be used.

In addition, by co-extruding the resin composition constituting the first resin layer and the material constituting the adhesive layer, a laminated film is obtained (co-extrusion molding method), and by providing a second resin layer thereto, a dicing film can be produced have.

Moreover, it is good also considering the layer of an adhesive composition as an adhesive layer by heat-crosslinking as needed.

Moreover, you may stick a separator on the surface of an adhesion layer.

Example

Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. In addition, unless otherwise indicated, "part" is a mass basis.

1. Resin (A)

As the resin (A), an ionomer of the following ethylene/unsaturated carboxylic acid copolymer (hereinafter referred to as "ionomer") and an ethylene/unsaturated carboxylic acid copolymer (hereinafter, abbreviated as "copolymer") prepared In addition, the melt flow rate (MFR) of the following resin is the value measured based on JISK7210 (1999) at 190 degreeC and a 2160 g load.

・Ionomer 1 (IO1)

Ethylene content: 80 mass %, methacrylic acid content: 10 mass %, acrylic acid butyl ester content: 10 mass %, neutralization degree: 70% Zinc neutralization, MFR: 1 g/10min

・Ionomer 2 (IO2)

Ethylene content: 85 mass %, methacrylic acid content: 15 mass %, neutralization degree: 59% Zinc neutralization, MFR: 1 g/10 min.

・Ionomer 3 (IO3)

Ethylene content: 89 mass%, methacrylic acid content: 11 mass%, neutralization degree: 65% Zinc neutralization, MFR: 5 g/10 min

・Ionomer 4 (IO4)

Ethylene content: 85 mass %, methacrylic acid content: 15 mass %, neutralization degree: 23% Zinc neutralization, MFR: 5 g/10 min.

・Ionomer 5 (IO5)

Ethylene content: 90 mass %, methacrylic acid content: 10 mass %, neutralization degree: 50% sodium neutralization, MFR: 1 g/10 min.

・Copolymer (EMAA1)

Ethylene content: 91 mass %, methacrylic acid content: 9 mass %, MFR 3g/10min

・Copolymer (EMAA2)

Ethylene content: 79 mass %, methacrylic acid content: 11 mass %, acrylic acid butyl ester: 10 mass %, MFR 10 g/10min

2. Resin (B)

As resin (B), the following resin was prepared.

Polyamide 1 (PA1): Nylon 6 (Amilan CM1021XF manufactured by Toray Corporation)

Polyamide 2 (PA2): Nylon 6-12 (UBE Nylon 7024B manufactured by Ube Kogsan Co., Ltd.)

・Polyurethane (TPU): Thermoplastic polyurethane elastomer (Miractran P485RSUI manufactured by Tosoh Corporation)

3. Antistatic agent (C)

As the antistatic agent (C), the following compound was prepared.

Polyether esteramide (PEEA): Pelestat 230 manufactured by Sanyo Chemical Industry Co., Ltd.

4. Resin (D)

As resin (D), the following resin was prepared.

・Ionomer 1 (IO1) (same as used as resin (A))

Ethylene content: 80 mass %, methacrylic acid content: 10 mass %, acrylic acid butyl ester content: 10 mass %, neutralization degree: 70% Zinc neutralization, MFR: 1 g/10min

・Ethylene/unsaturated carboxylic acid copolymer (EMAA1)

Ethylene content: 91 mass %, methacrylic acid content: 9 mass %, MFR: 3 g/10min

・Other resins (LDPE1)

Low Density Polyethylene, MFR: 1.6 g/10 min, Density: 921 kg/m ³

(Example 1)

Resin (A) and resin (B) of the ratio (mass %) shown in Table 1 were dry-blended. Next, the resin composition for 1st resin layers was obtained by injecting|throwing-in the dry-blended mixture to the resin inlet of a 30 mm (phi) twin screw extruder, and melt-kneading at the die temperature of 230 degreeC.

About the obtained resin composition for 1st resin layers, based on JISK7210 (1999), MFR was measured by 230 degreeC and 2160g load, and it described in Table 1.

The obtained resin composition for the 1st resin layer and the resin (D) for the 2nd resin layer are injected|thrown-in to each extruder using the 2 type 2 layer 40mmφ T die film molding machine, and the processing temperature of 240 degreeC It molded under the conditions to produce a two-layer, two-layer T-die film having a thickness of 100 µm.

By the above, a 100-micrometer-thick laminated film having a two-layer structure (thickness ratio of the first layer and the second layer = 50/50) was obtained. The obtained laminated|multilayer film was made into the dicing film base material, and the following method evaluated. The evaluation results are shown in Table 1.

(1) 160℃ heat resistance

The dicing film base material was cut out to MD direction (Machine Direction) 10cm x TD direction (Transverse Direction) 3cm, respectively, and it was set as the film for evaluation. The MD direction center part of the film for evaluation WHEREIN: The mark line of length 60mm was written in MD direction.

After each film for evaluation was left to stand for 2 minutes under 160 degreeC and a 5g load, the length of the marked line was measured, and the length of the marked line after a heating test was computed with respect to the length of the marked line before a heating test.

Length of marked line after heating test [%] = (length of marked line after heating test / 60 mm) x 100

A mark length of 100 means that the film is not changed by heating, and when the mark length exceeds 100, it means that the film is elongated by heating, and when the mark length is less than 100 , means that the film has been reduced by heating.

160 degreeC heat resistance was evaluated according to the following criteria based on the length of the marked line after a heating test.

(double-circle): The length of the marked line after a 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

△: The length of the marked line after the heating test is 110.1 to 115.0, or 86.0 to 89.9

x: the length of the marked line after the heating test is 115.1 or more, or 85.9 or less

(2) interlayer adhesion

The adhesive strength between the 1st layer and the 2nd layer of a dicing film base material is the strength (N/15) when peeling with a peeling angle 90 degree (T peel), a peeling rate 300 mm/min, and a test piece width|variety 15 mm. mm).

Moreover, based on the adhesive strength, the following criteria evaluated interlayer adhesiveness.

(circle): The interlayer adhesive strength of a 1st resin layer and a 2nd resin layer is 5 N/15 mm or more

x: The interlayer adhesive strength of a 1st resin layer and a 2nd resin layer is less than 5 N/15 mm

(3) surface resistivity

According to JIS K6911, using Hiresta-UP manufactured by Mitsubishi Chemical Co., Ltd., the applied voltage was 500 V and the measurement time was 30 seconds in an atmosphere of 23°C and 50% relative humidity, and the surface resistivity was measured.

(4) Scalability (scalability)

A rectangle of 300 mm or more in the MD direction x 300 mm or more in the TD direction was cut out from the dicing film substrate, and a square of 141 mm in width and height was drawn therein using a writing implement such as an oil-based pen (hereinafter, measurement target). A measurement target was set in a wafer expansion device for 8-inch wafers (a wafer expansion device TEX-218G GR-8 manufactured by Technovision Corporation). At this time, it was set so that the center of the stage of the wafer expansion apparatus and the center of the square drawn on the measurement object coincided. Next, after raising the stage by 15 mm and expanding the dicing film base material, it left still for 60 second, and the length (side length) of each side of the square drawn on the measurement object was measured. For each of the obtained two side lengths in the MD direction, the elongation rate (%) (= side length after extension/side length before extension × 100) was calculated, and the average value was set as the extension rate [%]. The expansion ratio is preferably 103% or more.

(5) Tensile test (modulus)

The dicing film base material was cut into the rectangular shape of 10 mm width, and it was set as the measurement object. Based on JIS K7127, the 25% modulus in each of the MD direction and TD direction of a measurement object was measured. In addition, the test speed was set to 500 mm/min.

The 25% modulus is preferably 8 Mpa or more from the viewpoint of chip breakability.

(Examples 2-15, Comparative Examples 1-5)

The resin (A), the resin (B), the antistatic agent (C), the type and amount of the resin (D), and the thickness of the first resin layer and the second resin layer were changed as shown in Tables 1 and 2 Other than that, similarly to Example 1, the laminated|multilayer film containing a 1st resin layer and a 2nd resin layer were produced. In addition, the amount of Table 1 was dry-blended and used for the antistatic agent (C) with resin (A) and resin (B).

The obtained laminated|multilayer film was used as a dicing film base material, and said method evaluated. The evaluation results are shown in Tables 1 and 2.

As is apparent from the results shown in Tables 1 and 2, the dicing film substrates of Examples 1 to 15 having a resin (A) and a first resin layer comprising a resin composition containing the resin (B) as essential components were , compared with Comparative Example 1 having a first resin layer composed of resin (A) alone, there was little change in the film after the 160°C heat resistance test, and more excellent heat resistance was exhibited.

Further, the second resin layer contains at least one resin (D) selected from the group consisting of an ethylene/unsaturated carboxylic acid copolymer and an ionomer of the ethylene/unsaturated carboxylic acid copolymer. Examples 1 to The dicing film substrate of No. 15 had a high adhesion between the film layers, and no delamination was found in the dicing film substrate of Comparative Example 2, which had a second resin layer made of another resin (low-density polyethylene). Such excellent interlayer adhesiveness was recognized even when either an ethylene/unsaturated carboxylic acid copolymer (EMAA) or an ionomer (IO) of an ethylene/unsaturated carboxylic acid copolymer was used as the resin (D).

In addition, in Comparative Example 4 containing an excessive amount of the antistatic agent (C), and Comparative Example 5 containing an excessive amount (however, 40 parts by mass or more and less than 60 parts by mass) of the resin (B), the resin composition was used Although it was possible to shape|mold a film, the extrusion of the 1st resin layer became unstable, and since the thickness precision of a film was inadequate, various physical properties could not be measured. However, in Comparative Example 3 containing an excess amount (60 parts by mass or more) of the resin (B), although molding of a laminated film having the first resin layer and the second resin layer was possible, the interlayer adhesive force of the film was low. .

This application claims the priority based on Japanese Patent Application No. 2016-253244 of the application on December 27, 2016. All the content described in the said application specification is integrated in this specification.

The dicing film base material of this invention has the outstanding heat resistance, and is excellent in the balance of chip breaking property and expandability. Therefore, by using the dicing film substrate and the dicing film of the present invention, the dicing process and the subsequent expansion process at the time of semiconductor manufacturing can be smoothly performed, and the semiconductor can be manufactured without remaining tape or deformation.

1 first resin layer
2 second resin layer
10 Dicing film substrate
11 adhesive layer
20 dicing film

Claims (5)

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-based copolymer and an ionomer of the ethylene-unsaturated carboxylic acid-based 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;
1st resin layer which consists of a resin composition containing 0 mass parts or more and 30 mass parts or less of antistatic agent (C) (however, let the sum total of a component (A), a component (B), and a component (C) be 100 mass parts). class,
A second resin layer comprising at least one resin (D) selected from the group consisting of an ethylene-unsaturated carboxylic acid-based copolymer and an ionomer of the ethylene-unsaturated carboxylic acid-based copolymer,
In the resin (A), the ethylene/unsaturated carboxylic acid-based copolymer is an ethylene/unsaturated carboxylic acid binary copolymer or an ethylene/unsaturated carboxylic acid/unsaturated carboxylic acid ester terpolymer,
In the resin (B), the polyurethane is a thermoplastic polyurethane elastomer,
The antistatic agent (C) includes a conductive moiety and a non-conductive moiety, a polymeric antistatic agent having a molecular weight of 300 or more, a cationic antistatic agent having a cationic group, an anionic antistatic agent having an anionic group, a positive antistatic agent and at least one selected from the group consisting of a nonionic antistatic agent (provided that when the resin (B) is polyamide and the antistatic agent (C) is a polymer type antistatic agent, the antistatic agent (C) The structural moiety derived from the polyamide of
In the resin (D), the ethylene/unsaturated carboxylic acid copolymer is a binary copolymer in which ethylene and unsaturated carboxylic acid are copolymerized, or a ternary copolymer in which a third copolymer component is copolymerized in the binary copolymer. The dicing film base material which is the above multi-component copolymer. The method of claim 1,
The dicing film base material whose content of the said antistatic agent (C) is 0 mass parts. The method of claim 1,
The dicing film base material whose content of the said antistatic agent (C) is 5 mass parts or more and 30 mass parts or less. delete The dicing film base material in any one of Claims 1-3;
A dicing film having an adhesive layer laminated on at least one surface of the dicing film substrate.

Images