KR102448152B1 - A film for forming a protective film, a composite sheet for forming a protective film, and a method for manufacturing a semiconductor chip - Google Patents

Abstract

The present invention relates to a film (13) for forming an energy ray-curable protective film, wherein the film (13) for forming a protective film is affixed to a semiconductor wafer, and the protective film is formed with respect to a gloss value (G1) measured after irradiating an energy ray. Decrease rate (G1-G2)/G1×100 of gloss value (G2) measured after affixing the film 13 to a semiconductor wafer, irradiating an energy ray, and heating at 260°C for 5 minutes is 30% or less to be.

Description

A film for forming a protective film, a composite sheet for forming a protective film, and a method for manufacturing a semiconductor chip

The present invention relates to a film for forming a protective film, a composite sheet for forming a protective film, and a method for manufacturing a semiconductor chip.

This application claims priority based on the patent application 2017-208437 for which it applied to Japan on October 27, 2017, and uses the content here.

In recent years, semiconductor devices to which a mounting method called a so-called face down method is applied has been manufactured. In the face-down method, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are joined to the substrate. For this reason, the back surface on the opposite side to the circuit surface of the semiconductor chip can be exposed.

A resin film containing an organic material is formed on the back surface of this exposed semiconductor chip as a protective film, and can be introduced into a semiconductor device as a semiconductor chip on which the protective film is formed.

The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, the composite sheet for protective film formation which comprises the film for protective film formation for forming a protective film on a support sheet is used, for example. The film for protective film formation can form a protective film by hardening. A support sheet can be used in order to fix a semiconductor wafer, when dividing|segmenting the film for protective film formation or the semiconductor wafer provided with the protective film on the back surface to a semiconductor chip. In addition, the support sheet can be used as a dicing sheet, and it is also possible to use the composite sheet for protective film formation as what the film for protective film formation and a dicing sheet were integrated.

As such a composite sheet for forming a protective film, for example, one provided with a film for forming a protective film for thermosetting by curing by heating has been mainly used until now. However, since a long time is normally required for about several hours for heat hardening of the film for thermosetting protective film formation, shortening of hardening time is calculated|required. On the other hand, using the (energy-ray-curable) protective film formation film which can be hardened by irradiation of energy rays, such as an ultraviolet-ray, for formation of a protective film is examined.

Patent document 1 is disclosing the energy-beam hardening-type chip protection film affixed on the back surface of a wafer circuit formation surface. This energy ray hardening type protective film for chip|tip protection has a peeling film and the energy ray hardening type protective film forming layer formed on the peeling film. The energy ray-curable protective film forming layer contains a non-energy ray-curable component as a binder polymer component in addition to the energy ray-curable component.

Japanese Patent Laid-Open No. 2010-056328

The semiconductor chip in which the protective film was formed using the energy ray hardening-type chip protective film of patent document 1 is bonded to a desired apparatus by heating. By this heating, a relatively low molecular weight component (a so-called bleed-out component) among the non-energy-ray-cured components contained in the protective film is segregated on the surface of the protective film, and the surface gloss of the protective film can be significantly reduced. Thereby, the fall of the designability of a protective film, and a fall of visibility arise when it prints on the protective film surface.

Therefore, the present invention is a film for forming a protective film that can suppress a decrease in the surface gloss of the protective film even when a semiconductor chip having a protective film, which is a cured product of the film for forming a protective film on the back surface, is heated for purposes such as bonding, the protective film formation It makes it a subject to provide the manufacturing method of the semiconductor chip using the composite sheet for protective film formation provided with the film for use, and the said film for protective film formation, or the said composite sheet for protective film formation.

In order to solve the above problems, the present invention is a film for forming an energy ray-curable protective film, wherein the film for forming a protective film is attached to a semiconductor wafer, and the film for forming a protective film for the gloss value measured after irradiating the energy ray. The film for protective film formation whose reduction rate of the gloss value measured after affixing on a semiconductor wafer, irradiating an energy ray, and also heating at 260 degreeC for 5 minutes is 30 % or less provides the film for protective film formation.

The present invention provides a composite sheet for forming a protective film including a support sheet and comprising the film for forming a protective film on the support sheet.

The present invention provides a step of attaching the protective film forming film or the protective film forming film in the protective film forming composite sheet to a semiconductor wafer, and irradiating ultraviolet rays to the protective film forming film after affixing to the semiconductor wafer to form a protective film There is provided a method for manufacturing a semiconductor chip, comprising: a step; and a step of dividing the semiconductor wafer by cutting the semiconductor wafer together with the protective film or film for forming a protective film to obtain a plurality of semiconductor chips.

The film for protective film formation of this invention can suppress the fall of the surface glossiness of a protective film even when the semiconductor chip provided with the protective film which is hardened|cured material of the film for protective film formation on the back surface is heated for the objective, such as bonding. Moreover, according to this invention, the composite sheet for protective film formation provided with the said film for protective film formation, and the manufacturing method of the semiconductor chip using the said film for protective film formation or the said composite sheet for protective film formation are provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the film for protective film formation which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.
It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of the semiconductor chip in the case of using the film for protective film formation.
It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of the semiconductor chip in the case of using the composite sheet for protective film formation.

◇Film for the protective film formation

The film for forming a protective film according to an embodiment of the present invention is a film for forming an energy ray-curable protective film, wherein the film for forming a protective film is attached to a semiconductor wafer, and the protective film is formed with respect to a gloss value measured after irradiating an energy ray. The reduction rate of the gloss value measured after affixing a film for a semiconductor wafer, irradiating an energy ray, and heating at 260 degreeC for 5 minutes is 30 % or less, It is preferable that it is 25 % or less, It is more preferable that it is 20 % or less. do.

If the decrease rate of the gloss value is below the upper limit, the decrease in the surface gloss of the protective film can be suppressed even when a semiconductor chip having a protective film, which is a cured product of the film for forming a protective film on the back surface, is heated for purposes such as bonding.

Although it is most preferable that the reduction rate of the gloss value is 0%, even when a semiconductor chip having a protective film, which is a cured product of a film for forming a protective film on the back surface, is heated for purposes such as bonding, the decrease in the surface gloss of the protective film can be sufficiently suppressed. The decrease rate may be as low as possible. From this viewpoint, 1 % or more may be sufficient as the fall rate of the said gloss value, and 2 % or more may be sufficient as it.

As a combination of an upper limit and a lower limit, 0 % or more and 30 % or less, 1 % or more and 25 % or less, 2 % or more and 20 % or less are mentioned.

A gloss value can be measured on conditions whose incident angle is 60 degrees with a gloss meter (for example, "VG7000" manufactured by Nippon Denshoku Industries Co., Ltd.).

In the present specification, the "reduction rate of the gloss value" can be obtained by dividing the difference between the gloss value before heating and the gloss value after heating by the gloss value before heating.

As mentioned later, the composite sheet for protective film formation can be comprised by forming the said film for protective film formation on a support sheet.

The said film for protective film formation hardens by irradiation of an energy ray, and turns into a protective film. This protective film protects the back surface (surface opposite to the electrode formation surface) of a semiconductor wafer or a semiconductor chip. The film for protective film formation is soft and can be affixed to a sticking target object easily.

Since the said film for protective film formation is energy-beam sclerosis|hardenability, it can form a protective film by hardening in a shorter time than the film for thermosetting protective film formation.

In this specification, a "film for protective film formation" means the thing before hardening, and a "protective film" means what hardened the film for protective film formation.

The said film for protective film formation contains an energy-beam sclerosing|hardenable component at least. As the energy ray-curable component, an energy ray-curable acrylic polymer obtained by reacting a non-energy ray-curable acrylic polymer with a compound containing an energy ray-polymerizable group and introduced an energy ray-curable group into an acrylic polymer (hereinafter referred to as "adduct type") It is also referred to as "acrylic polymer").

It is preferable that it is non-hardened, and, as for an energy-ray-curable component, it is preferable to have adhesiveness, and it is more preferable to have non-hardening and adhesiveness.

In the present invention, an "energy beam" means having an energy quantum in an electromagnetic wave or a charged particle beam, and an ultraviolet-ray, a radiation, an electron beam, etc. are mentioned as an example.

Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light or an LED lamp, etc. as an ultraviolet-ray source. The electron beam can irradiate what was generated by an electron beam accelerator etc.

In the present invention, "energy ray curability" means a property hardened by irradiating an energy ray, and "non-energy ray sclerosis|hardenability" means a property which does not harden even if it irradiates an energy ray.

One layer (single layer) may be sufficient as the film for protective film formation, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

In this specification, without limitation in the case of the film for protective film formation, "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, and even if only some layers are the same," ' and "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

It is preferable that it is 1-100 micrometers, as for the thickness of the film for protective film formation, it is more preferable that it is 3-75 micrometers, It is especially preferable that it is 5-50 micrometers. Since the thickness of the film for protective film formation is more than the said lower limit, a protective film with a higher protective ability can be formed. Since the thickness of the film for protective film formation is below the said upper limit, it is suppressed that a protective film becomes excessive thickness.

Here, the "thickness of the film for protective film formation" means the thickness of the whole film for protective film formation, For example, the thickness of the film for protective film formation which consists of multiple layers is the sum total of all the layers which comprise the film for protective film formation. means thickness.

The curing conditions at the time of curing the protective film formation film to form a protective film are not particularly limited as long as the protective film has a degree of hardening sufficient to exhibit its function, and may be appropriately selected according to the type of the protective film formation film.

For example, it is preferable that the illumination intensity of the energy ray at the time of hardening of the film for protective film formation is 4-280 mW/cm<2>. And it is preferable that the light quantity of the energy ray at the time of the said hardening is 3-1000 mJ/cm<2>.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the film for protective film formation which concerns on one Embodiment of this invention. In the drawings used in the following description, in order to make it easier to understand the features of the present invention, for convenience, the main parts may be enlarged and shown, and the dimensional ratio of each component is not limited to the same as in reality.

The film 13 for protective film formation shown here is equipped with the 1st peeling film 151 on the one surface (in this specification, it may call a "first surface") 13a, The 2nd peeling film 152 is provided on the other surface (in this specification, the "2nd surface" may be called) 13b on the opposite side to the 1 surface 13a.

Such a film 13 for forming a protective film is suitable for storage in a roll shape, for example.

The film 13 for forming a protective film can be formed using a composition for forming a protective film, which will be described later.

The film 13 for forming a protective film is energy-beam curable.

Both the 1st peeling film 151 and the 2nd peeling film 152 may be a well-known thing.

The 1st peeling film 151 and the 2nd peeling film 152 may be mutually the same, for example, the thing different from each other, such as the peeling force required at the time of peeling from the film 13 for protective film formation mutually different. okay

As for the film 13 for protective film formation shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is affixed on the exposed surface produced by removing either the 1st peeling film 151 and the 2nd peeling film 152. And the exposed surface produced by removing the other one of the 1st peeling film 151 and the 2nd peeling film 152 becomes the pasting surface of a support sheet.

<<Composition for forming a protective film>>

The said film for protective film formation can be formed using the composition for protective film formation containing the constituent material. For example, the film for protective film formation can be formed in the target site|part by coating the composition for protective film formation on the formation target surface of the film for protective film formation, and drying as needed.

In the composition for protective film formation, the content ratio of components which do not vaporize at normal temperature becomes the same as content ratio of the said components of the film for protective film formation normally. In this specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and for example, a temperature of 15 to 25°C and the like.

Coating of the composition for forming a protective film may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater , a method using various coaters, such as a Meyer bar coater and a Keith coater, is mentioned.

Although the drying conditions of the composition for protective film formation are not specifically limited, When the composition for protective film formation contains the solvent mentioned later, it is preferable to heat-dry. It is preferable to dry the composition for protective film formation containing a solvent under conditions for 10 second - 5 minutes at 70-130 degreeC, for example.

<Composition for forming a protective film (IV-1)>

As a composition for protective film formation, the composition (IV-1) for protective film formation containing at least an energy ray-curable component (a) is mentioned.

[Energy-ray-curable component (a)]

The energy-beam-curable component (a) is a component hardened|cured by irradiation of an energy-beam, and is also a component for providing film formability, flexibility, etc. to the film for protective film formation.

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 or more and less than 80000. . The polymer (a1) may be at least partially crosslinked with a crosslinking agent (f) described later, or may not be crosslinked.

In this specification, unless otherwise indicated, a weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000)

Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000 include the above-mentioned adduct type acrylic polymer (a1-1). The adduct type acrylic polymer (a1-1) is an energy ray-curable compound having an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and an energy ray-curable group such as an energy ray-curable double bond with a group reacting with the functional group It can be obtained by reacting (a12).

The functional group capable of reacting with the group of other compounds includes, for example, a hydroxyl group, a carboxy group, an amino group, a substituted amino group (hereinafter, “substituted amino group” refers to a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. means), an epoxy group, etc. are mentioned. However, it is preferable that the said functional group is groups other than a carboxy group from the point of preventing corrosion of circuits, such as a semiconductor wafer and a semiconductor chip.

Among these, it is preferable that the said functional group is a hydroxyl group.

- Acrylic polymer having a functional group (a11)

Examples of the acrylic polymer having the functional group (a11) include those obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer not having the functional group. In addition to these monomers, monomers other than the acrylic monomer ( Non-acrylic monomers) may be copolymerized.

The acrylic polymer (a11) may be a random copolymer or a block copolymer.

Examples of the acrylic monomer having a functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

As the hydroxyl group-containing monomer, for example, (meth) acrylate hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) ) hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic-type unsaturated alcohols (unsaturated alcohol which does not have a (meth)acryloyl skeleton), such as vinyl alcohol and allyl alcohol, etc. are mentioned.

In this specification, let "(meth)acrylic acid" be a concept including both "acrylic acid" and "methacrylic acid." The same is true for terms similar to (meth)acrylic acid.

Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

The number of the acrylic monomers having the functional group constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

As the acrylic monomer having no functional group, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate ) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate ) acrylate isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl (( Also called lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also called myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ((meth)acrylate The alkyl group constituting the alkyl ester such as palmityl acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also called stearyl (meth)acrylate) is a chain structure having 1 to 18 carbon atoms ( meth)acrylic acid alkyl ester etc. are mentioned.

The acrylic monomer having no functional group includes, for example, alkoxyalkyl group-containing (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl, (meth)acrylate ethoxyethyl, etc. meth)acrylic acid ester; (meth)acrylic acid esters having an aromatic group including (meth)acrylic acid aryl esters such as (meth)acrylic acid phenyl; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid ester etc. which have non-crosslinkable tertiary amino groups, such as (meth)acrylic-acid N,N- dimethylaminoethyl, (meth)acrylic-acid N,N- dimethylaminopropyl, etc. are mentioned.

The number of the acrylic monomers having no functional group constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; Styrene etc. are mentioned.

The number of the non-acrylic monomers constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the acrylic polymer (a11) is preferably 0.1 to 50% by mass, 1 It is more preferable that it is -40 mass %, and it is especially preferable that it is 3-30 mass %. When the ratio is within this range, the content of the energy ray-curable group in the adduct type acrylic polymer (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) is cured of the protective film. It becomes easy to control the degree of in a desirable range.

The number of the acrylic polymer (a11) constituting the adduct type acrylic polymer (a1-1) may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

In the composition (IV-1) for forming a protective film, the content of the adduct type acrylic polymer (a1-1) is preferably 1 to 50 mass % with respect to the total mass of the composition (IV-1) for forming a protective film. , It is more preferable that it is 5-40 mass %, and it is especially preferable that it is 10-35 mass %.

・Energy-ray-curable compound (a12)

The energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a11), and as the group It is more preferable to have an isocyanate group. When the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

It is preferable to have 1-5 of the said energy-beam curable groups in 1 molecule, and, as for the said energy-beam-curable compound (a12), it is more preferable to have 1-3.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1,1- (bisacryloyloxymethyl)ethyl isocyanate;

Acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound, and hydroxyethyl (meth)acrylate;

The acryloyl monoisocyanate compound etc. which are obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate are mentioned.

Among these, it is preferable that the said energy-beam-curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

The number of the energy ray-curable compound (a12) constituting the adduct type acrylic polymer (a1-1) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

In the adduct type acrylic polymer (a1-1), the content ratio of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 1 It is preferable that it is -90 mol%, It is more preferable that it is 5-80 mol%, It is still more preferable that it is 10-70 mol%, It is especially preferable that it is 20-40 mol%. When the said content ratio is such a range, the adhesive force of the protective film formed by hardening becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group per molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is a polyfunctional ( In the case of a compound having two or more of the above groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

It is preferable that it is 100000-200000, and, as for the weight average molecular weight (Mw) of the said polymer (a1), it is more preferable that it is 300,000-1500000.

When the polymer (a1) is at least partially crosslinked by the crosslinking agent (f), the polymer (a1) does not correspond to any of the above-mentioned monomers described as constituting the acrylic polymer (a11), In addition, a monomer having a group reactive with the crosslinking agent (f) may be crosslinked in a group reacting with the crosslinking agent (f) by polymerization, or crosslinking in a group reactive with the functional group derived from the energy ray-curable compound (a12) okay

The number of polymers (a1) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

(The compound (a2) having an energy ray-curable group and having a molecular weight of 100 or more and less than 80000)

Among the compounds (a2) having an energy ray-curable group and having a molecular weight of 100 or more and less than 80000, the energy ray-curable group includes a group containing an energy ray-curable double bond, preferably a (meth)acryloyl group, a vinyl group, etc. can be heard

The compound (a2) is not particularly limited as long as it satisfies the above conditions. Examples of the compound (a2) include a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and a phenol resin having an energy ray curable group.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include a polyfunctional monomer or an oligomer, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth). Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxy diethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy) ) Phenyl] propane, tricyclodecane dimethanol di (meth) acrylate (tricyclodecane dimethylol di (meth) acrylate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di ( meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetra Methylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth) 2 such as acryloxyethoxy)phenyl]propane, neopentylglycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane functional (meth)acrylate;

Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri (meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol polyfunctional (meth)acrylates such as poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

Polyfunctional (meth)acrylate oligomers, such as a urethane (meth)acrylate oligomer, etc. are mentioned.

Among the compounds (a2), as an epoxy resin having an energy ray-curable group and a phenol resin having an energy ray-curable group, those described in Paragraph 0043 of, for example, “Unexamined Patent Application Publication No. 2013-194102” can be used. . Although this resin also corresponds to resin which comprises the thermosetting component (h) mentioned later, in this invention, it handles as said compound (a2).

It is preferable that it is 100-30000, and, as for the molecular weight of the said compound (a2), it is more preferable that it is 300-10000.

When the compound (a2) is a monomer, the molecular weight can be calculated from the food. On the other hand, when the compound (a2) is an oligomer, the molecular weight means a weight average molecular weight.

The number of compounds (a2) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When the film for forming a protective film (composition for forming a protective film) contains the energy ray-curable component (a), the energy ray-curable component (a) is polymerized by an energy ray-curable group by ultraviolet irradiation for using the film for forming a protective film as a protective film, , as a result that the low molecular weight polymer is hardly contained in the protective film, the low molecular weight polymer is less likely to segregate on the protective film surface even when the protective film is heated.

When the film for forming a protective film (composition for forming a protective film) contains the energy ray-curable component (a), the film for forming a protective film is affixed to a semiconductor wafer and the gloss value measured after irradiating the energy ray with respect to the protective film formation After the film is affixed to a semiconductor wafer, irradiated with an energy ray, and further heated at 260°C for 5 minutes, the decrease rate of the measured gloss value becomes a low value of 30% or less.

[Polymer (b) having no energy ray-curable group]

The composition (IV-1) for protective film formation and the film for protective film formation may contain the polymer (b) which does not have an energy-beam curable group.

The polymer (b) may be crosslinked at least partly by a crosslinking agent (f) described later, or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include acrylic polymer, phenoxy resin, urethane resin, polyester, rubber resin, acrylic urethane resin, polyvinyl alcohol (PVA), butyral resin, polyester urethane resin. and the like.

Among these, it is preferable that the said polymer (b) is an acrylic polymer (Hereinafter, it may abbreviate as "acrylic polymer (b-1)").

The acrylic polymer (b-1) may be a known one, for example, may be a homopolymer of one type of acrylic monomer, may be a copolymer of two or more types of acrylic monomers, or may be one type or two or more types of acrylic monomer and one type. Or a copolymer of monomers other than 2 or more types of acrylic monomers (non-acrylic monomers) may be sufficient.

As the acrylic monomer constituting the acrylic polymer (b-1), for example, (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid ester, hydroxyl group-containing ( and meth)acrylic acid esters and substituted amino group-containing (meth)acrylic acid esters. Here, the "substituted amino group" is as described above.

Examples of the (meth)acrylic acid alkyl ester include (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, (meth)acrylate ) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate ) acrylate isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl (( Also called lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also called myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ((meth)acrylate The alkyl group constituting the alkyl ester such as palmityl acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (also called stearyl (meth)acrylate) is a chain structure having 1 to 18 carbon atoms ( meth)acrylic acid alkyl ester etc. are mentioned.

Examples of the (meth)acrylic acid ester having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as (meth)acrylic acid isobornyl and (meth)acrylic acid dicyclopentanyl;

(meth)acrylic acid aralkyl esters, such as (meth)acrylic acid benzyl;

(meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester;

(meth)acrylic acid cycloalkenyloxyalkyl esters, such as (meth)acrylic-acid dicyclopentenyloxyethyl ester, etc. are mentioned.

As said glycidyl group containing (meth)acrylic acid ester, (meth)acrylic acid glycidyl etc. are mentioned, for example.

As the hydroxyl group-containing (meth)acrylic acid ester, for example, (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxy propyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl, (meth)acrylic acid 4-hydroxybutyl, etc. are mentioned.

As said substituted amino-group containing (meth)acrylic acid ester, (meth)acrylic-acid N-methylaminoethyl etc. are mentioned, for example.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; Styrene etc. are mentioned.

Examples of the polymer (b) having no energy ray-curable group at least partially crosslinked with the cross-linking agent (f) include those in which the reactive functional group in the polymer (b) reacted with the cross-linking agent (f).

The reactive functional group may be appropriately selected according to the type of the crosslinking agent (f), and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxy group, and an amino group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent (f) is an epoxy compound, the reactive functional group includes a carboxy group, an amino group, an amide group, and the like, and among these, a carboxy group having high reactivity with an epoxy group is preferable. However, it is preferable that the said reactive functional group is a group other than a carboxy group from the point of preventing corrosion of the circuit of a semiconductor wafer or a semiconductor chip.

As a polymer (b) which does not have an energy-beam curable group which has the said reactive functional group, what was obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer may be used as a monomer constituting the acrylic polymer (b-1), having the reactive functional group. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerization of a hydroxyl group-containing (meth)acrylic acid ester. In addition, in the above-mentioned acrylic monomer or non-acrylic monomer, one or two What is obtained by superposing|polymerizing the monomer which consists of two or more hydrogen atoms substituted with the said reactive functional group is mentioned.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the structural unit constituting it is preferably 1 to 25% by mass, , it is more preferable that it is 2-20 mass %. When the said ratio is in such a range, in the said polymer (b), the degree of crosslinking becomes a more preferable range.

When the content of the polymer (b) having no low molecular weight energy ray-curable group in the film for forming a protective film is large, when the semiconductor chip having a protective film, which is a cured product of the film for forming a protective film, is heated for the purpose of bonding, etc., the protective film The surface gloss is reduced.

It is preferable that the weight average molecular weight (Mw) of the polymer (b) which does not have an energy-ray-curable group is 200000 or more, It is more preferable that it is 250000 or more, It is still more preferable that it is 300000 or more. If the weight average molecular weight of the polymer (b) having no energy ray-curable group is equal to or greater than the lower limit, the gloss of the surface of the protective film is improved even when a semiconductor chip having a protective film, which is a cured product of the film for forming a protective film on the back surface, is heated by bonding or the like. hard to lower The upper limit of the weight average molecular weight of the polymer (b) not having an energy ray curable group is not particularly limited, but from the viewpoint of easy production of the composite sheet for forming a protective film, the weight average molecular weight of the polymer (b) not having an energy ray curable group is It is preferable that it is 2000000 or less. The dispersibility in the composition (IV-1) for protective film formation becomes favorable that the weight average molecular weight of the polymer (b) which does not have an energy-ray-curable group is 2000000 or less.

As a combination of an upper limit and a lower limit, 200000 or more and 2000000 or less, 250000 or more and 2000000 or less, and 300000 or more and 2000000 or less are mentioned.

When the weight average molecular weight (Mw) of the polymer (b) not having an energy ray curable group is less than the above lower limit, the polymer (b) not having an energy ray curable group is used as an adduct body, and an energy ray curable group such as an energy ray curable double bond is It is preferable to introduce

Specifically, the adduct body of the polymer (b) not having an energy ray-curable group includes a polymer (b) not having an energy ray-curable group having a functional group capable of reacting with a group of another compound, and a group reactive with the functional group and energy ray-curable group. It can obtain by reacting an energy-beam curable compound which has energy-beam curable groups, such as a double bond.

When the polymer (b) which does not have an energy ray-curable group is an acrylic polymer, an adduct body can be obtained by the method similar to the above-mentioned adduct type acrylic polymer (a1-1).

When the polymer (b) not having an energy ray-curable group is used as an adduct body and an energy ray-curable group such as an energy ray-curable double bond is introduced, polymerization is performed by the energy ray-curable group by ultraviolet irradiation to make the film for forming a protective film as a protective film. Therefore, the low molecular weight polymer is hardly contained in the protective film, and even when the protective film is heated, it becomes difficult for the low molecular weight polymer to segregate on the protective film surface.

When the polymer (b) not having an energy ray-curable group is used as an adduct body and an energy ray-curable group such as an energy ray-curable double bond is introduced, the film for forming a protective film is affixed to a semiconductor wafer, and the gloss measured after irradiation with an energy ray The decrease rate of the gloss value measured after affixing the said film for protective film formation with respect to a value to a semiconductor wafer, irradiating an energy ray, and heating at 260 degreeC for 5 minute(s) becomes a low value of 30 % or less.

The composition (IV-1) for forming a protective film and the polymer (b) having no energy ray-curable group contained in the film for forming a protective film may be one type, or two or more types, and in the case of two or more types, these combinations and ratios are can be chosen arbitrarily.

The composition (IV-1) for forming a protective film preferably contains the compound (a2) and the polymer (a1). It is also preferable that the composition (IV-1) for forming a protective film contains the polymer (a1) and the compound (a2) and does not contain the polymer (b) having no energy ray-curable group. The composition (IV-1) for forming a protective film may contain the said polymer (a1) without containing the said compound (a2).

The polymer (a1) is preferably an adduct type acrylic polymer (a1-1).

When the composition (IV-1) for forming a protective film contains the polymer (a1) and the compound (a2), the content of the compound (a2) in the composition (IV-1) for forming a protective film is the polymer (a1). ) with respect to 100 mass parts of total content, it is preferable that it is 10-400 mass parts, and it is more preferable that it is 30-350 mass parts.

In the composition (IV-1) for forming a protective film, the content of the energy ray-curable component (a) with respect to the total content of components other than the solvent is preferably 12 to 90 mass%, more preferably 15 to 80 mass% It is preferable, and it is especially preferable that it is 20-70 mass %, For example, any of 25-60 mass % and 30-50 mass % may be sufficient. When the said content is such a range, the energy-beam sclerosis|hardenability of the film for protective film formation becomes more favorable.

When the composition (IV-1) for forming a protective film contains the adduct-type acrylic polymer (a1-1), in the composition (IV-1) for forming a protective film and the film for forming a protective film, the polymer (a1-1) It is preferable that content of is 30-100 mass parts with respect to content of 100 mass parts of energy-beam curable component (a), It is more preferable that it is 50-95 mass parts, It is especially preferable that it is 70-90 mass parts. When the said content of the said polymer (a1-1) is such a range, the energy-beam sclerosis|hardenability of the film for protective film formation becomes more favorable.

The composition (IV-1) for forming a protective film is a photopolymerization initiator (c), a filler (d), a coupling agent (e) other than the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group depending on the purpose , a crosslinking agent (f), a colorant (g), a thermosetting component (h), a curing accelerator (i), and a general-purpose additive (z) may contain one or more selected from the group consisting of.

For example, by using the composition (IV-1) for forming a protective film containing the energy ray-curable component (a) and the thermosetting component (h), the formed film for forming a protective film has an adhesive strength to an adherend by heating. It improves and the intensity|strength of the protective film formed from this film for protective film formation also improves.

[Photoinitiator (c)]

Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, and the like. benzoin compounds; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; Benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H benzophenone compounds such as -carbazol-3-yl]-,1-(O-acetyloxime); peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone etc. are mentioned.

As a photoinitiator (c), For example, Quinone compounds, such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. can also be used.

The number of photoinitiators (c) contained in the composition (IV-1) for protective film formation may be one, and two or more types may be sufficient as them, and in the case of two or more types, these combinations and a ratio can be selected arbitrarily.

When using a photoinitiator (c), in the composition (IV-1) for protective film formation, content of a photoinitiator (c) is 0.01-20 mass parts with respect to content of 100 mass parts of energy ray-curable compound (a) It is preferable, It is more preferable that it is 0.03-15 mass parts, It is especially preferable that it is 0.05-10 mass parts.

[Filling material (d)]

When the film for protective film formation contains a filler (d), adjustment of a thermal expansion coefficient becomes easy for the protective film obtained by hardening|curing the film for protective film formation. And the reliability of the package obtained using the composite sheet for protective film formation improves more by optimizing this thermal expansion coefficient with respect to the formation target of a protective film. When the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced, or heat dissipation can also be improved.

As a filler (d), what consists of a thermally conductive material is mentioned, for example.

Although any of an organic filler and an inorganic filler may be sufficient as a filler (d), it is preferable that it is an inorganic filler.

Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned.

Among these, the inorganic filler is preferably silica or alumina.

Although the average particle diameter of a filler (d) is not specifically limited, It is preferable that it is 0.01-20 micrometers, It is more preferable that it is 0.1-15 micrometers, It is especially preferable that it is 0.3-10 micrometers. When the average particle diameter of the filler (d) is within such a range, a decrease in the transmittance of light of the protective film can be suppressed while maintaining the adhesiveness to the object to be formed of the protective film.

In this specification, unless otherwise indicated, "average particle diameter" means the value of the particle diameter (D50) at ₅₀ % of the integrated value in the particle size distribution curve calculated|required by the laser diffraction scattering method.

The number of fillers (d) which the composition (IV-1) for protective film formation and the film for protective film formation contain may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and ratio can be selected arbitrarily.

When the filler (d) is used, in the composition (IV-1) for forming a protective film, the content ratio of the filler (d) to the total content of all components other than the solvent (that is, the filler (d) in the film for forming a protective film) content) is preferably 10-85 mass%, more preferably 20-80 mass%, particularly preferably 30-75 mass%, for example, 40-70 mass% and 45-65 mass%. % may be any. When content of a filler (d) is such a range, adjustment of the said thermal expansion coefficient becomes easier.

[Coupling agent (e)]

By using what has a functional group which can react with an inorganic compound or an organic compound as a coupling agent (e), the adhesiveness with respect to the to-be-adhered body of the film for protective film formation, and adhesiveness can be improved. By using a coupling agent (e), the protective film obtained by hardening the film for protective film formation does not impair heat resistance, but water resistance improves.

It is preferable that it is a compound which has a functional group which can react with the functional group which the energy ray-curable component (a), a polymer (b) which does not have an energy-beam curable group, etc. have, and, as for a coupling agent (e), it is more preferable that it is a silane coupling agent.

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltriethoxysilane. Cydyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-( 2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltri Ethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

The number of coupling agents (e) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When using a coupling agent (e), the composition (IV-1) for protective film formation and the film for protective film formation WHEREIN: Content of a coupling agent (e) with respect to content of 100 mass parts of energy ray-curable component (a), It is preferable that it is 0.03-20 mass parts, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.1-5 mass parts.

Since the said content of a coupling agent (e) is more than the said lower limit, the improvement of the dispersibility with respect to resin of a filler (d), the improvement of adhesiveness with the to-be-adhered body of the film for protective film formation, etc. In using a coupling agent (e) effect is obtained more significantly. Moreover, since the said content of a coupling agent (e) is below the said upper limit, generation|occurrence|production of an outgas is suppressed more.

[Crosslinking agent (f)]

By using the crosslinking agent (f) to crosslink the above-described energy ray-curable component (a) or the polymer (b) having no energy ray-curable group, the initial adhesive force and cohesive force of the film for forming a protective film can be adjusted.

Examples of the crosslinking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate crosslinking agent (crosslinking agent having a metal chelate structure), and an aziridine crosslinking agent (crosslinking agent having an aziridinyl group).

As said organic polyhydric isocyanate compound, For example, an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (Hereinafter, these compounds are collectively abbreviated as "aromatic polyvalent isocyanate compound etc."); trimers, isocyanurate compounds, and adducts such as the above aromatic polyvalent isocyanate compounds; The terminal isocyanate urethane prepolymer etc. which are obtained by making the said aromatic polyhydric isocyanate compound etc. react with a polyol compound are mentioned. The "adduct body" refers to the aromatic polyhydric isocyanate compound, aliphatic polyvalent isocyanate compound, or alicyclic polyvalent isocyanate compound, and low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. means reactants. As an example of the said adduct body, the xylylene diisocyanate adduct etc. which are mentioned later of trimethylol propane are mentioned. "Terminal isocyanate urethane prepolymer" means a prepolymer which has an isocyanate group in the terminal part of a molecule|numerator while having a urethane bond.

More specifically, as said organic polyhydric isocyanate compound, For example, 2, 4- tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; Compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate were added to all or some hydroxyl groups of polyols such as trimethylolpropane; Lysine diisocyanate etc. are mentioned.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine, etc. are mentioned.

When using an organic polyhydric isocyanate compound as a crosslinking agent (f), it is preferable to use a hydroxyl-containing polymer as an energy-beam curable component (a) or a polymer (b) which does not have an energy-beam curable group. When the crosslinking agent (f) has an isocyanate group, and the energy ray-curable component (a) or the polymer (b) not having an energy ray-curable group has a hydroxyl group, the cross-linking agent (f) and the energy ray-curable component (a) or energy ray-curable group By reaction of the polymer (b) which does not have, a crosslinked structure can be easily introduce|transduced into the film for protective film formation.

The number of crosslinking agents (f) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When a crosslinking agent (f) is used, in the composition (IV-1) for forming a protective film, the content of the crosslinking agent (f) is 100 total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group It is preferable that it is 0.01-20 mass parts with respect to mass part, It is more preferable that it is 0.1-10 mass parts, It is especially preferable that it is 0.5-5 mass parts. Since the said content of a crosslinking agent (f) is more than the said lower limit, the effect by using a crosslinking agent (f) is acquired more remarkably. Since the said content of a crosslinking agent (f) is below the said upper limit, excessive use of a crosslinking agent (f) is suppressed.

[Colorant (g)]

As a coloring agent (g), well-known things, such as an inorganic type pigment, an organic type pigment, and organic type dye, are mentioned, for example.

The organic pigments and organic dyes include, for example, aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squarylium pigments, azrenium pigments, polymethine pigments, and naphthoquinone pigments. , pyrylium pigment, phthalocyanine pigment, naphthalocyanine pigment, naphtholactam pigment, azo pigment, condensed azo pigment, indigo pigment, perinone pigment, perylene pigment, dioxazine pigment, quinacridone pigment, Isoindolinone pigment, quinophthalone pigment, pyrrole pigment, thioindigo pigment, metal complex pigment (metal complex dye), dithiol metal complex pigment, indole phenol pigment, triarylmethane pigment, anthra A quinone type pigment|dye, a naphthol type pigment|dye, an azomethine type pigment|dye, a benzimidazolone type pigment|dye, a pyranthrone type pigment|dye, a srene type pigment|dye, etc. are mentioned.

Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium pigments). A tin oxide) type pigment|dye, ATO (antimony tin oxide) type pigment|dye, etc. are mentioned.

The number of the colorants (g) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When using a coloring agent (g), what is necessary is just to adjust content of the coloring agent (g) of the composition (IV-1) for protective film formation and the film for protective film formation suitably according to the objective. For example, when the print visibility is adjusted by adjusting the content of the colorant (g) to control the light transmittance of the protective film, in the composition (IV-1) for forming a protective film, the total content of all components other than the solvent is It is preferable that the content ratio of the coloring agent (g) (that is, content of the coloring agent (g) of the film for protective film formation) is 0.1-10 mass %, It is more preferable that it is 0.4-7.5 mass %, It is 0.8-5 mass % It is particularly preferred. Since the said content of a coloring agent (g) is more than the said lower limit, the effect by using a coloring agent (g) is acquired more remarkably. Since the said content of a coloring agent (g) is below the said upper limit, excessive use of a coloring agent (g) is suppressed.

[thermosetting component (h)]

The number of thermosetting components (h) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

Examples of the thermosetting component (h) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters and silicone resins, and epoxy thermosetting resins are preferred.

(epoxy thermosetting resin)

The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).

The number of epoxy thermosetting resins contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

・Epoxy resin (h1)

A well-known thing is mentioned as an epoxy resin (h1), For example, polyfunctional epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, ortho cresol novolac epoxy resin, dicyclopentadiene. Bifunctional or more than bifunctional epoxy compounds, such as a type|mold epoxy resin, a biphenyl type epoxy resin, a bisphenol A type|mold epoxy resin, a bisphenol F type|mold epoxy resin, and a phenylene skeleton type|mold epoxy resin, are mentioned.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group may be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. For this reason, the reliability of the package obtained using the composite sheet for protective film formation improves by using the epoxy resin which has an unsaturated hydrocarbon group.

As the epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a part of the epoxy groups of the polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group is exemplified. Such a compound is obtained, for example, by addition-reacting (meth)acrylic acid or its derivative(s) to an epoxy group.

Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple|bonded with the aromatic ring which comprises an epoxy resin etc. are mentioned, for example.

The unsaturated hydrocarbon group is an unsaturated group having polymerizability, and specific examples thereof include an ethenyl group (also called a vinyl group), a 2-propenyl group (also called an allyl group), a (meth)acryloyl group, a (meth)acrylamide group, and the like. These are mentioned, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000, more preferably 400 to 10000, and more preferably 500 to 3000 is particularly preferred.

In this specification, unless otherwise indicated, "number average molecular weight" means the number average molecular weight represented by the standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method. It is preferable that it is 100-1000 g/eq, and, as for the epoxy equivalent of an epoxy resin (h1), it is more preferable that it is 150-800 g/eq.

In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

An epoxy resin (h1) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, these combinations and a ratio can be selected arbitrarily.

· Thermosetting agent (h2)

The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).

As a thermosetting agent (h2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. The functional group includes, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acid group is anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrideized is preferable, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrized. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenol resins. can

Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.

Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin, etc. can

The said unsaturated hydrocarbon group in a thermosetting agent (h2) is the same thing as the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermal curing agent (h2), the thermal curing agent (h2) preferably has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the supporting sheet.

In this specification, a "glass transition temperature" is represented by the temperature of the inflection point of the DSC curve obtained by measuring the DSC curve of a sample using a differential scanning calorimeter.

Among the thermosetting agents (h2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-based phenol resin, and an aralkyl phenol resin is preferably 300 to 30000, It is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Although the molecular weight of non-resin components, such as a biphenol and dicyandiamide, among thermosetting agents (h2) is not specifically limited, For example, it is preferable that it is 60-500.

A thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, these combinations and a ratio can be selected arbitrarily.

When using a thermosetting component (h), the composition for protective film formation (IV-1) and the film for protective film formation WHEREIN: Content of a thermosetting agent (h2) is 0.01-0.01 with respect to content of 100 mass parts of an epoxy resin (h1). It is preferable that it is 20 mass parts.

When a thermosetting component (h) is used, in the composition (IV-1) for protective film formation and the film for protective film formation, content of the thermosetting component (h) (for example, an epoxy resin (h1) and a thermosetting agent (h2)) It is preferable that the total content of) is 1-500 mass parts with respect to content 100 mass parts of a polymer (b) which does not have an energy-beam curable group.

[curing accelerator (i)]

A hardening accelerator (i) is a component for adjusting the cure rate of the film for protective film formation.

As a preferable hardening accelerator (i), For example, tertiary amines, such as triethylenediamine, benzyldimethylamine, a triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 - imidazoles, such as hydroxymethyl imidazole; organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine; Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. are mentioned.

A hardening accelerator (i) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, these combinations and a ratio can be selected arbitrarily.

When using hardening accelerator (i), content of the hardening accelerator (i) of the composition (IV-1) for protective film formation and the film for protective film formation is not specifically limited, What is necessary is just to select suitably according to the component used together.

[Universal Additive (z)]

The general-purpose additive (z) may be a well-known one, can be arbitrarily selected according to the purpose, and is not particularly limited, and preferable examples thereof include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, and the like.

The number of general-purpose additives (z) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

When using a general-purpose additive (z), content of the composition (IV-1) for protective film formation and the general-purpose additive (z) of the film for protective film formation is not specifically limited, What is necessary is just to select suitably according to the objective.

[menstruum]

It is preferable that the composition (IV-1) for protective film formation further contains a solvent. The handleability of the composition (IV-1) for protective film formation containing a solvent becomes favorable.

The solvent is not particularly limited, but is preferably, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

The number of solvents contained in the composition (IV-1) for forming a protective film may be one, or two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The solvent contained in the composition (IV-1) for forming a protective film is preferably methyl ethyl ketone, toluene or ethyl acetate, etc. from the viewpoint of more uniformly mixing the components contained in the composition (IV-1) for forming a protective film. .

One aspect of the present invention is that the film for forming a protective film is a polymer (a1) having an energy ray-curable group, and the adduct type acrylic polymer (a1-1) is used in an amount of 25 to 35 mass % with respect to the total mass of the film for forming a protective film, energy ray 5-15 mass % of ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate as the compound (a2) having a curable group with respect to the total mass of the film for forming a protective film, 2-( 0.3-0.9 mass % of dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone relative to the total mass of the film for forming a protective film, and a silica filler as a filler (d) for forming a protective film It is a film for protective film formation containing 52-62 mass % with respect to the gross mass of a film, 0.1-0.7 mass % of 3-methacryloxypropyl trimethoxysilane as a coupling agent (e) with respect to the gross mass of the film for protective film formation .

On the other hand, the adduct-type acrylic polymer (a1-1) is an acrylic polymer (a11) formed by copolymerizing methyl acrylate and 2-hydroxyethyl acrylate, and 2-methacryloyloxyethyl isocyanate as the energetically curable compound (a12). It is preferably obtained by reacting

Moreover, it is preferable that the content ratio of the energy ray-curable group derived from the said energetic sclerosing|hardenable compound (a12) with respect to content of the functional group derived from the said acrylic polymer (a11) is 5-50 mol%, and it is 20-40 mol % is more preferable. Moreover, 2-15 mol% may be sufficient as the said ratio.

Moreover, it is preferable that the said film for protective film formation does not contain the polymer (b) which does not have an energy-beam curable group.

In another aspect of the present invention, 25-40 parts by mass of a phthalocyanine-based blue dye, 10-25 parts by mass of an isoindolinone-based yellow dye, and 40-60 parts by mass of an anthraquinone-based red dye are mixed as a colorant (g) further, It is preferable that it is a film for protective film formation containing 1-5 mass % of the pigment obtained by pigmentation so that it may become the sum total of the said three types of pigment/styrene acrylic resin amount = 1/3 (mass ratio) with respect to the total mass of the film for protective film formation. .

<<The manufacturing method of the composition for protective film formation>>

A composition for forming a protective film, such as the composition (IV-1) for forming a protective film, is obtained by blending each component constituting the composition.

The order of addition at the time of mixing|blending each component is not specifically limited, You may add 2 or more types of components simultaneously.

When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and this compounding component may be used by diluting in advance, and the solvent may be mixed with these compounding components without diluting any compounding component other than the solvent in advance. You may use it by

A method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Manufacturing method of film for protective film formation

The said film for protective film formation can be manufactured by coating the composition for protective film formation on a peeling film (preferably, the peeling process surface), and drying it as needed. The manufacturing method at this time is as described above.

As shown, for example in FIG. 1, the film for protective film formation is normally stored in the state by which the peeling film was pasted on the both surfaces. For this purpose, the release film (preferably the peeling-treated surface) may be further bonded to the exposed surface (the surface opposite to the side provided with the release film) of the film for forming a protective film formed on the release film as described above. .

◇How to use the film for the protective film formation

As mentioned above, the said film for protective film formation can comprise the composite sheet for protective film formation by forming on a support sheet. The composite sheet for protective film formation is affixed on the back surface (surface opposite to an electrode formation surface) of a semiconductor wafer with the film for protective film formation. Then, in this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method mentioned later.

In addition, you may form the said film for protective film formation first on the back surface of a semiconductor wafer instead of a support sheet. For example, first, the film for forming a protective film is affixed to the back surface of a semiconductor wafer, and a support sheet is bonded to the exposed surface (surface opposite to the side affixed to the semiconductor wafer) of this film for protective film formation, or this affixing After irradiating an energy ray to the film for forming a protective film in one state, curing it to form a protective film, and bonding a support sheet to the exposed surface of this protective film (the surface opposite to the side affixed to the semiconductor wafer), the protective film formation composite make it a sheet Then, in this state, the target semiconductor chip and semiconductor device can be manufactured by the manufacturing method mentioned later.

◇Composite sheet for the protective film formation

The composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet, and the film for forming a protective film is provided on the support sheet.

In the present invention, even after the film for forming a protective film is cured, as long as the laminate structure of the support sheet and the cured product of the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, this laminated structure is referred to as “for forming a protective film”. composite sheet".

Although the thickness of the semiconductor wafer which is the object of use of the composite sheet for forming a protective film of the present invention is not particularly limited, in terms of easier division into semiconductor chips to be described later, it is preferably 30 to 1000 µm, and 100 to 400 µm more preferably.

Hereinafter, the structure of the composite sheet for protective film formation is demonstrated in detail.

◎Support sheet

The said support sheet may consist of one layer (single layer), and may consist of multiple layers of two or more layers. When a support sheet consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited unless the effect of this invention is impaired.

Preferred support sheets include, for example, those having a base material and having a pressure-sensitive adhesive layer laminated on the base material in direct contact with each other (a base material and a pressure-sensitive adhesive layer being laminated in direct contact with each other in this order); a base material, an intermediate|middle layer, and an adhesive layer being laminated|stacked in direct contact with these in these thickness direction in this order; What consists only of a base material, etc. are mentioned.

An example of the composite sheet for protective film formation of this invention is demonstrated, referring drawings for every kind of such a support sheet below.

It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention.

In the drawings after FIG. 2, the same components as those shown in the previously described drawings are given the same reference numerals as in the illustrated drawings, and detailed descriptions thereof are omitted.

The composite sheet 1A for protective film formation shown here is equipped with the base material 11, The adhesive layer 12 is provided on the base material 11, The film 13 for protective film formation is provided on the adhesive layer 12. are being prepared The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 , and the composite sheet 1A for forming a protective film is, in other words, one surface of the support sheet 10 (in this specification, the “first It has a structure in which the film 13 for protective film formation was laminated|stacked on 10a (sometimes referred to as "surface"). 1 A of composite sheet|seats for protective film formation are equipped with the peeling film 15 on the film 13 for protective film formation further.

In 1A of composite sheet for protective film formation, the adhesive layer 12 is laminated|stacked on one surface (in this specification, it may call a "first surface") 11a of the base material 11, and an adhesive layer The film 13 for forming a protective film is laminated|stacked on the whole surface of the one surface (in this specification, the "first surface" may be called) 12a of (12), the 1st of the film 13 for protective film formation. The adhesive layer 16 for a jig is laminated on a part of the surface 13a, that is, in a region near the periphery, and the adhesive layer 16 for a jig is laminated on the first surface 13a of the film 13 for forming a protective film. The release film 15 is laminated|stacked on the surface 16a (upper surface and side surface) of the surface which is not and the adhesive bond layer 16 for jig|tools.

In the composite sheet 1A for forming a protective film, the film 13 for forming a protective film contains an energy ray-curable component (a), and it is preferable that the adduct type acrylic polymer (a1-1) is used as (a). .

The adhesive layer 16 for a jig may have a single-layer structure containing an adhesive component, or may have a multi-layer structure in which layers containing an adhesive component are laminated on both surfaces of a sheet serving as a core material.

In the composite sheet 1A for forming a protective film shown in Fig. 2, in a state in which the release film 15 is removed, the back surface of a semiconductor wafer (not shown) is affixed to the first surface 13a of the film 13 for forming a protective film, In addition, the upper surface of the surface 16a of the adhesive bond layer 16 for jigs is affixed to jigs, such as a ring frame, and is used.

3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to another embodiment of the present invention.

The composite sheet 1B for protective film formation shown here is the same as that of 1 A of composite sheets for protective film formation shown in FIG. 2 except the point which is not equipped with the adhesive bond layer 16 for jig|tools. That is, in the composite sheet 1B for protective film formation, the adhesive layer 12 is laminated|stacked on the 1st surface 11a of the base material 11, The protective film on the whole surface of the 1st surface 12a of the adhesive layer 12. The film 13 for formation is laminated|stacked, and the release film 15 is laminated|stacked on the whole surface of the 1st surface 13a of the film 13 for protective film formation.

In the composite sheet 1B for forming a protective film, the film 13 for forming a protective film contains an energy ray-curable component (a), and as (a), it is preferable that the adduct type acrylic polymer (a1-1) is used. .

The composite sheet 1B for forming a protective film shown in Fig. 3 is a semiconductor wafer (shown in the figure) in a central portion of the first surface 13a of the film for forming a protective film 13 in a state in which the release film 15 is removed. abbreviation) is pasted, and the area|region in the vicinity of a periphery is further pasted to jigs, such as a ring frame, and is used.

4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.

1 C of composite sheets for protective film formation shown here are the same as 1A of composite sheets for protective film formation shown in FIG. 2 except the point which is not equipped with the adhesive layer 12. As shown in FIG. That is, in 1 C of composite sheets for protective film formation, the support sheet 10 consists only of the base material 11. As shown in FIG. And the film 13 for protective film formation is laminated|stacked on the 1st surface 11a of the base material 11 (1st surface 10a of the support sheet 10), and the 1st surface of the film 13 for protective film formation A part of (13a), that is, the adhesive layer 16 for a jig is laminated in a region near the periphery, and the adhesive layer 16 for a jig is not laminated on the first surface 13a of the film 13 for forming a protective film. The release film 15 is laminated|stacked on the surface 16a (upper surface and side surface) of the area|region where it is not and the adhesive bond layer 16 for a jig|tool.

In the composite sheet for forming a protective film (1C), the film for forming a protective film (13) contains an energy ray-curable component (a), and the adduct type acrylic polymer (a1-1) is preferably used as the (a). .

The composite sheet 1C for protective film formation shown in FIG. 4 is the state from which the peeling film 15 was removed similarly to 1 A of composite sheets for protective film formation shown in FIG. 2, The 1st of the film 13 for protective film formation The back surface of a semiconductor wafer (not shown) is affixed to the surface 13a, and the upper surface among the surfaces 16a of the adhesive bond layer 16 for jigs is affixed to jigs, such as a ring frame, and is used further.

5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.

The composite sheet 1D for protective film formation shown here is the same as 1C of composite sheets for protective film formation shown in FIG. 4 except the point which is not equipped with the adhesive bond layer 16 for jig|tools. That is, in the composite sheet 1D for protective film formation, the film 13 for protective film formation is laminated|stacked on the 1st surface 11a of the base material 11, The 1st surface 13a of the film 13 for protective film formation A release film 15 is laminated on the entire surface of the

In the composite sheet 1D for forming a protective film, the film 13 for forming a protective film contains an energy ray-curable component (a), and as (a), the adduct type acrylic polymer (a1-1) is preferable. .

The composite sheet 1D for protective film formation shown in FIG. 5 is the state from which the peeling film 15 was removed similarly to the composite sheet 1B for protective film formation shown in FIG. 3, The 1st surface of the film 13 for protective film formation In (13a), the back surface of a semiconductor wafer (not shown) is affixed to a central-side part area|region, and the area|region in the vicinity of a periphery is attached and used by jigs, such as a ring frame.

6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.

The composite sheet 1E for protective film formation shown here is the same as that of the composite sheet 1B for protective film formation shown in FIG. 3 except the point from which the shape of the film for protective film formation differs. That is, the composite sheet 1E for forming a protective film includes a substrate 11 , a pressure-sensitive adhesive layer 12 on the substrate 11 , and a film 23 for forming a protective film on the pressure-sensitive adhesive layer 12 . is done by The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 , and the composite sheet 1E for forming a protective film, in other words, forms a protective film on the first surface 10a of the support sheet 10 . It has a structure in which the film 23 for use was laminated|stacked. The composite sheet 1E for protective film formation is further equipped with the peeling film 15 on the film 23 for protective film formation.

In the composite sheet 1E for protective film formation, the adhesive layer 12 is laminated|stacked on the 1st surface 11a of the base material 11, and the 1st surface 12a of the adhesive layer 12 is a part, ie, the center. The film 23 for forming a protective film is laminated|stacked on the side area|region. And peeling on the area|region on which the film 23 for protective film formation is not laminated|stacked among the 1st surface 12a of the adhesive layer 12, and the surface 23a (upper surface and side surface) of the film 23 for protective film formation Films 15 are laminated.

When the composite sheet 1E for protective film formation is looked down from the top and planar view, the film 23 for protective film formation has a smaller surface area than the adhesive layer 12, For example, it has shapes, such as a circular shape.

In the composite sheet 1E for forming a protective film, the film 23 for forming a protective film contains an energy ray-curable component (a), and as (a), the adduct type acrylic polymer (a1-1) is preferable. .

In the composite sheet 1E for forming a protective film shown in Fig. 6, the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the film 23 for forming a protective film in a state in which the release film 15 is removed, and further The area|region on which the film 23 for protective film formation is not laminated|stacked among the 1st surface 12a of the furnace adhesive layer 12 is affixed to jigs, such as a ring frame, and is used.

In the composite sheet 1E for protective film formation shown in FIG. 6, among the 1st surface 12a of the adhesive layer 12, in the area|region where the film 23 for protective film formation is not laminated|stacked, shown in FIG. 2 and FIG. The adhesive layer for jig|tools may be laminated|stacked similarly to the thing (not shown). The composite sheet 1E for forming a protective film provided with such an adhesive layer for a jig is used by affixing the surface of the adhesive layer for a jig to a jig such as a ring frame, similarly to the composite sheet for forming a protective film shown in FIGS. 2 and 4 .

Thus, whatever form the support sheet and the film for protective film formation may be provided with the adhesive bond layer for jigs, the composite sheet for protective film formation may be sufficient as it. However, normally, as shown in FIG.2 and FIG.4, as a composite sheet for protective film formation provided with the adhesive bond layer for jigs, it is preferable that the adhesive bond layer for jigs was provided on the film for protective film formation.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to that shown in Figs. 2 to 6, and within a range that does not impair the effects of the present invention, some configurations of those shown in Figs. What has been changed or deleted, or what has been described so far may be one in which another configuration is added.

For example, in the composite sheet for protective film formation shown in FIG.4 and FIG.5, the intermediate|middle layer may be formed between the base material 11 and the film 13 for protective film formation. As the intermediate layer, any one can be selected depending on the purpose.

In the composite sheet for protective film formation shown in FIG. 2, FIG. 3, and FIG. 6, the intermediate|middle layer may be formed between the base material 11 and the adhesive layer 12. As shown in FIG. That is, the composite sheet for protective film formation of this invention WHEREIN: As for a support sheet, the base material, an intermediate|middle layer, and an adhesive layer may be laminated|stacked in this order in these thickness direction. Here, an intermediate|middle layer is the same as that of the intermediate|middle layer which may be formed in the composite sheet for protective film formation shown in FIG.4 and FIG.5.

As for the composite sheet for protective film formation shown to FIGS. 2-6, layers other than the said intermediate|middle layer may be formed in arbitrary positions.

In the composite sheet for protective film formation, a part of clearance gap may arise between the peeling film and the layer in direct contact with this peeling film.

In the composite sheet for forming a protective film, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

In the composite sheet for forming a protective film of the present invention, it is preferable that the layer in direct contact with the film for forming a protective film of a supporting sheet such as an adhesive layer is non-energy-ray-curable so as to be described later. Such a composite sheet for forming a protective film enables easier pickup of the semiconductor chip on which the protective film is formed.

The support sheet may be transparent, may be opaque, or may be colored according to the purpose.

Especially, in this invention in which the film for protective film formation has energy-beam sclerosis|hardenability, it is preferable for a support sheet to permeate|transmit an energy-beam.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance|permeability of the said light is such a range and an energy ray (ultraviolet ray) is irradiated to the film for protective film formation through a support sheet, the hardening degree of the film for protective film formation improves more.

In addition, in a support sheet, the upper limit of the transmittance|permeability of the light whose wavelength is 375 nm is not specifically limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.

When the transmittance of the light is within such a range, the film for forming a protective film or the protective film through a support sheet is irradiated with laser light and printed on them more clearly.

In addition, in a support sheet, the upper limit of the transmittance|permeability of the light whose wavelength is 532 nm is not specifically limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is within such a range, the film for forming a protective film or the protective film through a support sheet is irradiated with laser light and printed on them more clearly.

In addition, in a support sheet, the upper limit of the transmittance|permeability of the light whose wavelength is 1064 nm is not specifically limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1342 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is within this range, the modified layer can be more easily formed on the semiconductor wafer by irradiating laser light to the semiconductor wafer through the support sheet and the film or protective film for forming a protective film.

In addition, in a support sheet, the upper limit of the transmittance|permeability of the light whose wavelength is 1342 nm is not specifically limited. For example, the transmittance of the light may be 95% or less.

Next, each layer constituting the support sheet will be described in more detail.

○ Mention

The said base material is a sheet form or a film form, and various resin is mentioned as the constituent material, for example.

Examples of the resin include polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-norbornene copolymer (copolymer obtained using ethylene as a monomer) ; vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymer (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyester in which all structural units have an aromatic ring group; a copolymer of two or more of the above polyesters; poly(meth)acrylic acid ester; Polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene oxide; polyphenylene sulfide; polysulfone; Polyether ketone etc. are mentioned.

As said resin, polymer alloys, such as a mixture of the said polyester and other resin, are also mentioned, for example. In the polymer alloy of the polyester and other resins, it is preferable that the amount of the resin other than the polyester is relatively small.

Examples of the resin include a crosslinked resin in which one or two or more of the above-mentioned resins are crosslinked; Modified resins, such as an ionomer using 1 type(s) or 2 or more types of the said resin illustrated so far, are also mentioned.

The number of resins constituting the substrate may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The base material may consist of one layer (single layer), may be composed of two or more layers, and when composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited. does not

It is preferable that it is 50-300 micrometers, and, as for the thickness of a base material, it is more preferable that it is 60-100 micrometers. When the thickness of a base material is such a range, the flexibility of the said composite sheet for protective film formation, and the sticking property with respect to a semiconductor wafer or a semiconductor chip improve more.

Here, the "thickness of a base material" means the thickness of the whole base material, for example, the thickness of the base material which consists of multiple layers means the total thickness of all the layers which comprise a base material.

In this specification, "thickness" is a value which measures 5 arbitrary places of an object with a contact-type thickness measuring machine, and shows the average.

It is preferable that the base material has a high thickness accuracy, that is, a thickness variation is suppressed irrespective of the site. Among the above-mentioned constituent materials, examples of the material usable for constituting the substrate having such a high precision in thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like.

The base material may contain various well-known additives, such as a filler, a coloring agent, an antistatic agent, antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer), in addition to the main constituent materials, such as the said resin.

It is preferable that the optical properties of the substrate satisfy the optical properties of the support sheet described above. For example, the base material may be transparent, may be opaque, may be colored according to the objective, and another layer may be vapor-deposited.

And in this invention in which the film for protective film formation has energy-beam sclerosis|hardenability, it is preferable for a base material to permeate|transmit an energy-beam.

In order to improve the adhesion of the substrate with other layers such as the pressure-sensitive adhesive layer formed thereon, concavo-convex treatment by sandblasting treatment, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, The surface may be subjected to oxidation treatment such as flame treatment, chromic acid treatment, or hot air treatment.

The base material may have the surface treated with a primer.

The base material is an antistatic coating layer; When the composite sheet for forming a protective film is stacked and stored, it may have a layer or the like that prevents the base material from adhering to another sheet or from adhering the base material to the adsorption table.

The substrate can be prepared by a known method. For example, the base material containing a resin can be manufactured by shaping|molding the resin composition containing the said resin.

○Adhesive layer

The pressure-sensitive adhesive layer is in the form of a sheet or a film, and contains an adhesive.

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferable.

In the present invention, "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, for example, not only the resin itself has adhesiveness, but also combined use with other components such as additives. Resins exhibiting adhesiveness due to the presence of a trigger such as heat or water, and the like are also included.

The pressure-sensitive adhesive layer may be composed of one layer (single layer) or may be composed of multiple layers of two or more layers. doesn't happen

It is preferable that it is 1-100 micrometers, as for the thickness of an adhesive layer, it is more preferable that it is 1-60 micrometers, It is especially preferable that it is 1-30 micrometers.

Here, the "thickness of an adhesive layer" means the thickness of the whole adhesive layer, for example, the thickness of the adhesive layer which consists of multiple layers means the total thickness of all the layers which comprise an adhesive layer.

It is preferable that the optical properties of the pressure-sensitive adhesive layer satisfy the optical properties of the support sheet described above. For example, an adhesive layer may be transparent, may be opaque, and may be colored according to the objective.

And in this invention in which the film for protective film formation has energy-beam sclerosis|hardenability, it is preferable that an adhesive layer permeate|transmits an energy-beam.

The pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive or may be formed using a non-energy-ray-curable pressure-sensitive adhesive. The pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily control physical properties before and after curing.

<<Adhesive composition>>

The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site|part by coating an adhesive composition on the formation target surface of an adhesive layer, and drying it as needed. A more specific method of forming the pressure-sensitive adhesive layer will be described in detail next together with the method of forming other layers. The content ratio of the components which do not vaporize at normal temperature in an adhesive composition is the same as the content ratio of the said components of an adhesive layer normally.

The pressure-sensitive adhesive composition may be coated by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, and a Meyer bar. The method using various coaters, such as a coater and a kiss coater, is mentioned.

Although the drying conditions of an adhesive composition are not specifically limited, When the adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. It is preferable to dry the adhesive composition containing a solvent on conditions for 10 second - 5 minutes at 70-130 degreeC, for example.

When the pressure-sensitive adhesive layer is energy-ray-curable, the pressure-sensitive adhesive composition containing the energy-ray-curable pressure-sensitive adhesive, that is, the energy-ray-curable pressure-sensitive adhesive composition, includes, for example, a non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter referred to as "adhesive resin ( I-1a)") and a pressure-sensitive adhesive composition (I-1) containing an energy ray-curable compound; Energy ray-curable pressure-sensitive adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)") containing pressure-sensitive adhesive composition (I-2); The adhesive composition (I-3) containing the said adhesive resin (I-2a) and an energy-beam curable compound, etc. are mentioned.

<Adhesive composition (I-1)>

As described above, the pressure-sensitive adhesive composition (I-1) contains a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) and an energy ray-curable compound.

[Adhesive resin (I-1a)]

The adhesive resin (I-1a) is preferably an acrylic resin.

As said acrylic resin, the acrylic polymer which has a structural unit derived from (meth)acrylic-acid alkylester at least is mentioned, for example.

The number of structural units which the said acrylic resin has may be 1 type, and 2 or more types may be sufficient as it, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Examples of the (meth)acrylic acid alkyl ester include those having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the alkyl group is preferably linear or branched.

More specifically, as (meth)acrylic acid alkylester, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) Isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Isooctyl acrylate, (meth)acrylic acid n-octyl, (meth)acrylic acid n-nonyl, (meth)acrylic acid isononyl, (meth)acrylic acid decyl, (meth)acrylic acid undecyl, (meth)acrylic acid dodecyl ((meth)acrylate (Also called lauryl acrylate), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl ((meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl ((meth)acrylic acid palmityl), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl), (meth)acrylic acid nonadecyl, (meth)acrylic acid icosyl, etc. are mentioned.

It is preferable that the said acrylic polymer has the structural unit derived from the (meth)acrylic-acid alkylester whose carbon number of the said alkyl group is 4 or more from the point which the adhesive force of an adhesive layer improves. It is preferable that carbon number of the said alkyl group is 4-12, and, as for the point which the adhesive force of an adhesive layer improves more, it is more preferable that it is 4-8. It is preferable that the (meth)acrylic-acid alkylester of C4 or more of the said alkyl group is a methacrylic-acid alkylester.

It is preferable that the said acrylic polymer has the structural unit derived from a functional group containing monomer further in addition to the structural unit derived from the (meth)acrylic-acid alkylester.

As the functional group-containing monomer, for example, when the functional group reacts with a crosslinking agent described later, it becomes a starting point of crosslinking, or when the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later, introduction of an unsaturated group into the side chain of the acrylic polymer. what makes it possible is

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, and an epoxy group.

That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxy group containing monomer, an amino group containing monomer, an epoxy group containing monomer, etc. are mentioned, for example.

As the hydroxyl group-containing monomer, for example, (meth) acrylate hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) ) hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic-type unsaturated alcohols (unsaturated alcohol which does not have a (meth)acryloyl skeleton), such as vinyl alcohol and allyl alcohol, etc. are mentioned.

Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

The number of functional group-containing monomers constituting the acrylic polymer may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

The said acrylic polymer WHEREIN: It is preferable that content of the structural unit derived from a functional group containing monomer is 1-35 mass % with respect to the total mass of a structural unit, It is more preferable that it is 2-32 mass %, It is 3-30 mass % It is particularly preferred.

The said acrylic polymer may have the structural unit derived from another monomer other than the structural unit derived from the (meth)acrylic-acid alkylester, and the structural unit derived from a functional group containing monomer further.

The said other monomer will not be specifically limited if it can copolymerize with (meth)acrylic-acid alkylester etc.

Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

The number of the other monomers constituting the acrylic polymer may be one, two or more, and in the case of two or more, combinations and ratios thereof may be arbitrarily selected.

The acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1a).

On the other hand, among the acrylic polymers, those obtained by reacting a functional group with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the above-described energy ray curable adhesive resin (I-2a).

The number of adhesive resins (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5-99 mass%, and 10-95 mass%, with respect to the total mass of the pressure-sensitive adhesive composition (I-1). It is more preferable, and it is especially preferable that it is 15-90 mass %.

[Energy-ray-curable compound]

As said energy-beam-curable compound which an adhesive composition (I-1) contains, it has an energy-beam polymerizable unsaturated group, and the monomer or oligomer which can be hardened by irradiation of an energy-beam is mentioned.

Among the energy ray-curable compounds, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyvalent (meth)acrylates such as 1,4-butylene glycol di(meth)acrylate and 1,6-hexanediol (meth)acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; Epoxy (meth)acrylate etc. are mentioned.

Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerization of the monomers exemplified above.

An energy ray-curable compound has a comparatively large molecular weight, and urethane (meth)acrylate and a urethane (meth)acrylate oligomer are preferable at the point which it is hard to reduce the storage elastic modulus of an adhesive layer.

The number of said energy-beam curable compounds contained in an adhesive composition (I-1) may be one, and two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

Said adhesive composition (I-1) WHEREIN: It is preferable that content of the said energy-beam curable compound is 1-95 mass % with respect to the gross mass of the said adhesive composition (I-1), It is preferable that it is 5-90 mass % More preferably, it is especially preferable that it is 10-85 mass %.

[crosslinking agent]

When using the above acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkylester as the adhesive resin (I-1a), the adhesive composition (I-1) is additionally a crosslinking agent It is preferable to contain

The crosslinking agent reacts with the functional group to crosslink the adhesive resins (I-1a).

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; metal chelate-based crosslinking agents such as aluminum chelates (crosslinking agents having a metal chelate structure); isocyanurate-based crosslinking agent (crosslinking agent having isocyanuric acid skeleton); and the like.

It is preferable that the crosslinking agent is an isocyanate type crosslinking agent from points, such as the point which improves the cohesion force of an adhesive and improves the adhesive force of an adhesive layer, and an acquisition is easy.

The number of crosslinking agents contained in the adhesive composition (I-1) may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

In the said adhesive composition (I-1), it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to content of 100 mass parts of adhesive resin (I-1a), It is more preferable that it is 0.1-20 mass parts, It is 0.3 It is especially preferable that it is -15 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photoinitiator. The adhesive composition (I-1) containing a photoinitiator fully advances hardening reaction even if it irradiates comparatively low energy energy rays, such as an ultraviolet-ray.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, etc. phosphorus compounds; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone etc. are mentioned.

Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. can also be used.

The number of photoinitiators contained in the pressure-sensitive adhesive composition (I-1) may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

The pressure-sensitive adhesive composition (I-1) WHEREIN: It is preferable that content of a photoinitiator is 0.01-20 mass parts with respect to content 100 mass parts of the said energy-beam sclerosing|hardenable compound, It is more preferable that it is 0.03-10 mass parts, It is more preferable, 0.05-5 It is especially preferable that it is a mass part.

[Other additives]

The adhesive composition (I-1) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect of this invention.

Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders, crosslinking accelerators ( catalyst) and other known additives.

With a reaction retarder, it suppresses that crosslinking reaction which is not aimed at advances in the adhesive composition (I-1) during preservation|save by the action|action of the catalyst mixed in the adhesive composition (I-1), for example. Examples of the reaction retardant include those that form a chelate complex by chelating with a catalyst, and more specifically, those having two or more carbonyl groups (-C(=O)-) in one molecule. .

One type may be sufficient as the other additive which adhesive composition (I-1) contains, and 2 or more types may be sufficient as it, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The pressure-sensitive adhesive composition (I-1) WHEREIN: Content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-1) may contain a solvent. By containing the solvent, the adhesive composition (I-1) improves the coating aptitude with respect to the coating object surface.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; Esters, such as ethyl acetate (carboxylate ester); ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; Alcohol, such as 1-propanol and 2-propanol, etc. are mentioned.

As the solvent, for example, the solvent used in the preparation of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without removing it from the adhesive resin (I-1a), or the adhesive resin ( A solvent of the same or different type as that used in the preparation of I-1a) may be separately added during the preparation of the pressure-sensitive adhesive composition (I-1).

The number of solvents contained in the pressure-sensitive adhesive composition (I-1) may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-1), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<Adhesive composition (I-2)>

As described above, the pressure-sensitive adhesive composition (I-2) contains the energy ray-curable pressure-sensitive adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a).

[Adhesive resin (I-2a)]

The adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.

The unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.

Examples of the energy ray polymerizable unsaturated group include a (meth)acryloyl group, a vinyl group (also called an ethenyl group), and an allyl group (also called a 2-propenyl group), and a (meth)acryloyl group is preferable

Examples of the group capable of bonding with a functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding with a carboxy group or an epoxy group.

As said unsaturated group containing compound, (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, etc. are mentioned, for example.

The number of adhesive resins (I-2a) which the adhesive composition (I-2) contains may be one, and two or more types may be sufficient as them, and in the case of two or more types, these combinations and a ratio can be selected arbitrarily.

The pressure-sensitive adhesive composition (I-2) WHEREIN: It is preferable that content of adhesive resin (I-2a) is 5-99 mass % with respect to the gross mass of the said adhesive composition (I-2), It is 10-95 mass % It is more preferable, and it is especially preferable that it is 10-90 mass %.

[crosslinking agent]

When using the acrylic polymer having the same structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a), for example, as the adhesive resin (I-2a), the pressure-sensitive adhesive composition (I-2) is Furthermore, you may contain a crosslinking agent.

As said crosslinking agent in an adhesive composition (I-2), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The number of crosslinking agents contained in the pressure-sensitive adhesive composition (I-2) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

In the said adhesive composition (I-2), it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to content 100 mass parts of adhesive resin (I-2a), It is more preferable that it is 0.1-20 mass parts, It is 0.3 It is especially preferable that it is -15 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-2) may further contain a photoinitiator. The adhesive composition (I-2) containing a photoinitiator fully advances hardening reaction even if it irradiates comparatively low energy energy rays, such as an ultraviolet-ray.

As said photoinitiator in adhesive composition (I-2), the thing similar to the photoinitiator in adhesive composition (I-1) is mentioned.

One type may be sufficient as the photoinitiator which adhesive composition (I-2) contains, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

PSA composition (I-2) WHEREIN: It is preferable that content of a photoinitiator is 0.01-20 mass parts with respect to content 100 mass parts of adhesive resin (I-2a), It is more preferable that it is 0.03-10 mass parts, 0.05 It is especially preferable that it is -5 mass parts.

[Other additives]

The adhesive composition (I-2) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect of this invention.

As said other additive in an adhesive composition (I-2), the thing similar to the other additive in an adhesive composition (I-1) is mentioned.

One type may be sufficient as the other additive which adhesive composition (I-2) contains, and 2 or more types may be sufficient as it, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The pressure-sensitive adhesive composition (I-2) WHEREIN: Content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in adhesive composition (I-2), the thing similar to the solvent in adhesive composition (I-1) is mentioned.

The number of solvents which the pressure-sensitive adhesive composition (I-2) contains may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-2), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<Adhesive composition (I-3)>

As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive resin (I-2a) and an energy ray-curable compound.

PSA composition (I-3) WHEREIN: It is preferable that content of adhesive resin (I-2a) is 5-99 mass % with respect to the gross mass of the said adhesive composition (I-3), It is 10-95 mass % It is more preferable, and it is especially preferable that it is 15-90 mass %.

[Energy-ray-curable compound]

Examples of the energy-beam-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy-beam polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition (I-1) contains The same thing as an energy-ray-curable compound is mentioned.

The number of said energy-beam curable compounds contained in an adhesive composition (I-3) may be one, and two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a). It is preferable, and it is especially preferable that it is 0.05-100 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-3) may further contain a photoinitiator. Even if the pressure-sensitive adhesive composition (I-3) containing a photoinitiator is irradiated with energy rays of relatively low energy such as ultraviolet rays, the curing reaction proceeds sufficiently.

As said photoinitiator in an adhesive composition (I-3), the thing similar to the photoinitiator in an adhesive composition (I-1) is mentioned.

The number of photoinitiators which the pressure-sensitive adhesive composition (I-3) contains may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

PSA composition (I-3) WHEREIN: It is preferable that content of a photoinitiator is 0.01-20 mass parts with respect to 100 mass parts of total content of adhesive resin (I-2a) and the said energy-beam curable compound, and 0.03-10 mass It is more preferable that it is negative, and it is especially preferable that it is 0.05-5 mass parts.

[Other additives]

The adhesive composition (I-3) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect of this invention.

As said other additive, the thing similar to the other additive in adhesive composition (I-1) is mentioned.

One type may be sufficient as the other additive which adhesive composition (I-3) contains, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

In the adhesive composition (I-3), content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in an adhesive composition (I-3), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

The number of solvents which the pressure-sensitive adhesive composition (I-3) contains may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

In the adhesive composition (I-3), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

<Adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3)>

So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described, but what has been described as these contained components is an overall pressure-sensitive adhesive composition ( In this specification, it can be used similarly also to "a pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3)”).

As an adhesive composition other than adhesive composition (I-1) - (I-3), a non-energy-ray-curable adhesive composition is also mentioned other than energy-beam curable adhesive composition.

Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy-ray-curable pressure-sensitive adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins (I-1a). ) containing the adhesive composition (I-4) is mentioned, and it is preferable to contain an acrylic resin.

It is preferable that the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) contain one or more crosslinking agents, and the content thereof is the same as that of the pressure-sensitive adhesive composition (I-1) or the like described above. can do.

<Adhesive composition (I-4)>

As a preferable adhesive composition (I-4), the thing containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)]

As adhesive resin (I-1a) in adhesive composition (I-4), the thing similar to adhesive resin (I-1a) in adhesive composition (I-1) is mentioned.

The number of adhesive resins (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be one, two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

The pressure-sensitive adhesive composition (I-4) WHEREIN: It is preferable that content of adhesive resin (I-1a) is 5-99 mass % with respect to the gross mass of the said adhesive composition (I-4), It is 10-95 mass % It is more preferable, and it is especially preferable that it is 15-90 mass %.

[crosslinking agent]

When using the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylic acid alkylester as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I-4) is further It is preferable to contain a crosslinking agent.

As a crosslinking agent in an adhesive composition (I-4), the thing similar to the crosslinking agent in an adhesive composition (I-1) is mentioned.

The number of crosslinking agents contained in the adhesive composition (I-4) may be one, or two or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

In the said adhesive composition (I-4), it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to content of 100 mass parts of adhesive resin (I-1a), It is more preferable that it is 0.1-20 mass parts, It is 0.3 It is especially preferable that it is -15 mass parts.

[Other additives]

The adhesive composition (I-4) may contain the other additive which does not correspond to any component mentioned above within the range which does not impair the effect of this invention.

As said other additive, the thing similar to the other additive in adhesive composition (I-1) is mentioned.

One type may be sufficient as the other additive which adhesive composition (I-4) contains, and 2 or more types may be sufficient as them, and when 2 or more types, these combinations and a ratio can be selected arbitrarily.

The pressure-sensitive adhesive composition (I-4) WHEREIN: Content of another additive is not specifically limited, What is necessary is just to select suitably according to the kind.

[menstruum]

The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

As said solvent in an adhesive composition (I-4), the thing similar to the solvent in an adhesive composition (I-1) is mentioned.

The number of solvents which the pressure-sensitive adhesive composition (I-4) contains may be one, two or more, and in the case of two or more, these combinations and ratios can be arbitrarily selected.

In the adhesive composition (I-4), content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

In the composite sheet for forming a protective film, the pressure-sensitive adhesive layer is preferably non-energy ray-curable. This is because if an adhesive layer is energy-beam sclerosis|hardenability, when hardening the film for protective film formation by irradiation of an energy-beam, it is because it may not be able to suppress that an adhesive layer also hardens simultaneously. When the pressure-sensitive adhesive layer is cured at the same time as the film for forming a protective film, the film for forming a protective film and the pressure-sensitive adhesive layer after curing may be adhered to such an extent that it cannot be peeled off at their interface. In that case, it becomes difficult to peel the film for forming a protective film after curing, that is, a semiconductor chip having a protective film on its back surface (semiconductor chip with a protective film on its back side) from the support sheet having an adhesive layer after curing, and the semiconductor chip having a protective film formed thereon normally cannot be picked up. The said support sheet WHEREIN: By making an adhesive layer a non-energy-ray-curable thing, such a problem can be avoided reliably, and the semiconductor chip with a protective film can be picked up more easily.

Here, although the effect when an adhesive layer is non-energy-ray-curable was demonstrated, even if the layer which is in direct contact with the film for protective film formation of a support sheet is a layer other than an adhesive layer, if this layer is non-energy-ray-curable, the same effect indicates

<<The manufacturing method of an adhesive composition>>

The pressure-sensitive adhesive compositions (I-1) to (I-3) and pressure-sensitive adhesive compositions (I-4), such as pressure-sensitive adhesive compositions (I-1) to (I-3), other than the pressure-sensitive adhesive composition (I-3), the pressure-sensitive adhesive and, if necessary It is obtained by mix|blending each component for comprising adhesive compositions, such as components other than the said adhesive.

The order of addition at the time of mixing|blending each component is not specifically limited, You may add 2 or more types of components simultaneously.

When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and this compounding component may be used by diluting in advance, and the solvent may be mixed with these compounding components without diluting any compounding component other than the solvent in advance. You may use it by

A method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as the method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

◇Manufacturing method of composite sheet for protective film formation

The said composite sheet for forming a protective film can be manufactured by laminating|stacking each layer mentioned above so that it may become a corresponding positional relationship. A method of forming each layer is the same as described above.

For example, when manufacturing a support sheet and laminating|stacking an adhesive layer on a base material, what is necessary is just to coat the adhesive composition mentioned above on a base material, and to dry as needed.

On the other hand, for example, in the case of further laminating a film for forming a protective film on the pressure-sensitive adhesive layer laminated on the substrate, it is possible to directly form the film for forming a protective film by coating the composition for forming a protective film on the pressure-sensitive adhesive layer. do. Layers other than the film for protective film formation can also laminate this layer on an adhesive layer by the same method using the composition for forming this layer. As described above, in the case of forming a continuous two-layer laminate structure using any one composition, it is possible to form a new layer by further coating the composition on the layer formed from the composition.

However, among these two layers, the layer to be laminated later is previously formed using the composition on another release film, and the side of the formed layer in contact with the release film sets the opposite exposed surface to expose the remaining layers already formed. It is preferable to form the laminated structure of two continuous layers by bonding together with a surface. At this time, it is preferable to apply the said composition to the peeling process surface of a peeling film. What is necessary is just to remove a peeling film after formation of a laminated structure as needed.

For example, a composite sheet for forming a protective film in which an adhesive layer is laminated on a substrate and a film for forming a protective film is laminated on the adhesive layer (a composite sheet for forming a protective film in which the support sheet is a laminate of a substrate and an adhesive layer) In the case of doing so, the pressure-sensitive adhesive composition is applied on the substrate and dried as necessary, the pressure-sensitive adhesive layer is laminated on the substrate, and separately, the composition for forming a protective film is coated on the release film and dried as necessary. A film for forming a protective film is formed on the film. And the composite sheet for protective film formation is obtained by bonding the exposed surface of this film for protective film formation together with the exposed surface of the adhesive layer laminated|stacked on the base material, and laminating|stacking the film for protective film formation on the adhesive layer.

When laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive layer on the release film by coating the pressure-sensitive adhesive composition on the release film and drying if necessary. may be formed and the pressure-sensitive adhesive layer may be laminated on the substrate by bonding the exposed surface of this layer to one surface of the substrate.

What is necessary is just to remove a peeling film at arbitrary timings in any method, after forming the laminated structure made into the objective.

In this way, since all layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming in advance on the release film and bonding them to the surface of the target layer, such a process is adopted as necessary. What is necessary is just to select the layer to be used suitably and to manufacture the composite sheet for protective film formation.

The composite sheet for protective film formation is normally stored in the state by which the peeling film was pasted on the surface of the outermost layer (for example, film for protective film formation) on the opposite side to the support sheet. Therefore, on this peeling film (preferably, the peeling-treated surface), the composition for forming the layer which comprises outermost layers, such as a composition for protective film formation, is coated, and by drying as needed, the outermost layer on a peeling film. A layer constituting the layer is formed, and the remaining respective layers are laminated on the exposed surface opposite to the side in contact with the release film of this layer by any one of the methods described above, and the release film is bonded without removing it. Also by carrying out, the composite sheet for protective film formation is obtained.

◇Semiconductor chip manufacturing method

The film for forming a protective film and the composite sheet for forming a protective film can be used for manufacturing a semiconductor chip.

As the manufacturing method of the semiconductor chip at this time, for example, a step of affixing a film for forming a protective film that does not constitute the composite sheet for forming a protective film, or a film for forming a protective film in the composite sheet for forming a protective film, on a semiconductor wafer ( Hereinafter, it may be abbreviated as "adhesive process"), and a step of forming a protective film by irradiating the film for forming a protective film with ultraviolet rays after affixing to the semiconductor wafer (hereinafter, abbreviated as "protective film formation process") and dividing the semiconductor wafer by cutting together with the protective film or film for forming a protective film to obtain a plurality of semiconductor chips (hereinafter, may be abbreviated as a "division process").

Hereinafter, the above-described manufacturing method will be described with reference to the drawings. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of the semiconductor chip in the case of using the film for protective film formation which does not comprise the composite sheet for protective film formation. It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of the semiconductor chip at the time of using the composite sheet for protective film formation which integrated the film for protective film formation with the support sheet previously.

<<The manufacturing method of the semiconductor chip in the case of using the film for protective film formation which does not comprise the composite sheet for protective film formation>>

First, about one Embodiment of the manufacturing method in the case of using the film for protective film formation which does not comprise the composite sheet for protective film formation, the case where the film for protective film formation is shown in FIG. 1 is taken as an example and demonstrated (this Example) A form may be called "manufacturing method (1)").

In the above-mentioned sticking process of the manufacturing method (1), as shown to Fig.7 (a), the film 13 for protective film formation on the back surface (surface opposite to the electrode formation surface) 9b of the semiconductor wafer 9. paste the Here, when the 1st peeling film 151 is removed from the film 13 for protective film formation, and the 1st surface 13a of the film 13 for protective film formation is bonded to the back surface 9b of the semiconductor wafer 9 represents Here, in the semiconductor wafer 9, illustration of bumps on a circuit surface, etc. are abbreviate|omitted.

After the pasting process of the manufacturing method (1), in the said protective film formation process, ultraviolet-ray is irradiated to the film 13 for protective film formation after affixing to the semiconductor wafer 9, as shown in FIG. 7(b), A protective film 13 ′ is formed on the semiconductor wafer 9 . You may perform irradiation of an ultraviolet-ray, after removing the 2nd peeling film 152 from the film 13 for protective film formation.

After the protective film forming step of the manufacturing method 1, before the dividing step, as shown in FIG. 7C, the surface of the protective film 13' on the side to which the semiconductor wafer 9 is pasted (this specification In this case, the support sheet 10 on a surface (in this specification, sometimes referred to as a "second surface") 13b' on the opposite side to the "first surface") 13a' affix the The support sheet 10 is shown in FIG. 2 etc., and is affixed to the protective film 13' by the adhesive layer 12.

Next, in the above division step of the manufacturing method 1, the semiconductor wafer 9 is divided together with the protective film 13' by dicing or the like to divide the semiconductor wafer 9, as shown in Fig. 7(d). As described above, a plurality of semiconductor chips 9' are obtained. At this time, the protective film 13' is cut (divided) at a position along the periphery of the semiconductor chip 9'. The protective film 13' after this cut is indicated by reference numeral 130'.

In FIG. 7, after performing a protective film formation process, the case where the support sheet 10 is affixed to the protective film 13' is shown. However, in the manufacturing method (1), after affixing the support sheet 10 to the film 13 for protective film formation, you may perform a protective film formation process.

In the manufacturing method (1), the dividing step is performed after the protective film forming step, but in the semiconductor chip manufacturing method according to the present embodiment, the dividing step is performed without performing the protective film forming step, and the protective film forming step is performed after the dividing step also be

<<The manufacturing method of the semiconductor chip in the case of using the composite sheet for protective film formation which integrated the film for protective film formation with the support sheet beforehand>>

Next, about one Embodiment of the manufacturing method in the case of using the composite sheet for protective film formation which integrated the film for protective film formation with the support sheet beforehand, the case where the composite sheet for protective film formation is shown in FIG. 2 is taken as an example and demonstrated (this embodiment may be called "manufacturing method (2)").

In the said pasting process of the manufacturing method (2), as shown to Fig.8 (a), the film 13 for protective film formation in 1 A of composite sheets for protective film formation on the back surface 9b of the semiconductor wafer 9. paste the

1 A of composite sheets for protective film formation remove the peeling film 15, and are used.

After the pasting process of the manufacturing method (2), in the said protective film formation process, ultraviolet-ray is irradiated to the film 13 for protective film formation after affixing on the semiconductor wafer 9, as shown in FIG.8(b), A protective film 13 ′ is formed on the semiconductor wafer 9 . At this time, an ultraviolet-ray is irradiated to the film 13 for protective film formation through the support sheet 10.

Here, the composite sheet for protective film formation after the film 13 for protective film formation turns into the protective film 13' is shown by code|symbol 1A'. This is the same also in the following drawings.

After the pasting step of the manufacturing method (2), in the above division step of the manufacturing method (2), the semiconductor wafer 9 is divided by cutting the semiconductor wafer 9 together with the protective film 13' by dicing or the like, As shown in Fig. 8C, a plurality of semiconductor chips 9' are obtained. At this time, the protective film 13' is cut (divided) at a position along the periphery of the semiconductor chip 9' to become the protective film 130'.

By the above, the target semiconductor chip 9' is obtained as a semiconductor chip in which the protective film was formed.

In the manufacturing method (2), the dividing step is performed after the protective film forming step, but in the semiconductor chip manufacturing method according to the present embodiment, the dividing step is performed without performing the protective film forming step, and the protective film forming step is performed after the dividing step also be

Here, the manufacturing method of the semiconductor chip at the time of using the film 13 for protective film formation shown in FIG. 1, the support sheet 10 shown in FIG. 2, and the composite sheet 1A for protective film formation shown in FIG. 2 was demonstrated. , the method for manufacturing a semiconductor chip of the present invention is not limited thereto.

For example, when the composite sheet for forming a protective film is used, the composite sheets for forming a protective film (1B) to (1E) shown in Figs. Even if it uses things other than 1 A of composite sheets for protective film formation shown in FIG. 2, a semiconductor chip can be manufactured similarly.

As described above, a semiconductor chip can be manufactured similarly even if a support sheet uses a thing other than the support sheet 10 shown in FIG.

In this way, when using the composite sheet or support sheet for forming a protective film of another embodiment, based on the difference in the structure of these sheets, in the above-described manufacturing method, steps are appropriately added, changed, deleted, etc. What is necessary is just to manufacture a semiconductor chip.

◇Semiconductor device manufacturing method

After obtaining a semiconductor chip by the above-mentioned manufacturing method, this semiconductor chip is separated from a support sheet and picked up in the state in which the protective film after division|segmentation was stuck (that is, as a semiconductor chip with a protective film formed) (not shown).

The obtained semiconductor chip of the semiconductor chip with a protective film is arrange|positioned on the circuit surface of a board|substrate by a face-down method, and after flip-chip connection by heating the surface on which the protective film of the semiconductor chip was formed at 100-280 degreeC, it is set as a semiconductor package. And what is necessary is just to manufacture the target semiconductor device using this semiconductor package (not shown).

Example

Hereinafter, the present invention will be described in more detail by way of specific examples. However, this invention is not limited to the Example shown below at all.

<The raw material for manufacturing the composition for forming a protective film>

The raw material used for manufacture of the composition for protective film formation is shown below.

[Energy-ray-curable component (a1-1)]

(a1-1)-1: 2-hydroxyethyl acryl of an acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass) An ultraviolet curable group is formed in the side chain obtained by reacting 2-methacryloyloxyethyl isocyanate ("Karenz MOI (registered trademark)" manufactured by Showa Denko Co., Ltd.) in an amount equivalent to 10 moles with respect to 100 moles of the hydroxyl groups derived from the rate. Adduct type acrylic polymer introduced (weight average molecular weight 350000, glass transition temperature 6°C).

(a1-1)-2: Quantity corresponding to 30 mol with respect to 100 mol of hydroxyl groups derived from 2-hydroxyethyl acrylate of the acrylic polymer formed by copolymerizing methyl acrylate (85 parts by mass) and HEA (15 parts by mass) of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd.), an adduct-type acrylic polymer in which an ultraviolet curable group was introduced into the side chain (weight average molecular weight 350000, glass transition temperature 6°C).

[Energy-ray-curable component (a2)]

(a2)-1:ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate (“A-9300-1CL” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional ultraviolet curable compound).

[Polymer (b) having no energy ray-curable group]

(b)-1: The acrylic polymer (weight average molecular weight 350000, glass transition temperature 6 degreeC) formed by copolymerizing methyl acrylate (85 mass parts) and HEA (15 mass parts).

[Photoinitiator (c)]

(c) -1:2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (“Irgacure (registered trademark) 369” manufactured by BASF).

[Filling material (d)]

(d)-1: Silica filler (molten quartz filler, average particle diameter of 8 µm).

[Coupling agent]

(e) -1:3-methacryloxypropyl trimethoxysilane ("KBM-503" by Shin-Etsu Chemical Industry Co., Ltd., silane coupling agent).

[Colorant (g)]

(g)-1: 32 parts by mass of a phthalocyanine-based blue pigment (Pigment Blue 15: 3), 18 parts by mass of an isoindolinone-based yellow pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone-based red pigment (Pigment Red 177) The pigment obtained by mixing parts and making it pigment so that it may become the total amount/styrene acrylic resin amount=1/3 (mass ratio) of the said 3 types of pigment|dye.

The weight average molecular weight of the adduct type acrylic polymer ((a1-1)-1, (a1-1)-2) and the polymer ((b)-1) which does not have an energy-beam curable group is obtained according to the following method. Using tetrahydrofuran as a solvent, 1 mL of a sample sample containing 0.005 g of a polymer ((a1-1)-1, (a1-1)-2, or (b)-1) was used at room temperature as a mobile phase From the data obtained by measuring by the gel permeation chromatography method using tetrahydrofuran, the weight average molecular weight was obtained as polystyrene conversion value.

[Example 1]

<Production of the composite sheet for forming a protective film>

(Preparation of composition (IV-1) for forming a protective film)

With respect to 100 mass parts of solid content, 10 mass parts of energy-beam sclerosing|hardenable component ((a2)-1), 28 mass parts of adduct type acrylic polymer ((a1-1)-1), a photoinitiator ((c)- Methyl ethyl ketone so that 1) may be 0.6 mass parts, a filler ((d)-1) may be 57 mass parts, a coupling agent ((e)-1) may be 0.4 mass parts, and a coloring agent ((g)-1) may be 3 mass parts. The composition (IV-1) for forming a protective film whose solid content concentration is 50 mass % was prepared by melt|dissolving or making it disperse|distribute to 23 degreeC and stirring at 23 degreeC.

(Preparation of adhesive composition (I-4))

Contains an acrylic polymer (100 parts by mass, solid content) and an isocyanate-based crosslinking agent ("Coronate L" manufactured by Nippon Polyurethane, a tolylene diisocyanate trimer adduct of trimethylolpropane) (5 parts by mass, solid content), and further Solid content concentration containing methyl ethyl ketone as a solvent prepared the non-energy-ray-curable adhesive composition (I-4) whose solid content concentration is 30 mass %. The acrylic polymer has a weight average molecular weight of 600000 obtained by copolymerizing methacrylic acid-2-ethylhexyl (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)

The pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated side of the release film (“SP-PET381031” manufactured by Lintec, 38 µm thick) in which one side of the polyethylene terephthalate film was released by silicone treatment. It coated and made to heat-dry at 120 degreeC for 2 minute(s), and the 10 micrometers-thick non-energy-ray-curable adhesive layer was formed.

Next, by bonding a polypropylene-based film (thickness 80 µm) as a substrate to the exposed surface of this pressure-sensitive adhesive layer, a support sheet in which the substrate, the pressure-sensitive adhesive layer, and the release film are laminated in this order in the thickness direction was obtained. .

(Manufacture of a composite sheet for forming a protective film)

For forming a protective film obtained above on the release-treated surface of the release film (the second release film, "SP-PET382150" manufactured by Lintec Co., Ltd. "SP-PET382150", 38 µm thick) in which one side of the polyethylene terephthalate film has been released by silicone treatment The 25-micrometer-thick film for energy-beam curable protective film formation was manufactured by coating composition (IV-1) and drying at 100 degreeC for 2 minute(s).

By bonding the peeling surface of the peeling film (1st peeling film, Lintec company "SP-PET381031", 38 micrometers in thickness) to the exposed surface of the side which is not equipped with the 2nd peeling film of the obtained film for protective film formation further, bonding together, The 1st peeling film was provided in one surface of the film for protective film formation, and the laminated|multilayer film provided with the 2nd peeling film in the other surface was obtained.

Next, the peeling film was removed from the adhesive layer of the support sheet obtained above. The 1st peeling film was removed from the laminated|multilayer film obtained above. And a base material, an adhesive layer, the film for protective film formation, and a 2nd peeling film by bonding together the exposed surface of the adhesive layer produced by removing the said peeling film, and the exposed surface of the film for protective film formation produced by removing the said 1st peeling film. In this order, the composite sheet for protective film formation laminated|stacked in these thickness directions was produced.

<Evaluation of the protective film>

(Measurement of the gloss value (glossy) of the protective film)

The 1st peeling film was removed from the laminated|multilayer film obtained above, and the exposed surface of the film for protective film formation produced by this was affixed on the #2000 grinding|polishing surface of an 8-inch silicon wafer (300 micrometers in thickness).

Next, the 2nd peeling film was removed from this film for protective film formation, and the film for protective film formation was exposed. The peeling film was removed from the adhesive layer of the support sheet obtained above, and the adhesive layer was exposed. And by bonding the exposed surface of the pressure-sensitive adhesive layer to the exposed surface of the film for forming a protective film and pasting it on a ring frame, the base material, the pressure-sensitive adhesive layer, the film for forming a protective film, and the silicon wafer are in this order, in their thickness direction. The laminated body was fixed to the ring frame, and it left still for 30 minutes.

Then, using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), under the conditions of an illuminance of 195 mW/cm 2 and a light amount of 170 mJ/cm 2 , the film for forming a protective film is irradiated with ultraviolet rays through the substrate and the pressure-sensitive adhesive layer, The film for protective film formation was hardened and it was set as the protective film.

The gloss value (gloss value before heating) on the surface of the formed protective film was measured using a gloss meter ("VG7000" manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition that the incident angle is 60°. Table 1 shows the measured gloss values (gloss values before heating).

Next, the silicon wafer with a protective film was heated at 260 degreeC for 5 minutes using oven. Then, the gloss value (gloss value after heating) of the protective film surface was measured under the same conditions as the measurement of the gloss value before heating. The case where the decrease rate of the gloss value after heating from the gloss value before heating was 30 % or less was judged as favorable. Table 1 shows the measured gloss values before heating, gloss values after heating, and reduction rates of the gloss values after heating.

[Example 2]

Conducted except that the adduct-type acrylic polymer ((a1-1)-1) at the time of manufacture of the composition (IV-1) for protective film formation was made into the adduct-type acrylic polymer ((a1-1)-2) In the same manner as in Example 1, a film for forming a protective film and a composite sheet for forming a protective film were produced, and the protective film was evaluated. A result is shown in Table 1.

[Comparative Example 1]

Conducted except that the adduct-type acrylic polymer ((a1-1)-1) at the time of manufacture of the composition (IV-1) for protective film formation was made into the polymer ((b)-1) which does not have an energy-beam curable group. In the same manner as in Example 1, a film for forming a protective film and a composite sheet for forming a protective film were produced, and the protective film was evaluated. A result is shown in Table 1.

As is evident from the above results, in Example 1, both the gloss value before heating and the gloss value after heating on the surface of the protective film were as high as 80 and 65, and the reduction rate of the gloss value after heating was also as low as 19%. In Example 2, both the gloss value before heating and the gloss value after heating of the protective film surface were as high as 80 and 72, and the reduction rate of the gloss value after heating was also as low as 10%. This is considered that because the adduct type acrylic polymer was polymerized by irradiation with ultraviolet rays, the low molecular weight polymer was hardly contained in the protective film, and the low molecular weight polymer did not segregate on the protective film surface even when the protective film was heated.

On the other hand, in Comparative Example 1, the gloss value before heating on the surface of the protective film was as high as 80, whereas the gloss value after heating fell to 9. Compared with Examples 1 and 2, Comparative Example 1 contains a large amount of polymer (b) having no low molecular weight energy ray-curable group in the protective film, and the low molecular weight polymer segregates on the surface of the protective film by heating the protective film. Because of this, it is thought that the gloss value fell.

From the results of these Examples and Comparative Examples, it is clear that the decrease in gloss value due to heating on the surface of the protective film is suppressed by using the polymer (b) having no energy ray-curable group in the protective film as the adduct-type acrylic polymer (a1-1). Confirmed.

INDUSTRIAL APPLICABILITY The present invention is applicable to the manufacture of semiconductor devices.

1A, 1A', 1B, 1C, 1D, 1E... A composite sheet for forming a protective film, 10 ... support sheet, 10a... The surface (first surface) of the support sheet, 11 ... Subscription, 11a... The surface of the substrate (first side), 12 . . . pressure-sensitive adhesive layer, 12a... The surface (first surface) of the pressure-sensitive adhesive layer, 13, 23... Films for forming a protective film, 13a, 23a... The surface (1st surface) of the film for protective film formation, 13b... The surface (second side) of the film for forming a protective film, 13'... Shield, 130'… Protective film after cutting, 15... release film, 151... 1st release film, 152... 2nd release film, 16... Adhesive layer for a jig, 16a... The surface of the adhesive layer for a jig, 9... semiconductor wafer, 9b... The back surface of the semiconductor wafer, 9'... semiconductor chip

Claims (3)

A film for forming an energy ray-curable protective film, comprising:
The film for forming a protective film is affixed to a semiconductor wafer, and the film for forming a protective film is attached to a semiconductor wafer for the gloss value measured after irradiating an energy ray, irradiated with an energy ray, and further heated at 260° C. for 5 minutes The film for protective film formation whose reduction rate of the gloss value measured after carrying out is 30 % or less. A composite sheet for forming a protective film comprising a support sheet and comprising the film for forming a protective film according to claim 1 on the support sheet. A step of affixing the film for forming a protective film according to claim 1 or the film for forming a protective film in the composite sheet for forming a protective film according to claim 2 to a semiconductor wafer;
A step of forming a protective film by irradiating an ultraviolet ray to the film for forming a protective film after being pasted on the semiconductor wafer, and cutting the semiconductor wafer together with the protective film or film for forming a protective film to divide the semiconductor wafer to form a plurality of semiconductor chips A method for manufacturing a semiconductor chip comprising the steps of:

Images