KR102332694B1 - A film for forming a protective film and a composite sheet for forming a protective film - Google Patents

Abstract

This film for protective film formation is energy-beam sclerosis|hardenability, and when it is irradiated with an energy-beam and it is set as a protective film, the tensile elasticity modulus of a protective film will be 1x10<^8> Pa or more. The composite sheet for forming a protective film includes a support sheet, the film for forming a protective film is provided on the support sheet, and when the film for forming a protective film is irradiated with energy rays to form a protective film, the adhesive force between the protective film and the support sheet is 50 to 1500 mN/25 mm.

Description

A film for forming a protective film and a composite sheet for forming a protective film

The present invention relates to a film for forming a protective film and a composite sheet for forming a protective film.

This application claims priority based on Japanese Patent Application No. 2016-092015 for which it applied to Japan on April 28, 2016, and uses the content here.

DESCRIPTION OF RELATED ART In recent years, manufacture of the semiconductor device to which the mounting method called a so-called face down method is applied is performed. 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 opposite 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. In the composite sheet for forming a protective film, the film for forming a protective film can form a protective film by curing, and the support sheet can be used as a dicing sheet, and it is possible to integrate the film for forming a protective film and the dicing sheet.

As such a composite sheet for forming a protective film, one provided with a film for forming a thermosetting protective film that forms a protective film by curing by heating, for example, has been mainly used until now. In this case, for example, a composite sheet for forming a protective film is affixed with a film for forming a thermosetting protective film on the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer, and then the film for forming a protective film is cured by heating to obtain a protective film, , the semiconductor wafer is divided for each protective film by dicing to obtain a semiconductor chip. And the semiconductor chip is removed from the support sheet and picked up with this protective film affixed. In addition, hardening and dicing of the film for protective film formation may be performed in the reverse order to this.

However, since a long time is usually required for about several hours for heat-hardening of the film for thermosetting protective film formation, shortening of hardening time is desired. On the other hand, using the film for protective film formation which can be hardened by irradiation of energy rays, such as an ultraviolet-ray, for formation of a protective film is examined. For example, an energy ray-curable protective film formed on a release film (see Patent Document 1) and an energy ray-curable chip protective film (see Patent Document 2) that can form a protective film with high hardness and excellent adhesion to a semiconductor chip are disclosed. has been

On the other hand, as for a semiconductor wafer, the back surface which is the pasting object of the film for protective film formation is grind|ground normally, and it adjusts so that thickness may become the target value. As a result, the semiconductor chip will have this grinding mark (grinding mark) on the back surface. On the other hand, it is also calculated|required by the protective film to make it impossible to visually recognize the grinding mark of this back surface of a semiconductor chip, and to improve the external appearance of a semiconductor chip.

In addition, the protective film is usually printed on the surface opposite to the surface to be attached to the semiconductor wafer or semiconductor chip (that is, the surface facing the support sheet) by irradiation with laser light (in this specification, "laser printing") ) is carried out. And it is also calculated|required by the protective film that it is excellent in printing visibility. When the film for forming a protective film is energy ray-curable, laser printing is sometimes performed at the stage of the film for forming a protective film instead of the protective film.

Thus, it is common that a protective film and the film for protective film formation contain a coloring agent so that the external appearance of a semiconductor chip may be improved and it may be excellent in the visibility of the printing applied to itself.

By the way, when an energy ray is irradiated to a film for forming a protective film containing a colorant to form a protective film, the irradiated energy ray is under the influence of the colorant, the closer the region of the film for forming a protective film to the affixing surface to the semiconductor wafer or semiconductor chip becomes difficult to reach As a result, typically, the formed protective film has a high degree of curing on the side of the energy ray irradiation source, that is, the region close to the surface facing the support sheet, and the degree of curing on the opposite side, that is, the region close to the surface to be attached to the semiconductor wafer or semiconductor chip. lowers In this way, when a difference in curing degree occurs in the protective film in the thickness direction, the surface that faces the support sheet of the protective film when picking up the semiconductor chip on which the protective film is formed is picked up from the support sheet by a push-up method with a pin. , traces of push-up by the pins remain. If such a push-up trace remains, the visibility of laser printing applied to the same surface may be deteriorated.

On the other hand, neither the energy-beam hardening type protective film disclosed by patent document 1, nor the energy-beam curing type chip protection film disclosed by patent document 2 was aimed at the residual suppression of the push-up trace by such a pin.

Japanese Patent No. 5144433 Publication Japanese Patent Laid-Open No. 2010-031183

According to the present invention, a protective film can be formed on the back surface of a semiconductor wafer or semiconductor chip, and even if it contains a colorant, when a semiconductor chip having a protective film formed thereon is picked up by a push-up method by a pin, on the surface of the protective film, An object of the present invention is to provide a film for forming an energy ray-curable protective film capable of suppressing residual push-up traces, and a composite sheet for forming a protective film comprising the film.

The present invention provides a film for forming an energy ray-curable protective film, wherein the protective film has a tensile modulus of 1×10 ⁸ Pa or more when the protective film is irradiated with energy rays to form a protective film.

The film for forming a protective film of the present invention may have a shore D hardness of 55 or more of the protective film.

In addition, the present invention includes a support sheet, the film for forming a protective film is provided on the support sheet, and when the film for forming a protective film is irradiated with an energy beam to form a protective film, between the protective film and the support sheet It provides a composite sheet for forming a protective film having an adhesive force of 50 to 1500 mN/25 mm.

By using the film for forming a protective film and the composite sheet for forming a protective film of the present invention, a protective film can be formed on the back surface of a semiconductor wafer or semiconductor chip, and even if the film for forming a protective film contains a colorant, a semiconductor chip with a protective film When picked up, it is the surface of a protective film. WHEREIN: The residual of the push-up trace by a pin can be suppressed.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically one Embodiment of the film for protective film formation of this invention.
It is sectional drawing which shows typically one Embodiment of the composite sheet for protective film formation of this invention.
It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention.
It is sectional drawing which shows typically still another embodiment of the composite sheet for protective film formation of this invention.
It is sectional drawing which shows typically still another embodiment of the composite sheet for protective film formation of this invention.
It is sectional drawing which shows typically still another embodiment of the composite sheet for protective film formation of this invention.

◇ Film for forming protective film

The film for forming a protective film of the present invention is a film for forming an energy ray-curable protective film, and when the film for forming a protective film is irradiated with an energy ray to form a protective film, the protective film has a tensile modulus of 1×10 ⁸ Pa or more.

As mentioned later, the composite sheet for protective film formation can be comprised by forming the said film for protective film formation in 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 is for protecting 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 short time rather than the film for thermosetting protective film formation.

In addition, 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.

Examples of the film for forming a protective film include those containing an energy ray-curable component (a) described later, and it is preferable to further contain a colorant (g).

It is preferable that it is non-hardened, and, as for an energy-ray-curable component (a), it is preferable to have adhesiveness, and it is more preferable to have adhesiveness while being non-hardened.

In the present invention, the term "energy beam" means that it has energy protons in electromagnetic waves or charged particle beams, and examples thereof include ultraviolet rays, radiation, electron beams, and the like.

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

In the present invention, "energy ray curability" means a property that is cured by irradiating an energy ray, and "non-energy ray curability" means a property that does not harden even when irradiated with an energy ray.

The tensile modulus (Young's modulus) of the protective film obtained by irradiating the film for forming a protective film of the present invention with energy rays is 1×10 ⁸ Pa or more, ^{preferably 1.3×10 8} Pa or more, and more preferably 1.6×10 ⁸ Pa or more. , 1.9×10 ⁸ Pa or more is particularly preferred. When the tensile modulus of elasticity of the protective film is equal to or greater than the lower limit, the residual suppression effect of the push-up trace by the pin in the protective film is increased.

In addition, the upper limit of the tensile elasticity modulus of the said protective film is not specifically limited. For example, the tensile modulus of elasticity of the protective film may be any ^{of 6×10 9} Pa or less, 5.7×10 ⁹ Pa or less, and 5.4×10 ^{9 Pa or less.} These upper limits are a preferable example.

The tensile modulus of elasticity of the protective film can be measured in accordance with JIS K7161:1994.

The tensile modulus of elasticity of the protective film can be appropriately adjusted, for example, by adjusting the type and amount of components contained in the film for forming a protective film.

For example, the type and amount of the component contained in the film for forming a protective film may be adjusted according to the type and amount of the component contained in the composition for forming a protective film, which will be described later. And the tensile modulus of elasticity of a protective film can be adjusted more easily by adjusting the kind and content of an energy-beam-curable component (a2) among the components of the composition for protective film formation, for example.

It is preferable that the Shore D hardness of the protective film obtained by irradiating an energy ray to the film for protective film formation of this invention is 55 or more, It is more preferable that it is 58 or more, It is especially preferable that it is 62 or more. When the Shore D hardness of the protective film is equal to or greater than the lower limit, the protective film is difficult to plastically deform. more effective in suppressing

The upper limit of the Shore D hardness of the protective film is not particularly limited. However, from the viewpoint that the protective film has a higher suppression effect of weakening and the reliability of the protective film is further improved, the Shore D hardness of the protective film is preferably 90 or less, more preferably 80 or less, and particularly preferably 70 or less.

^{The protective film preferably has a Shore D hardness of 58 or more and a tensile modulus of 1×10 8} Pa or more in that the effect of suppressing the residual push-up trace by the pin is higher even if the push-up force by the pin is large. , It is more preferable that the Shore D hardness is 62 or more and the tensile modulus is 5×10 ^{9 Pa or more.}

^{In addition, the protective film preferably has a Shore D hardness of 90 or less and a tensile modulus of 9 × 10 10} Pa or less, and Shore D hardness in terms of further improving the reliability of the protective film while having a higher suppression effect of the aforementioned protective film from being weakened. It is more preferable that is 80 or less and the tensile modulus is 5×10 ^{10 Pa or less.}

The Shore D hardness of the protective film is obtained by curing a laminate of a protective film forming film having a total thickness of 6 mm in which a plurality of protective film forming films are laminated in their thickness direction to obtain a protective film laminate, It is a measured value obtained by measuring Shore D hardness about the laminated body of a protective film at 23 degreeC.

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 addition, in this specification, it is not limited to 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 only some layers may be the same. ', and further, "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 5-75 micrometers, It is especially preferable that it is 5-50 micrometers. When 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. Moreover, becoming excessive thickness is suppressed because the thickness of the film for protective film formation is below the said upper limit.

Here, "thickness of the film for forming a protective film" means the thickness of the entire film for forming a protective film, for example, the thickness of the film for forming a protective film comprising a plurality of layers is the total thickness of all the layers constituting the film for forming a protective film. it means.

The curing conditions for forming the protective film by curing the protective film for forming the 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 for forming the 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 one Embodiment of the film for protective film formation of this invention. On the other hand, in the drawings used in the following description, in order to make it easier to understand the characteristics of the present invention, for convenience, there are cases where the main parts are enlarged and shown, and the dimensional ratio of each component is not limited to the same as in reality. does not

The film 13 for protective film formation shown here is equipped with the 1st peeling film 151 on the one surface 13a, and 2nd peeling is provided on the other surface 13b opposite to the said surface 13a. A film 152 is provided.

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 tensile modulus of elasticity of the film 13 for protective film formation after hardening (that is, protective film) is 1x10<^8> Pa or more.

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

The 1st peeling film 151 and the 2nd peeling film 152 may be mutually the same, for example, even if they differ from each other, such as the peeling force required when peeling from the film 13 for protective film formation mutually different. do.

As for the film 13 for protective film formation shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is affixed to the exposed surface which either one of the 1st peeling film 151 and the 2nd peeling film 152 was removed and arose. And the exposed surface which the other one of the 1st peeling film 151 and the 2nd peeling film 152 was removed and produced|generated turns into the pasting surface of a support sheet.

<<The composition for forming a protective film>>

The 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. The ratio of content of the components which do not vaporize at normal temperature in the composition for protective film formation becomes the same as the ratio of content of the said components of the film for protective film formation normally. In addition, in this specification, "room temperature" means the temperature which is not specifically cooled or heated, ie, normal temperature, for example, the temperature of 15-25 degreeC etc. are mentioned.

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, The 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 adhesive composition contains the solvent mentioned later, it is preferable to heat-dry. The composition for forming a protective film containing a solvent is preferably dried at, for example, 70 to 130°C under the conditions of 10 seconds to 5 minutes.

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

As a composition for protective film formation, the composition (IV-1) etc. for protective film formation containing the said energy-beam curable component (a) are mentioned, for example.

[Energy-ray-curable component (a)]

An energy-beam-curable component (a) is a component hardened|cured by irradiation of an energy-beam, and is also a component for providing film-forming property, 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 to 80000. can The polymer (a1) may or may not be crosslinked at least partly by crosslinking with a crosslinking agent (f) described later.

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

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

As the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000, for example, an acrylic polymer (a11) 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 double The acrylic resin (a1-1) formed by superposing|polymerizing the energy-beam curable compound (a12) which has energy-beam curable groups, such as a bond, is mentioned.

Examples of the functional group capable of reacting with the group of other compounds include a hydroxyl group, a carboxy group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms), an epoxy group, and the like. . 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 (a11) having the functional group 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.

In addition, a random copolymer may be sufficient as the said acrylic polymer (a11), and a block copolymer may be sufficient as it.

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) acrylic acid 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 (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.

A hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable, and, as for the acryl-type monomer which has the said functional group, a hydroxyl-containing monomer is more preferable.

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 can be arbitrarily selected.

The acrylic monomer having no functional group includes, 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 (( (meth) acrylic acid lauryl), (meth) acrylic acid tridecyl, (meth) acrylic acid tetradecyl ((meth) acrylate myristyl), (meth) acrylic acid pentadecyl, (meth) acrylic acid hexadecyl ((meth) acrylate palmityl) , (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl (meth)acrylic acid alkyl ester, etc., in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms. can be heard

In addition, as an acryl-type monomer which does not have the said functional group, For example, alkoxyalkyl groups, such as (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl, (meth)acrylate ethoxyethyl containing (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, and (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 can 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 mass%, and 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, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12), the content of the energy ray-curable group is determined by the degree of curing of the protective film. can be easily adjusted to a desired range.

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

Composition (IV-1) for protective film formation WHEREIN: It is preferable that content of acrylic resin (a1-1) is 1-40 mass %, It is more preferable that it is 2-30 mass %, It is 3-20 mass % Especially preferred.

· 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 isocyanate as the group It is more preferable to have a 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 compounds (a12) constituting the acrylic resin (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 acrylic resin (a1-1), the ratio of the content 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 20 to 120 It is preferable that it is mol%, It is more preferable that it is 35-100 mol%, It is especially preferable that it is 50-100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film formed by curing becomes larger. Further, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is In the case of a functional compound (having two or more 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) A monomer having a group reactive with the crosslinking agent (f) is polymerized and may be crosslinked in a group reactive with the crosslinking agent (f), or in a group reactive with the functional group derived from the energy ray-curable compound (a12), crosslinked it may be

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.

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80000)

Examples of the energy-ray-curable group in the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80000 include a group containing an energy-ray-curable double bond, and preferable examples include a (meth)acryloyl group, a vinyl group, and the like. can

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.

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

As the acrylate-based compound, for example, 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, 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, ditrimethylol propane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta polyfunctional (meth)acrylates such as erythritol poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

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

As an epoxy resin which has an energy-beam curable group among the said compound (a2), and a phenol resin which has an energy-beam curable group, what is described in Paragraph 0043 of "Unexamined-Japanese-Patent No. 2013-194102" etc. can be used, for example. 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 weight average molecular weight of the said compound (a2), it is more preferable that it is 300-10000.

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.

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

When the composition (IV-1) for forming a protective film and the film for forming a protective film contain the compound (a2) as the energy ray-curable component (a), it is preferable that the polymer (b) having no energy ray-curable group is also contained. desirable.

The polymer (b) may be crosslinked at least partly by the crosslinking agent (f), 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, one type or two or more types of acrylic monomers; A copolymer of monomers (non-acrylic monomers) other than 1 type or 2 or more types of 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 (meth)acrylic acid esters containing a substituted amino group. 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 (( (meth) acrylic acid lauryl), (meth) acrylic acid tridecyl, (meth) acrylic acid tetradecyl ((meth) acrylate myristyl), (meth) acrylic acid pentadecyl, (meth) acrylic acid hexadecyl ((meth) acrylate palmityl) , (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)acrylic acid stearyl (meth)acrylic acid alkyl ester, etc., in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms. can be heard

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. In addition, 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 ray-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 to this, in the aforementioned acrylic monomer or non-acrylic monomer, one or What is obtained by superposing|polymerizing the monomer which consists of two or more hydrogen atoms substituted by 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.

It is preferable that the weight average molecular weight (Mw) of the polymer (b) which does not have an energy ray-curable group is 10000-200000, and it is 100000-150000 from the point which the film-forming property of the composition for protective film formation (IV-1) becomes more favorable. more preferably.

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 of one type, or two or more types, and in the case of two or more types, combinations and ratios thereof can be chosen arbitrarily.

Examples of the composition (IV-1) for forming a protective film include those containing either or both of the polymer (a1) and the compound (a2). In addition, when the composition (IV-1) for forming a protective film contains the compound (a2), it is preferable to further contain a polymer (b) having no energy ray-curable group, and in this case, further (a1) It is also preferable to contain In addition, the composition (IV-1) for protective film formation does not contain the said compound (a2), but may contain the said polymer (a1) and the polymer (b) which do not have an energy-beam curable group together.

When the composition (IV-1) for forming a protective film contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, in the composition (IV-1) for forming a protective film, It is preferable that it is 10-400 mass parts, and, as for content of a compound (a2), it is more preferable that it is 30-350 mass parts with respect to 100 mass parts of total content of the said polymer (a1) and the polymer (b) which does not have an energy-beam curable group. .

In the composition (IV-1) for forming a protective film, the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (that is, the protective film) It is preferable that it is 5-90 mass %, and, as for the total content of the said energy-beam curable component (a) and the polymer (b) which does not have an energy-beam curable group of the film for formation), it is more preferable that it is 10-80 mass %, 15 It is especially preferable that it is -70 mass %, For example, any of 15-60 mass % and 15-50 mass % may be sufficient. When the ratio of the said total 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 energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, in the composition (IV-1) for forming a protective film and the film for forming a protective film , It is preferable that it is 3-500 mass parts with respect to content of 100 mass parts of energy-beam sclerosing|hardenable component (a), and, as for content of the said polymer (b), it is more preferable that it is 6-450 mass parts. When the said content of the said polymer (b) 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), and a coupling agent (e) depending on the purpose, in addition to the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group. , a crosslinking agent (f), a colorant (g), a thermosetting component (h), and a general-purpose additive (z) may contain one or two 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.

In addition, by using the composition (IV-1) for forming a protective film containing the colorant (g), the protective film finally formed makes it impossible to visually recognize the grinding marks on the back surface of the semiconductor chip, so that the appearance of the semiconductor chip can be improved. have. In addition, this protective film has excellent visibility of laser printing applied to the surface facing the support sheet.

[Photoinitiator (c)]

As the photoinitiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, etc. 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.

Moreover, 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 0.03-16 mass parts, It is especially preferable that it is 0.05-14 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 object of a protective film. Moreover, when the film for protective film formation contains a filler (d), the moisture absorption 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 light transmittance of the protective film can be suppressed while maintaining the adhesiveness to the object to be formed of the protective film.

On the other hand, it indicates the value of the "average particle diameter" means a particle diameter (D ₅₀₎ of the integrated value of 50% in the particle size distribution curve obtained by a laser diffraction scattering method, unless otherwise specified in this specification.

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 ratio of the content 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 ) is preferably 5-83 mass%, more preferably 7-78 mass%, for example, 10-78 mass%, 20-78 mass%, 30-78 mass%, 40- Any of 78 mass % and 50-78 mass % may be sufficient. When content of a filler (d) is such a range, adjustment of said thermal expansion coefficient becomes easier.

[Coupling agent (e)]

By using as a coupling agent (e) what has a functional group which can react with an inorganic compound or an organic compound, the adhesiveness and adhesiveness with respect to the to-be-adhered body of the film for protective film formation can be improved. Moreover, water resistance improves the protective film obtained by hardening|curing the film for protective film formation by using a coupling agent (e), without impairing heat resistance.

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 protective film formation and the film for protective film formation 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 a coupling agent (e) is used, in the composition (IV-1) for forming a protective film and the film for forming a protective film, the content of the coupling agent (e) is an energy ray-curable component (a) and a polymer having no energy ray-curable group. It is preferable that it is 0.03-20 mass parts with respect to 100 mass parts of total content of (b), 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 the adhesiveness with the to-be-adhered body of the film for protective film formation, etc. to what used the 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 polyhydric isocyanate compound (Hereinafter, these compounds are collectively abbreviated as "aromatic polyvalent isocyanate compound etc."); a trimer, an isocyanurate body, and an adduct body, such as the said aromatic polyhydric isocyanate compound; 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" is a reaction product of the aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound, or alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. means As an example of the said adduct body, the xylylene diisocyanate adduct of trimethylol propane as mentioned later, etc. are mentioned. In addition, "terminal isocyanate urethane prepolymer" means a prepolymer which has a urethane bond and has an isocyanate group in the terminal part of a molecule|numerator.

As said organic polyhydric isocyanate compound, More specifically, 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 polyvalent 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 the 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. When 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. Moreover, excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.

[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 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 film for protective film formation suitably according to the objective. For example, printing of a protective film may be performed by laser irradiation, and printing visibility can be adjusted by adjusting content of the coloring agent (g) of the film for protective film formation, and adjusting the light transmittance of a protective film. In this case, in the composition (IV-1) for forming a protective film, the ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, the content of the colorant (g) in the film for forming a protective film) is 0.1 It is preferable that it is -10 mass %, It is more preferable that it is 0.4-7.5 mass %, It is especially preferable that it is 0.8-5 mass %. 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. Moreover, 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 which has an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than the epoxy resin which does not have an 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 (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth)acrylamide group, and the like, An acryloyl group is preferable.

Although the number average molecular weight of an epoxy resin (h1) is not specifically limited, It is preferable that it is 300-30000, It is more preferable that it is 400-10000, From the point of sclerosis|hardenability of the film for protective film formation, and the intensity|strength and heat resistance of a protective film, it is 500- 3000 is particularly preferred.

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.

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. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group in which an acid group is anhydrideized, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrized is preferable, and a phenolic hydroxyl group, an amino group, or an acid group is an anhydride group. 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. have.

Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter, may be abbreviated as “DICY”).

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.

Among the thermosetting agents (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resins, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins 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 epoxy resin (h1). It is preferable that it is 20 mass parts.

When using a thermosetting component (h), 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.

[Universal Additive (z)]

Although the general-purpose additive (z) may be a well-known thing, it can select arbitrarily according to the objective, Although it does not specifically limit, As a preferable thing, a plasticizer, antistatic agent, antioxidant, a gettering agent, etc. are mentioned, for example.

The number of general-purpose additives (z) containing 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.

Although the said solvent is not specifically limited, As a preferable thing, For example, Hydrocarbons, such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (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 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.

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

<<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.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent and the 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

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of mixing by rotating a stirrer, a stirring blade, etc.; How to mix 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.

Similar to the composite sheet for forming a protective film of the present invention, which will be described later, it is affixed on the back surface opposite to the circuit surface of a semiconductor wafer or semiconductor chip. There is a bonding sheet.

However, the adhesive layer included in the dicing die bonding sheet functions as an adhesive when the semiconductor chip is picked up from the support sheet together with the semiconductor chip, and then the semiconductor chip is mounted on a substrate, lead frame, or other semiconductor chip. On the other hand, although the film for protective film formation in the composite sheet for protective film formation of this invention is the same as the said adhesive bond layer in the point which is picked up from a support sheet together with a semiconductor chip, it finally turns into a protective film by hardening and is pasted semiconductor. It has a function of protecting the back side of the chip. Thus, the film for protective film formation in this invention differs in a use from the adhesive bond layer in a dicing die-bonding sheet|seat, and the performance calculated|required also differs naturally. And compared with the adhesive bond layer in a dicing die-bonding sheet normally, the film for protective film formation tends to be hard reflecting this difference of use. It is usually difficult to divert the adhesive bond layer in a dicing die-bonding sheet as a film for protective film formation in the composite sheet for protective film formation as it is.

◇ Manufacturing method of film for forming protective film

The film for protective film formation of this invention 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.

On the other hand, 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. To that end, when the release film (preferably the release-treated surface) is 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, do.

◇ How to use the film for forming a protective film

As mentioned above, the film for protective film formation of this invention can comprise the composite sheet for protective film formation by forming in a support sheet. The composite sheet for protective film formation is affixed and used on the back surface (surface opposite to an electrode formation surface) of a semiconductor wafer with the film for protective film formation. Thereafter, by the same method as in the case of the composite sheet for forming a protective film mentioned later, dicing, pickup of a semiconductor chip with a protective film, etc. may be performed, and the target semiconductor device may be manufactured.

In addition, you may provide the film for protective film formation of this invention first on the back surface of a semiconductor wafer instead of a support sheet. That is, the film for protective film formation is affixed on the back surface of a semiconductor wafer. Next, an energy ray is irradiated to the film for protective film formation, the film for protective film formation is hardened, and it is set as a protective film. Next, by bonding a support sheet to the exposed surface (surface opposite to the side affixed to the semiconductor wafer) of this protective film, it is set as the composite sheet for protective film formation in a state in which the film for protective film formation became a protective film. Thereafter, dicing, pick-up of a semiconductor chip with a protective film, etc. may be performed in the same manner as above to manufacture a target semiconductor device.

In addition, here, after hardening the film for protective film formation to set it as a protective film, the case where this protective film is bonded together with a support sheet was demonstrated. However, when using the film for protective film formation of this invention, the procedure of performing these processes is The opposite may be true. That is, after affixing the film for protective film formation on the back surface of a semiconductor wafer, by bonding a support sheet to the exposed surface (surface opposite to the side affixed to the semiconductor wafer) of the film for protective film formation, the film for protective film formation is not A composite sheet for forming a protective film in a cured state is used. Next, an energy ray is irradiated to the film for protective film formation, the film for protective film formation is hardened, and it is set as a protective film. Thereafter, dicing, pick-up of a semiconductor chip with a protective film, etc. may be performed in the same manner as above to manufacture a target semiconductor device.

◇ Composite sheet for forming a protective film

The composite sheet for forming a protective film of the present invention includes a support sheet, the film for forming a protective film is provided on the support sheet, and when the protective film is irradiated with energy rays to form a protective film, the protective film and The adhesive force between the supporting sheets will be 50 to 1500 mN/25 mm.

The composite sheet for forming a protective film of the present invention is previously provided with a function as a dicing sheet.

In the composite sheet for forming a protective film, the tensile modulus of elasticity of the protective film is within the above range, and the adhesive force between the protective film and the supporting sheet is within the above range. The residual suppression effect of the push-up traces by the pin in the existing surface increases.

In the present invention, even after the film for forming a protective film is cured, as long as the laminated structure of the support sheet and the cured product of the film for forming a protective film (that is, the support sheet and the protective film) is maintained, this laminated structure is referred to as a "composite for forming a protective film. It's called a "sheet".

In the composite sheet for forming a protective film of the present invention, the adhesive force between the protective film and the supporting sheet is 50 to 1500 mN/25 mm, preferably 50 to 1450 mN/25 mm, more preferably 50 to 1400 mN/25 mm, For example, any of 50-1350 mN/25 mm, 50-1300 mN/25 mm, and 50-1250 mN/25 mm may be sufficient. When the adhesive force between the protective film and the support sheet is equal to or greater than the lower limit, the protective film can be stably maintained on the support sheet from the formation of the protective film until the semiconductor chip on which the protective film is formed is picked up. In addition, since the adhesive force between the protective film and the supporting sheet is equal to or less than the upper limit, when picking up the semiconductor chip on which the protective film is formed by a push-up method by a pin, it can be easily picked up even with a light push-up. The effect of suppressing the residual push-up traces by the pins is increased.

The adhesive force between a protective film and a support sheet can be measured by the following method.

That is, the composite sheet for protective film formation of which width is 25 mm and length is arbitrary is affixed to a to-be-adhered body with the film for protective film formation.

Next, after irradiating an energy ray to harden the film for protective film formation and forming a protective film, a support sheet is peeled from this protective film affixed to a to-be-adhered body at a peeling rate of 300 mm/min. The peeling at this time is so-called 180° peeling, in which the supporting sheet is peeled in the longitudinal direction (longitudinal direction of the composite sheet for forming a protective film) so that the surfaces of the protective film and the supporting sheet in contact with each other form an angle of 180°. . And the load (peel force) at the time of this 180 degree peeling is measured, and let the measured value be the said adhesive force (mN/25mm).

Although the length of the composite sheet for protective film formation used for a measurement will not be specifically limited if it is a range which can detect adhesive force stably, It is preferable that it is 100-300 mm. In addition, at the time of a measurement, it is preferable to make the composite sheet for protective film formation into the state affixed to a to-be-adhered body, and to stabilize the pasted state of the composite sheet for protective film formation.

In the present invention, the adhesive force between the film for forming a protective film and the supporting sheet is not particularly limited, and for example, 80 mN/25 mm or more may be sufficient, but 100 mN/25 mm or more is preferable, and 150 mN/25 mm or more is more It is preferable, and it is especially preferable that it is 200 mN/25 mm or more. When the said adhesive force is 100 mN/25 mm or more, at the time of dicing, peeling of the film for protective film formation and a support sheet is suppressed, For example, scattering from the support sheet of the semiconductor chip provided with the film for protective film formation on the back surface. this is suppressed

In addition, the upper limit of the adhesive force between the film for protective film formation and a support sheet is not specifically limited. For example, any of 4000 mN/25 mm or less, 3500 mN/25 mm or less, 3000 mN/25 mm or less may be sufficient as the said adhesive force. However, these upper limits are a preferable example.

The adhesive force between the protective film forming film and the support sheet can be measured in the same manner as the adhesive force between the protective film and the support sheet described above, except that the protective film forming film provided for measurement is not cured by irradiation with energy rays. have.

The above-described adhesive force between the protective film and the support sheet and the adhesive force between the protective film forming film and the support sheet is, for example, the type and amount of components contained in the protective film forming film, and the layer forming the protective film forming film in the support sheet. It can be suitably adjusted by adjusting the constituent material of this layer, the surface state of this layer, etc.

For example, the type and amount of the component contained in the film for forming a protective film can be adjusted by the type and amount of the component contained in the composition for forming a protective film. And, among the components of the composition for forming a protective film, for example, by adjusting the type and content of the polymer (b) not having an energy ray-curable group, the content of the filler (d), or the content of the crosslinking agent (f), the protective film or The adhesive force between the film for forming a protective film and the support sheet can be more easily adjusted.

In addition, for example, when the layer forming the film for forming a protective film in the support sheet is a pressure-sensitive adhesive layer described later, the constituent material of the pressure-sensitive adhesive layer can be appropriately adjusted by adjusting the type and amount of components contained in the pressure-sensitive adhesive layer. have. In addition, the type and amount of the component contained in the pressure-sensitive adhesive layer can be adjusted by the type and amount of the component contained in the pressure-sensitive adhesive composition to be described later.

On the other hand, when the layer forming the film for forming a protective film in the support sheet is a base material to be described later, the adhesive force between the protective film or the film for forming a protective film and the support sheet can be adjusted not only in the constituent materials of the base material, but also in the surface state of the base material. . In addition, the surface state of the base material is, for example, a surface treatment described later as to improve adhesion to other layers of the base material, that is, a roughening treatment by sand blasting treatment, solvent treatment, or the like; oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; It can be adjusted by performing any of a primer treatment etc.

Although the thickness of the semiconductor wafer or semiconductor chip which is the object of use of the composite sheet for protective film formation of this invention is not specifically limited, It is preferable that it is 30-1000 micrometers, and it is 100-300 micrometers from the point which the effect of this invention is acquired more notably. 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 in which the pressure-sensitive adhesive layer is laminated in direct contact with the substrate, those in which the pressure-sensitive adhesive layer is laminated on the substrate through an intermediate layer, and those formed only by the substrate.

The example of the composite sheet for protective film formation of this invention is demonstrated with reference to drawings below for every kind of such a support sheet.

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

In addition, in the drawings after FIG. 2, the same code|symbol as the case of the case of the illustrated figure is attached|subjected to the component same as that shown in the previously demonstrated drawing, and the detailed description is abbreviate|omitted.

The composite sheet 1A for protective film formation shown here is equipped with the adhesive layer 12 on the base material 11, and is equipped with the film 13 for protective film formation on the adhesive layer 12. As shown in FIG. 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, a film for forming a protective film on one surface 10a of the support sheet 10 . (13) has a stacked configuration. Moreover, 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 the composite sheet 1A for protective film formation, the adhesive layer 12 is laminated|stacked on one surface 11a of the base material 11, The film 13 for protective film formation on the whole surface of the one surface 12a of the adhesive layer 12. ) is laminated, and the adhesive layer 16 for a jig is laminated on a part of one surface 13a of the film 13 for forming a protective film, that is, in a region near the periphery, and the surface 13a of the film 13 for forming a protective film ), the release film 15 is laminated|stacked on the area|region where the adhesive bond layer 16 for jig|tools is not laminated|stacked, and the surface 16a (upper surface and side surface) of the adhesive bond layer 16 for jig|tools.

In the composite sheet for forming a protective film 1A, the adhesive force between the protective film forming film 13 (that is, the protective film) and the support sheet 10 after curing, that is, the adhesive force between the protective film and the pressure-sensitive adhesive layer 12 is 50 to 1500mN/25mm.

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, the back surface of a semiconductor wafer (not shown) is affixed to the surface 13a of the film 13 for forming a protective film in a state in which the release film 15 is removed, and further The upper surface of the surface 16a of the adhesive bond layer 16 for furnace jigs is affixed to jigs, such as a ring frame, and is used.

It is sectional drawing which shows typically other embodiment of the composite sheet for protective film formation of this invention.

The composite sheet 1B for protective film formation shown here is the same thing as 1A 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 jigs. That is, in the composite sheet 1B for protective film formation, the adhesive layer 12 is laminated|stacked on one surface 11a of the base material 11, The film for protective film formation on the whole surface of the surface 12a of the adhesive layer 12. (13) is laminated|stacked, and the peeling film 15 is laminated|stacked on the whole surface of the surface 13a of the film 13 for protective film formation.

In the composite sheet 1B for forming a protective film shown in Fig. 3, in a state in which the release film 15 is removed, a semiconductor wafer (not shown) is placed in a central portion of the surface 13a of the film 13 for forming a protective film. The back surface is affixed, and the area|region in the vicinity of a periphery is affixed to jigs, such as a ring frame, and is used further.

It is sectional drawing which shows typically still another embodiment of the composite sheet for protective film formation of this invention.

The composite sheet 1C for protective film formation shown here is the same thing as 1 A 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 of only the base material 11. As shown in FIG. And the protective film formation film 13 is laminated|stacked on one surface 11a of the base material 11 (one surface 10a of the support sheet 10), and the surface 13a of the protective film formation film 13 A part, that is, the area|region where the adhesive bond layer 16 for jig|tools is laminated|stacked in the area|region near the periphery, and the area|region on which the adhesive bond layer 16 for jig|tools is not laminated|stacked among the surface 13a of the film 13 for protective film formation, and for jig|tools A release film 15 is laminated on the surface 16a (upper surface and side surface) of the adhesive layer 16 .

In the composite sheet for forming a protective film 1C, the adhesive force between the protective film forming film 13 (that is, the protective film) and the support sheet 10 after curing, that is, the adhesive force between the protective film and the base material 11 is 50 to 1500 mN /25mm.

The composite sheet 1C for forming a protective film shown in Fig. 4 is the same as 1A of the composite sheet for forming a protective film shown in Fig. 2, with the release film 15 removed, the surface of the film 13 for forming a protective film ( The back surface of a semiconductor wafer (not shown) is affixed to 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.

It is sectional drawing which shows typically still another embodiment of the composite sheet for protective film formation of this invention.

The composite sheet 1D for protective film formation shown here is the same thing as 1 C 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 one surface 11a of the base material 11, and peels on the whole surface of the surface 13a of the film 13 for protective film formation. Films 15 are laminated.

The composite sheet 1D for forming a protective film shown in Fig. 5 is the same as the composite sheet 1B for forming a protective film shown in Fig. 3, with the release film 15 removed, the surface of the film 13 for forming a protective film ( In 13a), the back surface of a semiconductor wafer (not shown) is affixed to the central side part area|region, and the area|region in the vicinity of a periphery is further pasted to jigs, such as a ring frame, and used.

It is sectional drawing which shows typically still another embodiment of the composite sheet for protective film formation of this 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 protective film formation comprises the adhesive layer 12 on the base material 11, and equips the adhesive layer 12 with the film 23 for protective film formation. 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 is, in other words, a film for forming a protective film on one surface 10a of the support sheet 10 . (23) has a stacked configuration. Moreover, the composite sheet 1E for protective film formation is equipped with the peeling film 15 on the film 23 for protective film formation further.

In the composite sheet 1E for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the substrate 11, and a protective film is formed on a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, in the central region. The film 23 for formation is laminated|stacked. And the release film 15 on the area|region where the film 23 for protective film formation is not laminated|stacked among the surface 12a of the adhesive layer 12, and the surface 23a (upper surface and side surface) of the film 23 for protective film formation. ) are stacked.

When the composite sheet 1E for protective film formation is looked down from upper direction 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 adhesive force between the protective film forming film 23 (that is, the protective film) and the support sheet 10 after curing, that is, the adhesive force between the protective film and the pressure-sensitive adhesive layer 12 is 50 to 1500mN/25mm.

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

In addition, in the composite sheet 1E for protective film formation shown in FIG. 6, in the area|region where the film 23 for protective film formation is not laminated|stacked among the surface 12a of the adhesive layer 12, what is shown in FIGS. 2 and 4 Similarly, the adhesive bond layer for jig|tools may be laminated|stacked (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 a 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 of this invention may be sufficient as it. However, normally, as shown in FIGS. 2 and 4, as the composite sheet for protective film formation of this invention provided with the adhesive bond layer for jig|tools, it is preferable that what was equipped with the adhesive bond layer for jigs on the film for protective film formation.

The composite sheet for forming a protective film of the present invention is not limited to that shown in Figs. 2 to 6, but within a range that does not impair the effects of the present invention, some configurations of those shown in Figs. 2 to 6 are changed or deleted, but now In addition to what has been described above, other configurations may be added.

For example, in the composite sheet for protective film formation shown in FIGS. 4 and 5, an 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 according to the purpose.

In addition, in the composite sheet for protective film formation shown in FIGS. 2, 3, and 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. 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 to FIGS.

In addition, 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 addition, in the composite sheet for protective film formation of this invention, a part of clearance gap may generate|occur|produce between the peeling film and the layer in direct contact with this peeling film.

In addition, in the composite sheet for forming a protective film of the present invention, 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 support 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, and may be colored according to the objective.

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.

Further, 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|permeability of the said light is this range, when a laser beam is irradiated to the film for protective film formation or a protective film through a support sheet, and it prints on these, it can print 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.

Further, 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|permeability of the said light is this range, when a laser beam is irradiated to the film for protective film formation or a protective film through a support sheet, and it prints on these, it can print more clearly.

In addition, in a support sheet, the upper limit of the transmittance|permeability of the light with a wavelength of 1064 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 further described in detail.

○ Description

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 polyethylenes 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; copolymers 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.

Moreover, 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.

Moreover, as said resin, For example, 1 type or 2 or more types of the said resin exemplified so far are crosslinked crosslinked resins; Modified resins, such as an ionomer using 1 type, or 2 or more types of the said resin illustrated so far, are also mentioned.

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

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 substrate may be composed 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, "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.

It is preferable that the base material has high precision in thickness, that is, that variation in thickness is suppressed regardless 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, and ethylene-vinyl acetate copolymer.

The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts and softeners (plasticizers) in addition to the main constituent materials such as the resin.

The optical properties of the substrate may satisfy the optical properties of the support sheet described above. That is, 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.

In addition, the surface to which the primer process was given may be sufficient as a base material.

In addition, the base material may have an antistatic coating layer and a layer preventing the base material from adhering to the adsorption table when the composite sheet for forming a protective film is stacked on top of each other and stored.

Among these, it is preferable that the surface of a base material given electron beam irradiation treatment is especially preferable from the point which generation|occurrence|production of the base material fragmentation by the friction of the blade at the time of dicing is suppressed.

The substrate can be prepared by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the 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 pressure-sensitive adhesive include adhesive resins such as acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins, and acrylic resins are preferred.

On the other hand, 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 with other components such as additives. Resin which shows adhesiveness by combined use, resin etc. which show adhesiveness by presence of triggers, such as heat or water, are also included.

An adhesive layer may consist of one layer (single layer), may consist of two or more layers, and may consist of multiple 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.

The optical properties of the pressure-sensitive adhesive layer may satisfy the optical properties of the support sheet described above. That is, transparent may be sufficient as an adhesive layer may be sufficient, and it 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 as needed. A more specific method of forming the pressure-sensitive adhesive layer will be described later in detail along with the method of forming other layers. The ratio of content of components which do not vaporize at normal temperature in an adhesive composition becomes the same as the ratio of content of the said components of an adhesive layer normally. Here, "room temperature" is the same as described above.

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, a Meyer bar. The method of 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 an 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 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, or 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.

As (meth)acrylic acid alkylester, more specifically, (meth)acrylic acid methyl, (meth)acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid isopropyl, (meth)acrylic acid n-butyl, (meth)acrylate 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) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl ((meth) acrylate ) acrylic acid lauryl), (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. And 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. Moreover, it is preferable that C4 or more of the said alkyl group (meth)acrylic-acid alkylester is an acrylic 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

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxy group, an amino group, an epoxy group, etc. are mentioned, for example.

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) acrylic acid 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 (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.

In the said acrylic polymer, 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 amount of structural units, 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 other monomer is not particularly limited as long as it can be copolymerized with (meth)acrylic acid alkylester or the like.

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, what made the functional group in the said acrylic polymer react the unsaturated-group containing compound which has an energy-beam polymerizable unsaturated group (energy-beam polymeric group) can be used as the above-mentioned energy-beam 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.

PSA composition (I-1) WHEREIN: It is preferable that content of adhesive resin (I-1a) is 5-99 mass %, It is more preferable that it is 10-95 mass %, It is especially preferable that it is 15-90 mass % do.

[Energy-ray-curable compound]

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

As a monomer among the energy ray-curable compounds, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1 polyvalent (meth)acrylates such as ,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.

As an oligomer among energy-beam-curable compounds, the oligomer etc. which form by superposing|polymerizing the monomer illustrated above are mentioned, for example.

The energy-beam-curable compound has a comparatively large molecular weight, and urethane (meth)acrylate and a urethane (meth)acrylate oligomer are preferable at the point that 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 sclerosing|hardenable compound is 1-95 mass %, It is more preferable that it is 5-90 mass %, 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).

As a crosslinking agent, For example, isocyanate type crosslinking agents (crosslinking agent which has an isocyanate group), such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the adduct body of these diisocyanate; 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 it is easy to obtain.

The number of crosslinking agents 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 crosslinking agent is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 20 parts by mass, and 0.3 to 100 parts by mass of the content of the adhesive resin (I-1a). It is especially preferable that it is -15 mass parts.

[Photoinitiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photoinitiator. Even if the pressure-sensitive adhesive composition (I-1) containing a photoinitiator is irradiated with energy rays of relatively low energy such as ultraviolet rays, the curing reaction proceeds sufficiently.

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.

Moreover, as said photoinitiator, For example, quinone compounds, such as 1-chloroantoraquinone; Photosensitizers, such as an amine, etc. can also be used.

The number of photoinitiators which the pressure-sensitive adhesive composition (I-1) contains 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 (catalysts) ) and other known additives.

Here, the reaction retarder suppresses the progress of an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1), for example. will do 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. .

The number of other additives 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: 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.

The solvent may be used as it is in the pressure-sensitive adhesive composition (I-1) without removing it from the pressure-sensitive adhesive resin (I-1a), for example, the solvent used in the production of the pressure-sensitive adhesive resin (I-1a), or the pressure-sensitive adhesive resin (I-1a) 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, combinations and ratios thereof 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.

As said energy-beam polymerizable unsaturated group, a (meth)acryloyl group, a vinyl group (ethenyl group), an allyl group (2-propenyl group) etc. are mentioned, for example, A (meth)acryloyl group is preferable.

Examples of the group capable of bonding with the 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.

One type may be sufficient as the adhesive resin (I-2a) 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.

PSA composition (I-2) WHEREIN: It is preferable that content of adhesive resin (I-2a) is 5-99 mass %, It is more preferable that it is 10-95 mass %, It is especially preferable that it is 10-90 mass % do.

[crosslinking agent]

When using, for example, the above-mentioned acrylic polymer having structural units derived from the same functional group-containing monomer as in the adhesive resin (I-1a) as the adhesive resin (I-2a), the pressure-sensitive adhesive composition (I-2) is additionally and 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 of 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. Even if it irradiates comparatively low energy energy rays, such as an ultraviolet-ray, hardening reaction fully advances hardening reaction of the adhesive composition (I-2) containing a photoinitiator.

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

The number of photoinitiators 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.

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 an adhesive composition (I-2), 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-2) contains 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-2) WHEREIN: 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 %, It is more preferable that it is 10-95 mass %, It is especially preferable that it is 15-90 mass % do.

[Energy-ray-curable compound]

Examples of the energy ray-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 ray-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 content 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 adhesive composition (I-3) containing a photoinitiator irradiates comparatively low energy energy rays, such as an ultraviolet-ray, hardening reaction fully advances.

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.

The pressure-sensitive adhesive composition (I-3) 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-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 type, two or more types, and in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 the overall pressure-sensitive adhesive composition ( In this specification, it can also be used similarly to "Adhesive compositions other than 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 two or more types of crosslinking agents, and the content thereof is the same as in the case of the above-described pressure-sensitive adhesive composition (I-1) and the like. can do.

<Adhesive composition (I-4)>

As a preferable thing of the 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.

PSA composition (I-4) WHEREIN: It is preferable that content of adhesive resin (I-1a) is 5-99 mass %, It is more preferable that it is 10-95 mass %, It is especially preferable that it is 15-90 mass % do.

[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 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.

In the pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the content of the adhesive resin (I-1a), 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 adhesive composition (I-4), the thing similar to the solvent in 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, combinations and ratios thereof can be arbitrarily selected.

The pressure-sensitive adhesive composition (I-4) WHEREIN: Content of a solvent is not specifically limited, What is necessary is just to adjust suitably.

The composite sheet for protective film formation of this invention WHEREIN: It is preferable that an adhesive layer is 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 may not be able to suppress that an adhesive layer also hardens simultaneously. When the pressure-sensitive adhesive layer is cured simultaneously with the film for forming a protective film, the film for forming a protective film and the pressure-sensitive adhesive layer after curing may be affixed to such an extent that peeling is impossible at these interfaces. In that case, it becomes difficult to peel the cured film for forming a protective film, that is, a semiconductor chip having a protective film on the back surface (semiconductor chip with a protective film) from the support sheet having an adhesive layer after curing, and the semiconductor chip with a protective film You will not be able to pick up normally. By making an adhesive layer into a non-energy-ray-curable thing in the support sheet in this invention, 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 composition (I-1) to (I-3) or the pressure-sensitive adhesive composition (I-4) other than the pressure-sensitive adhesive composition (I-1) to (I-3), such as the pressure-sensitive adhesive composition (I-4), It is obtained by mix|blending each component for comprising adhesive compositions, such as components other than an 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.

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent and the 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

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of mixing by rotating a stirrer, a stirring blade, etc.; How to mix 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 composite sheet for forming protective film

The composite sheet for forming a protective film of the present invention can be manufactured by sequentially laminating the above-described layers so as to have a corresponding positional relationship. A method of forming each layer is the same as described above.

For example, when manufacturing a support sheet, when laminating|stacking an adhesive layer on a base material, what is necessary is just to coat the above-mentioned adhesive composition on a base material, and just to dry it 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. Layers other than the film for forming a protective film can also be laminated on the pressure-sensitive adhesive layer in the same manner using the composition for forming the layer. As described above, in the case of forming a continuous two-layer laminate structure using any 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 exposed surface of the formed layer opposite to the side in contact with the release film is set as the exposed surface of the remaining layer already formed. It is preferable to form the laminated structure of two continuous layers by bonding together. 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 as needed after formation of a laminated structure.

For example, a composite sheet for forming a protective film in which a pressure-sensitive adhesive layer is laminated on a substrate and a film for forming a protective film is laminated on the pressure-sensitive adhesive layer (a composite sheet for forming a protective film in which the support sheet is a laminate of the substrate and the pressure-sensitive adhesive layer) In the case of doing so, the pressure-sensitive adhesive composition is applied on the base material and dried as needed, the pressure-sensitive adhesive layer is laminated on the base material, and separately, the composition for forming a protective film is coated on the release film and dried as needed. 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 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.

In addition, in the case of 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 composition is applied on the release film and dried as necessary, on the release film. An adhesive layer may be laminated|stacked on a base material by providing an adhesive layer and bonding the exposed surface of this layer with one surface of a base material.

In any method, what is necessary is just to remove a peeling film at arbitrary timings after formation of 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 use suitably and to manufacture the composite sheet for protective film formation.

In addition, 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 release film (preferably, the release-treated surface thereof), a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is coated and dried if necessary, so that the most The layers constituting the surface layer are formed, the remaining respective layers are laminated on the exposed surface on the opposite side to the side in contact with the release film of this layer by any of the methods described above, and the release film is left to be bonded without removing it. , a composite sheet for forming a protective film is obtained.

◇ How to use the composite sheet for forming a protective film

The composite sheet for protective film formation of this invention can be used by the method shown below, for example.

That is, the composite sheet for protective film formation is affixed with the film for protective film formation on the back surface (surface opposite to an electrode formation surface) of a semiconductor wafer. Next, an energy ray is irradiated to the film for protective film formation, the film for protective film formation is hardened, and it is set as a protective film. Then, the semiconductor wafer is divided for each protective film by dicing to obtain a semiconductor chip. And the semiconductor chip is removed from the support sheet and picked up, with this protective film affixed (namely, as a semiconductor chip with a protective film formed).

Thereafter, by the same method as the conventional method, the obtained semiconductor chip of the semiconductor chip provided with the protective film is flip-chip connected to the circuit surface of the substrate, and then, a semiconductor package is obtained. And what is necessary is just to manufacture the target semiconductor device using this semiconductor package.

In addition, although the case where dicing is performed after hardening the film for protective film formation and setting it as a protective film was demonstrated here, when using the composite sheet for protective film formation of this invention, the order of performing these processes may be reversed. That is, after affixing the composite sheet for protective film formation on the back surface of a semiconductor wafer, by dicing, a semiconductor wafer is divided|segmented for every film for protective film formation, and it is set as a semiconductor chip. Next, an energy ray is irradiated to the divided film for protective film formation, the film for protective film formation is hardened, and it is set as a protective film. After that, similarly to the above, the semiconductor chip provided with the protective film is removed from the support sheet and picked up, and what is necessary is just to produce the target semiconductor device.

Example

Hereinafter, the present invention will be described in more detail by way of specific examples. However, this invention is by no means limited to the Example shown below.

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

・Energy-ray-curable ingredients

(a2)-1: tricyclodecanedimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., bifunctional ultraviolet curable compound, molecular weight 304)

Polymers without energy ray-curable groups

(b)-1: butyl acrylate (hereinafter, abbreviated as “BA”) (10 parts by mass), methyl acrylate (hereinafter, abbreviated as “MA”) (70 parts by mass), glycidyl methacrylate (hereinafter, abbreviated as “MA”) , abbreviated as "GMA") (5 parts by mass) and acrylic acid-2-hydroxyethyl (hereinafter, abbreviated as "HEA") (15 parts by mass) of an acrylic polymer (weight average molecular weight 300000, glass transition) temperature -1°C).

・Photoinitiator

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

(c)-2: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) ("Irgacure" manufactured by BASF) (registered trademark) OXE02”)

·filling

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

・Coupling agent

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

·coloring agent

(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.

[Example 1]

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

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

Energy ray curable component ((a2)-1), polymer ((b)-1), photoinitiator ((c)-1), photoinitiator ((c)-2), filler ((d)-1), The coupling agent ((e)-1) and the colorant ((g)-1) were dissolved or dispersed in methyl ethyl ketone so that their contents (solid content, parts by mass) became the values shown in Table 1, and stirred at 23 ° C. By doing so, the composition for protective film formation (IV-1) whose solid content concentration is 50 mass % was prepared.

(Preparation of adhesive composition (I-4))

Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent The non-energy-ray-curable adhesive composition (I-4) whose solid content concentration to make is 30 mass % was prepared. The acrylic polymer has a weight average molecular weight of 600000 obtained by copolymerizing acrylic acid-2-ethylhexyl (hereinafter abbreviated as "2EHA") (36 parts by mass), BA (59 parts by mass) and HEA (5 parts by mass). .

(Manufacture of support sheet)

The pressure-sensitive adhesive composition (I-4) obtained above is coated on 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 has been subjected to release treatment by silicone treatment, , a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm was formed by heating and drying at 120° C. for 2 minutes.

Next, by bonding a polypropylene-based film (Young's modulus 400 MPa, thickness 80 µm) as a base material to the exposed surface of this pressure-sensitive adhesive layer, a support sheet (10)-1 having the pressure-sensitive adhesive layer on one surface of the base material is formed. got it

(Manufacture of composite sheet for forming a protective film)

The composition (IV-1) for forming a protective film obtained above was applied to the release-treated surface of a release film (“SP-PET381031” manufactured by Lintec, 38 µm thick) in which one side of the polyethylene terephthalate film was released by silicone treatment. The 25-micrometer-thick film ((13)-1) for energy-beam curable protective film formation was produced by coating with a knife coater and drying at 100 degreeC for 2 minutes.

Next, the release film is removed from the pressure-sensitive adhesive layer of the support sheet ((10)-1) obtained above, and the exposed surface of the protective film formation film ((13)-1) obtained above is attached to the exposed surface of the pressure-sensitive adhesive layer. In total, the composite sheet for protective film formation in which a base material, an adhesive layer, the film for protective film formation ((13)-1), and a peeling film are laminated|stacked in this order in these thickness direction was produced. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation>

(Tensile modulus of protective film)

The film for protective film formation ((13)-1) obtained above was cut out, and the test piece was produced.

Next, using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), the film for forming a protective film (13)-1 by irradiating the test piece with ultraviolet rays under the conditions of an illuminance of 195 mW/cm 2 and a light amount of 170 mJ/cm 2 ) was cured to obtain a protective film test piece.

Next, based on JIS K7161:1994, the tensile modulus (Young's modulus) of the said protective film test piece in 23 degreeC was measured. At this time, the width at the time of the measurement of the protective film test piece was 15 mm, the distance between chuck|zippers was 10 mm, and the tensile speed was 50 mm/min. A result is shown in Table 2.

(Shore D hardness of the protective film)

After laminating the film for forming a protective film ((13)-1) obtained above to have a total thickness of 6 mm, the obtained laminate is irradiated with ultraviolet rays under the same conditions as at the time of measuring the tensile modulus of elasticity of the protective film. The film for formation ((13)-1) was all hardened|cured and it was set as the protective film.

Next, about the laminated body of the obtained protective film, Shore D hardness was measured in 23 degreeC using the static pressure loader ("CL-150" by Polymer Instruments Co., Ltd.). A result is shown in Table 2.

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

(Adhesive force between the protective film and the supporting sheet)

The composite sheet for forming a protective film obtained above is cut to a size of 25 mm × 140 mm, the release film is removed from the composite sheet for forming a protective film, and one surface of the film for forming a protective film ((13)-1) is exposed, It was set as the test piece before hardening. On the other hand, what bonded the double-sided adhesive tape on the surface of the support plate (70 mm x 150 mm) made from SUS was prepared. Then, using a laminator (“LAMIPACKER LPD3214” manufactured by Fuji Corporation), the exposed surface of the film (13)-1 for forming a protective film of the test piece before curing is attached to the double-sided adhesive tape on the support plate. The test piece before hardening was affixed through the.

Next, 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 ((13)- 1) was cured to obtain a test piece after curing.

Next, using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation), under the conditions of a peeling angle of 180°, a measurement temperature of 23°C, and a tensile rate of 300 mm/min, the support sheet ((10)-1) A tensile test for peeling (the laminate of the pressure-sensitive adhesive layer and the base material before curing) from the protective film was performed, the load (peel force) at this time was measured, and the adhesive force between the protective film and the supporting sheet (10)-1 was taken. In addition, as the measured value of the said load, among the measured values when the support sheet (10)-1 was peeled over a length of 100 mm, the time of peeling only by a length of 10 mm first, and a length of 10 mm at the end The thing which removed each measured value at the time of peeling only by the effective value was employ|adopted. A result is shown in Table 2.

(Suppression of residual push-up traces by pins in the protective film)

The composite sheet for forming a protective film obtained above was affixed to the #2000 polished surface of a 6-inch silicon wafer (350 mu m thick) with the protective film forming film (13)-1, and this sheet was further fixed to a ring frame. So it was held for 30 minutes.

Then, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec Co., Ltd.), ultraviolet rays were applied to the composite sheet for forming a protective film from the support sheet (10)-1 side under the conditions of illuminance of 195 mW/cm 2 and light amount of 170 mJ/cm 2 By irradiating, the film for protective film formation ((13)-1) was hardened, and it was set as the protective film.

Next, using a dicing blade, the silicon wafer was diced for each protective film and separated into pieces to obtain a silicon chip of 5 mm x 5 mm.

Next, using a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.), the silicon wafer with one protective film was pushed up with one pin, and the silicon chip with 20 protective films was picked up. Then, for the silicon chips on which 10 protective films were formed, the presence or absence of residual push-up traces by pins on the surface facing the support sheet of the protective film was visually checked, and residual push-up traces were confirmed. When the number of silicon chips with a protective film is 0, "A" is determined, the case of 1 to 3 is determined as "B", and the case of 4 to 10 is determined as "C", The residual inhibitory effect of the push-up trace was evaluated. A result is shown in Table 2. The description in the column of "residual suppression of a push-up trace" in Table 2 is a corresponding result.

<Production and evaluation of a film for forming a protective film and a composite sheet for forming a protective film>

[Example 2]

The corona discharge treatment was performed on the surface of the same base material (polypropylene film, Young's modulus 400 MPa, thickness 80 micrometers) as used at the time of manufacture of the support sheet (10)-1). And, as shown in Table 2, in the same manner as in Example 1, except that the support sheet (10)-2 made only of the substrate subjected to this surface treatment was used instead of the support sheet (10)-1. The film for protective film formation and the composite sheet for protective film formation were manufactured and evaluated. A result is shown in Table 2. In addition, in this Example, the film (13)-1 for protective film formation was formed on the corona discharge-treated surface of the said base material corresponded to the support sheet (10)-2.

[Example 3]

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

(Preparation of adhesive composition (I-4))

Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (0.5 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent The non-energy-ray-curable adhesive composition (I-4) whose solid content concentration to make is 30 mass % was prepared. The acrylic polymer is obtained by copolymerizing BA (95 parts by mass) and HEA (5 parts by mass) and has a weight average molecular weight of 800,000.

(Manufacture of support sheet)

Except for using the pressure-sensitive adhesive composition (I-4) obtained above, in the same manner as in Example 1, a non-energy-ray-curable pressure-sensitive adhesive layer having a thickness of 10 µm was formed on the substrate to prepare a support sheet ((10)-3). did.

(Manufacture of composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1, except that the supporting sheet ((10)-3) obtained above was used instead of the supporting sheet (10)-1). Table 2 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation obtained above, and the composite sheet for protective film formation, the method similar to Example 1 evaluated. A result is shown in Table 2.

[Example 4]

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

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

As shown in Table 1, the content (blending amount) of the polymer ((b)-1) was 2 parts by mass instead of 22 parts by mass, and the content (blended amount) of the filler ((d)-1) was changed to 56 parts by mass. A composition (IV-1) for forming a protective film was prepared in the same manner as in Example 1 except that it was set to 76 parts by mass.

(Manufacture of composite sheet for forming a protective film)

A 25-micrometer-thick film ((13)-2) for forming an energy ray-curable protective film was produced in the same manner as in Example 1 except that the composition (IV-1) for forming a protective film obtained above was used.

And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except the point using this film for protective film formation ((13)-2) instead of the film ((13)-1) for protective film formation. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation obtained above, and the composite sheet for protective film formation, the method similar to Example 1 evaluated. A result is shown in Table 2.

[Example 5]

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

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

A composition (IV-1) for forming a protective film was prepared in the same manner as in Example 1.

(Production of film for forming a protective film)

The composition for forming a protective film (IV-1) obtained above on the release-treated surface of a release film (“SP-PET381031” manufactured by Lintec, 38 µm thick) in which one side of the polyethylene terephthalate film was released by silicone treatment. ) was coated with a knife coater and dried at 100°C for 2 minutes to prepare a film ((13)-1) for forming an energy ray-curable protective film having a thickness of 25 µm.

(Manufacture of support sheet)

A support sheet (10)-1 was produced in the same manner as in Example 1.

(Manufacture of composite sheet for forming a protective film)

The surface of the film for protective film formation ((13)-1) obtained above on the opposite side to the side on which the peeling film was formed was affixed to the #2000 polished surface of a 6-inch silicon wafer (350 micrometers in thickness).

Next, 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 protective film was irradiated with ultraviolet rays to the film for forming a protective film ((13)-1). The film for formation ((13)-1) was hardened and it was set as the protective film.

Next, the release film is removed from the protective film, the pressure-sensitive adhesive layer of the support sheet (10)-1 obtained above is bonded to the exposed surface, and the base material, the pressure-sensitive adhesive layer, the protective film and the silicon wafer are in this order in their thickness direction. A composite sheet for forming a protective film on which a silicon wafer laminated with was formed was produced. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation obtained above, and the composite sheet for protective film formation, the method similar to Example 1 evaluated. A result is shown in Table 2.

[Example 6]

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

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

As shown in Table 1, the composition for forming a protective film (IV-) in the same manner as in Example 1, except that the content (mixing amount) of the energy ray-curable component ((a2)-1) was 10 parts by mass instead of 20 parts by mass. 1) was prepared.

(Manufacture of composite sheet for forming a protective film)

A 25-micrometer-thick film ((13)-3) for forming an energy ray-curable protective film was produced in the same manner as in Example 1 except that the composition (IV-1) for forming a protective film obtained above was used.

And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except the point using this film for protective film formation ((13)-3) instead of the film ((13)-1) for protective film formation. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation obtained above, and the composite sheet for protective film formation, the method similar to Example 1 evaluated. A result is shown in Table 2.

[Example 7]

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

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

As shown in Table 1, the composition for forming a protective film (IV-) in the same manner as in Example 1, except that the content (mixing amount) of the energy ray-curable component ((a2)-1) was 5 parts by mass instead of 20 parts by mass. 1) was prepared.

(Manufacture of composite sheet for forming a protective film)

A 25-micrometer-thick film ((13)-4) for forming an energy ray-curable protective film was produced in the same manner as in Example 1 except that the composition (IV-1) for forming a protective film obtained above was used.

And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except the point using this film for protective film formation ((13)-4) instead of the film ((13)-1) for protective film formation. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation obtained above, and the composite sheet for protective film formation, the method similar to Example 1 evaluated. A result is shown in Table 2.

[Reference Example 1]

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

(Preparation of adhesive composition)

Acrylic polymer (100 parts by mass, solid content), a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (6.6 parts by mass, solid content) and a photopolymerization initiator (2-hydroxy-1-{4) -[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, "Irgacure (registered trademark) 127" manufactured by BASF) (3.0 parts by mass, solid content) was contained and the solid content concentration further containing methyl ethyl ketone as a solvent prepared the energy-beam curable adhesive composition which is 30 mass %. The acrylic polymer is a pre-copolymer formed by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass), 2-methacryloyloxyethyl isocyanate (21.4 parts by mass, isocyanate group with respect to 100 mol% of hydroxyl groups in HEA) It is an energy-beam curable acrylic polymer with a weight average molecular weight of 1100000 obtained by making it react (amount used as 80 mol%).

(Manufacture of support sheet)

A support sheet (90) having an energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 µm on a substrate in the same manner as in Example 1, except that the energy ray-curable pressure-sensitive adhesive composition obtained above was used instead of the pressure-sensitive adhesive composition (I-4). -1) was produced.

(Manufacture of composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1, except that the support sheet (90)-1 obtained above was used instead of the support sheet (10)-1). Table 3 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation and the composite sheet for protective film formation obtained above, the method similar to Example 1 evaluated. A result is shown in Table 3.

[Reference Example 2]

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

(Preparation of adhesive composition)

Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (0.5 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent The non-energy-ray-curable adhesive composition whose solid content concentration to make is 30 mass % was prepared. The acrylic polymer has a weight average molecular weight of 600000 obtained by copolymerizing BA (79 parts by mass), MA (16 parts by mass) and HEA (5 parts by mass).

(Manufacture of support sheet)

A support sheet ((90)-2) provided with a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 µm on a substrate was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained above was used.

(Manufacture of composite sheet for forming a protective film)

A composite sheet for forming a protective film was produced in the same manner as in Example 1, except that the support sheet (90)-2 obtained above was used instead of the support sheet (10)-1). Table 3 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation obtained above, and the composite sheet for protective film formation, the method similar to Example 1 evaluated. A result is shown in Table 3.

[Comparative Example 1]

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

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

As shown in Table 1, the composition for forming a protective film (IV-) in the same manner as in Example 1, except that the content (mixing amount) of the energy ray-curable component ((a2)-1) was 2 parts by mass instead of 20 parts by mass. 1) was prepared.

(Manufacture of composite sheet for forming a protective film)

A film ((93)-1) for forming an energy ray-curable protective film having a thickness of 25 µm was produced in the same manner as in Example 1 except that the composition (IV-1) for forming a protective film obtained above was used.

And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except the point using this film for protective film formation ((93)-1) instead of the film ((13)-1) for protective film formation. Table 3 shows the structure of the obtained composite sheet for forming a protective film.

<Evaluation of the film for protective film formation and the composite sheet for protective film formation>

About the film for protective film formation and the composite sheet for protective film formation obtained above, the method similar to Example 1 evaluated. A result is shown in Table 3.

As is clear from the above results, when the composite sheets for forming a protective film of Examples 1 to 7 were used, the tensile modulus of elasticity of the protective film was 2×10 ⁸ Pa or more, and the adhesive force between the protective film and the supporting sheet was 55 to 1400 mN/25 mm. As a result, the residual suppression effect of the push-up traces by the pins in the protective film was high. Moreover, in Examples 1-7, the Shore D hardness of the protective film was 56 or more.

On the other hand, when the composite sheet for forming a protective film of Reference Examples 1 and 2 was used, the adhesive force between the protective film and the supporting sheet was 3300 to 4860 mN/25 mm, so that the residual suppression effect of the push-up traces by the pins in the protective film was reduced. It was low.

In addition, when the composite sheet for forming a protective film of Comparative Example 1 was used, the protective film had a tensile elastic modulus of 9×10 ⁷ Pa, so that the residual suppression effect of the push-up traces by the pins in the protective film was low. The protective film in Comparative Example 1 had a lower Shore D hardness than the protective film in Reference Examples 1-2.

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

1A, 1B, 1C, 1D, 1E: Composite sheet for forming a protective film
10: support sheet
10a: the surface of the support sheet
11: description
11a: the surface of the substrate
12: adhesive layer
12a: the surface of the pressure-sensitive adhesive layer
13, 23: film for forming a protective film
13a, 23a: the surface of the film for forming a protective film (one surface)
13b: the surface of the film for forming a protective film (the other surface)
15: release film
151: first release film
152: second release film
16: adhesive layer for jig
16a: surface of adhesive layer for jig

Claims (3)

A support sheet is provided, and a film for forming an energy ray-curable protective film is provided on the support sheet,
When the protective film is irradiated with energy rays to form a protective film, the protective film has a tensile modulus of 1×10 ⁸ Pa or more and 5.4×10 ⁹ Pa or less,
Shore D hardness of the protective film is 55 or more and 70 or less,
A composite sheet for forming a protective film, wherein the adhesive force between the protective film and the supporting sheet is 50 to 1500 mN/25 mm. The method of claim 1,
A composite sheet for forming a protective film having an adhesive force of 690 to 1500 mN/25 mm. delete

Images