KR20230141435A - Protective film forming sheet, composite sheet for protective film formation, kit, and use of protective film forming sheet - Google Patents

Abstract

An energy-ray curable protective film forming film, wherein the rate of change in indentation depth measured by a specific method for measuring the rate of change in indentation depth is 60% or more.

Description

Protective film forming film, composite sheet for forming a protective film, kit, and use of the protective film forming film {PROTECTIVE FILM FORMING SHEET, COMPOSITE SHEET FOR PROTECTIVE FILM FORMATION, KIT, AND USE OF PROTECTIVE FILM FORMING SHEET}

The present invention relates to a protective film forming film, a composite sheet for forming a protective film, a kit, and the use of the protective film forming film.

This application claims priority based on Japanese Patent Application No. 2022-056435, filed in Japan on March 30, 2022, and uses the content here.

Wafers such as semiconductor wafers and insulator wafers have circuits formed on one side (circuit surface), and some have protruding electrodes such as bumps on that side (circuit surface). This wafer is divided into chips and mounted on the circuit board by connecting the protruding electrodes to connection pads on the circuit board by the so-called face-down method.

In such wafers and chips, the surface (back surface) opposite to the circuit surface is sometimes protected with a protective film to prevent damage such as cracks.

In order to form such a protective film, a protective film forming film for forming a protective film is attached to the back side of the wafer. The protective film forming film may be laminated on a support sheet for supporting it and used as a composite sheet for forming a protective film, and may be used without being laminated on a support sheet. After laser marking the protective film forming film, in order to increase the protection performance of the protective film forming layer, the semiconductor wafer is divided into chips by dicing and picked up after curing with heat or energy rays as necessary. Alternatively, the protective film forming film is cured by heat or energy rays, the formed protective film is laser marked, and then the semiconductor wafer is divided into chips by dicing and picked up. Next, the picked up semiconductor chip with the protective film is flip-chip connected to a connection pad on a circuit board such as a motherboard, and the protruding electrode on the chip with the protective film is melted by heating the circuit board (hereinafter referred to as a reflow process). , the electrical connection between the protruding electrode and the connection pad on the circuit board is strengthened, and it is mounted on the circuit board.

Protective film forming films include non-curable films that do not have curability and function as a protective film in that state. When a non-curable protective film forming film is used, a curing process is unnecessary, so a chip with a protective film can be manufactured at low cost using a simplified method. On the other hand, when a curable protective film forming film is used, the cured product serves as a protective film, which has the advantage of having a high wafer protection ability. In addition, the thermosetting protective film forming film that is cured by heating takes a relatively long time to heat during curing, but the energy ray curable protective film forming film that is cured by irradiation of energy rays is said to be completed in a short time. It has an advantage. Accordingly, the development of energy ray curable protective film forming films is progressing in various ways (see Patent Documents 1 to 3).

Japanese Patent Publication No. 2010-031183 International Publication No. 2017/188197 International Publication No. 2019/082977

However, in the conventional energy-ray curable protective film-forming film, even if the protective film-forming film is cured by energy rays, the protective film-forming film is not sufficiently cured and the protective film tends to peel off, resulting in insufficient adhesive strength and adhesive reliability. In this way, when the protective film forming film is not properly cured, there are cases where subsequent manufacturing of the semiconductor device is hindered.

The present invention is an energy-ray curable protective film-forming film, which can suitably cure the protective film-forming film when the protective film-forming film is cured by energy rays, and can produce chips with a highly reliable protective film in which peeling of the protective film is suppressed. The purpose is to provide a protective film-forming film, a composite sheet for forming a protective film comprising the same, a kit, and the use of the protective film-forming film.

The present invention has the following aspects.

[1] An energy ray curable protective film forming film,

A protective film forming film wherein the rate of change of the indentation depth as measured by the method for measuring the rate of change of the indentation depth of the protective film forming film below is 60% or more.

＜Method for measuring the rate of change of indentation depth＞

The protective film-forming film is irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2 to produce a cured protective film-forming film.

For the protective film forming film before and after curing, the indentation depth (μm) is measured using an ultra-micro hardness meter under the following conditions.

Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛

Measurement mode: load-unload test

Maximum load: 10mN

Hold time when reaching maximum load: 5 seconds

Load speed: 0.14mN/sec

Temperature: 23℃

Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing is calculated by the following formula (1), and this is taken as the rate of change of the indentation depth of the protective film-forming film.

Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One)

[2] The protective film forming film contains an acrylic resin (b) that does not have an energy ray curable group, and the acrylic resin (b) has a structural unit derived from 4-(meth)acryloylmorpholine, [1 ] The protective film forming film described in [ ].

[3] A composite sheet for forming a protective film comprising a support sheet and a protective film forming film formed on one side of the support sheet,

A composite sheet for forming a protective film, wherein the protective film forming film is the protective film forming film according to [1] or [2].

[4] A kit comprising a first laminate in which a first release film and a protective film-forming film are laminated in this order, a work to which the protective film-forming film is attached, and a support sheet used to support the protective film-forming film. as,

A kit wherein the protective film forming film is the protective film forming film according to [1] or [2].

[5] Use of a protective film forming film to form a protective film on the surface opposite to the circuit surface of a semiconductor wafer or semiconductor chip,

Use of a protective film forming film, wherein the protective film forming film is the protective film forming film according to [1] or [2].

[6] A composition for forming a protective film, wherein, when a protective film forming film is formed, the change rate of the indentation depth of the protective film forming film, as measured by the following method for measuring the rate of change of the indentation depth, is 60% or more.

＜Method for measuring the rate of change of indentation depth＞

The protective film-forming film is irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2 to produce a cured protective film-forming film.

For the protective film forming film before and after curing, the indentation depth (μm) is measured using an ultra-micro hardness meter under the following conditions.

Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛

Measurement mode: load-unload test

Maximum load: 10mN

Hold time when reaching maximum load: 5 seconds

Load speed: 0.14mN/sec

Temperature: 23℃

Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing is calculated by the following formula (1), and this is taken as the rate of change of the indentation depth of the protective film-forming film.

Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One)

[7] Use of a kit to form a protective film on the side opposite to the circuit side of a semiconductor wafer or semiconductor chip,

Use of a kit, wherein the kit is the kit described in [4].

[8] Use of a protective film-forming composition for producing a protective film-forming film, which is used to form a protective film on the side opposite to the circuit surface of a semiconductor wafer or semiconductor chip,

Use of a composition for forming a protective film, wherein the composition for forming a protective film is the composition for forming a protective film according to [6].

According to the present invention, as an energy ray-curable protective film forming film, when the protective film forming film is cured by energy rays, the protective film forming film can be cured preferably, and a chip with a highly reliable protective film in which peeling of the protective film is suppressed can be manufactured. A protective film-forming film capable of forming a protective film, a composite sheet for forming a protective film comprising the same, a kit, and the use of the protective film-forming film are provided.

1 is a cross-sectional view schematically showing an example of a protective film forming film according to an embodiment of the present invention.
Figure 2 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
Figure 3 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention.
Figure 4 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention.
Figure 5 is a cross-sectional view schematically showing another example of a composite sheet for forming a protective film according to an embodiment of the present invention.
Figure 6 is a cross-sectional view schematically showing an example of a kit according to an embodiment of the present invention.
Figure 7 is a cross-sectional view schematically illustrating an example of a method of manufacturing a chip with a protective film according to an embodiment of the present invention.
8 is a cross-sectional view schematically illustrating another example of a method of manufacturing a chip with a protective film according to an embodiment of the present invention.

◇Protective film forming film

The protective film forming film according to one embodiment of the present invention is an energy ray curable protective film forming film,

The change rate of the indentation depth of the protective film forming film as measured by the following method for measuring the rate of change of the indentation depth is 60% or more.

＜Method for measuring the rate of change of indentation depth＞

The protective film-forming film is irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2 to produce a cured protective film-forming film.

For the protective film forming film before and after curing, the indentation depth (μm) is measured using an ultra-micro hardness meter under the following conditions.

Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛

Measurement mode: load-unload test

Maximum load: 10mN

Hold time when reaching maximum load: 5 seconds

Load speed: 0.14mN/sec

Temperature: 23℃

Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing is calculated by the following formula (1), and this is taken as the rate of change of the indentation depth of the protective film-forming film.

Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One)

The protective film forming film of this embodiment is a film used to protect the chip by forming a protective film on the back side of the chip.

By using the protective film forming film of this embodiment or the composite sheet for forming a protective film provided with the same, a chip and a chip with a protective film including a protective film formed on the back side of the chip can be manufactured.

The chip with the protective film is formed, for example, by attaching a protective film forming film to the back of a wafer, then curing the protective film forming film to form a protective film, dividing the wafer into chips, and cutting the protective film along the outer periphery of the chip. It can be manufactured.

In this specification, “wafer” refers to a semiconductor wafer composed of elemental semiconductors such as silicon, germanium, and selenium, or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; Examples include insulator wafers made of insulators such as sapphire, glass, lithium niobate, and lithium tantalate.

Circuits are formed on one side of these wafers, and in this specification, the side of the wafer on which the circuits are formed is referred to as the “circuit surface.” The surface opposite to the circuit surface of the wafer is called the “back surface.”

The wafer is divided into chips by means such as dicing. In this specification, as in the case of a wafer, the surface of the chip on the side on which the circuit is formed is referred to as the “circuit surface,” and the surface on the opposite side from the circuit surface of the chip is referred to as the “back surface.”

Protruding electrodes such as bumps and pillars are formed on both the circuit surface of the wafer and the circuit surface of the chip. The protruding electrode is preferably made of solder.

Additionally, a substrate device can be manufactured by using the chip on which the protective film is formed.

In this specification, “substrate device” means that a chip on which a protective film is formed is flip-chip connected to a connection pad on a circuit board at a protruding electrode on the circuit surface. For example, if a semiconductor wafer is used as the wafer, a semiconductor device may be used as the substrate device.

The protective film forming film of this embodiment is energy ray curable, and may further be thermosetting or not thermosetting. When the protective film forming film of the present embodiment has the characteristics of both energy ray curability and thermosetting properties, the contribution of energy ray curing of the protective film forming film to the formation of the protective film is greater than the contribution of thermal curing.

In this specification, “energy ray” means an electromagnetic wave or charged particle ray that has energy quantum. Examples of energy rays include ultraviolet rays, radiation, and electron beams. For example, ultraviolet rays can be irradiated by using a high-pressure mercury lamp, fusion lamp, xenon lamp, black light, or LED lamp as the ultraviolet ray source. Electron beams generated by an electron beam accelerator, etc. can be irradiated.

In this specification, “energy ray curability” means the property of hardening by irradiating an energy ray, and “non-energy ray curability” means the property of not hardening even when irradiating an energy ray.

In addition, “non-hardening” means the property of not hardening by any means such as heating or irradiation of energy rays.

The curing conditions for energy beam curing of the protective film forming film and forming the protective film are not particularly limited as long as the degree of curing is sufficient for the protective film to sufficiently exert its function, and may be appropriately selected depending on the type of the protective film forming film.

For example, the illuminance of the energy ray during energy ray curing of the energy ray curable protective film forming film is preferably 60 to 320 mW/cm2. And, the amount of energy rays during curing is preferably 100 to 1000 mJ/cm2.

The protective film forming film of the present embodiment has a change rate of indentation depth of 60% or more as measured by the following method for measuring the rate of change of indentation depth of the protective film forming film.

＜Method for measuring the rate of change of indentation depth＞

The protective film-forming film is irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2 to produce a cured protective film-forming film.

For the protective film forming film before and after curing, the indentation depth (μm) is measured using an ultra-micro hardness meter under the following conditions.

Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛

Measurement mode: load-unload test

Maximum load: 10mN

Hold time when reaching maximum load: 5 seconds

Load speed: 0.14mN/sec

Temperature: 23℃

Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing is calculated by the following formula (1), and this is taken as the rate of change of the indentation depth of the protective film-forming film.

Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One)

When the change rate of the indentation depth obtained by equation (1) is 60% or more, when the protective film forming film is cured by energy rays, the protective film forming film is cured preferably, the adhesion of the protective film to the silicon wafer is improved, and the protective film is peeled off. You can prevent it from becoming easy to do.

The thickness of the protective film forming film used in the method for measuring the rate of change of indentation depth is preferably 20 to 50 μm, more preferably 22 to 48 μm, more preferably 24 to 46 μm, and 25 μm. Particularly desirable.

In the protective film forming film used in the method for measuring the rate of change of indentation depth, no other film such as a release film is laminated on the surface on which the indentation depth is measured.

In the protective film forming film of the present embodiment, the change rate of the indentation depth determined by equation (1) is 60% or more, the protective film forming film is suitably cured, the adhesion of the protective film to the silicon wafer is improved, and the protective film is prevented from peeling. In order to more preferably prevent this from happening, the change rate of the indentation depth calculated by equation (1) is preferably 65% or more, and more preferably 70% or more. The change rate of the indentation depth determined by equation (1) is preferably 100% or less, and more preferably 100%.

In order to preferably cure the protective film-forming film, improve the adhesion of the protective film to the silicon wafer, and more preferably prevent the protective film from peeling off, the indentation depth of the protective film-forming film before curing is preferably 8 μm or more, It is more preferable that it is 10㎛ or more, and it is even more preferable that it is 12㎛ or more. The indentation depth of the protective film forming film before curing is preferably 25 μm or less, more preferably 23 μm or less, and even more preferably 21 μm or less.

In order to preferably cure the protective film-forming film, improve the adhesion of the protective film to the silicon wafer, and more preferably prevent the protective film from peeling off, the indentation depth of the protective film-forming film after curing is preferably 5 μm or less, It is more preferable that it is 4 μm or less, and even more preferably it is 3 μm or less. The indentation depth of the protective film forming film after curing is preferably 0 μm or more, and more preferably 0 μm.

In order to suitably cure the protective film forming film, improve the adhesion of the protective film to the silicon wafer, and more preferably prevent the protective film from becoming easily peeled, the peeling strength of the protective film forming film (protective film) after curing is 3.0 N/10. It is preferable that it is mm or more, it is more preferable that it is 4.0N/10mm or more, and it is still more preferable that it is 5.0N/10mm or more.

Meanwhile, in this specification, the peeling strength of the protective film forming film (protective film) after curing can be measured by the method described in the Examples.

In order to suitably cure the protective film forming film, improve the adhesion of the protective film to the silicon wafer, and more preferably prevent the protective film from becoming easily peeled, the peeling strength of the protective film forming film (protective film) after curing is 500 N/10 mm. It is preferably less than 100N/10mm, more preferably less than 100N/10mm, more preferably less than 50N/10mm, especially preferably less than 25N/10mm, and most preferably less than 10N/10mm.

Examples of the protective film forming film include those containing an energy ray curable component (a) and an acrylic resin (b) which does not have an energy ray curable group.

The components contained in the protective film forming film will be described in detail later.

The protective film forming film may be composed of one layer (single layer) or may be composed of two or more layers. When the protective film forming film consists 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.

In this specification, it is not limited to the case of a protective film forming film, and "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 “the 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.”

The thickness of the protective film forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 5 to 60 μm. When the thickness of the protective film forming film is more than the above lower limit, a protective film with higher protective ability can be formed. When the thickness of the protective film forming film is below the above upper limit, it is possible to avoid excessive thickness of the chip on which the protective film is formed.

Here, “thickness of the protective film forming film” means the thickness of the entire protective film forming film, and for example, the thickness of the protective film forming film consisting of multiple layers means the total thickness of all layers constituting the protective film forming film. .

“Thickness” in this specification can be obtained by the method specified in JIS K 7130:1999 (ISO 4593:1993).

＜＜Composition for forming a protective film＞＞

The protective film forming film can be formed using an energy ray curable protective film forming composition (in this specification, it may simply be referred to as “protective film forming composition”) containing the constituent materials. For example, a protective film forming film can be formed by applying the protective film forming composition to the surface to be formed and drying it as necessary. The content ratio of components that do not vaporize at room temperature in the composition for forming a protective film is usually the same as the content ratio of the components in the protective film forming film. In this specification, “room temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples include a temperature of 18 to 28°C.

Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Methods include using various coaters such as a Mayer bar coater and a kiss coater.

Drying conditions for the composition for forming a protective film are not particularly limited. However, when the composition for forming a protective film contains a solvent described later, it is preferable to dry it by heating. In addition, the composition for forming a protective film containing a solvent is preferably dried by heating under conditions of, for example, 70 to 130°C for 10 seconds to 5 minutes. However, the thermosetting composition for forming a protective film is preferably dried by heating so that the composition itself and the thermosetting protective film forming film formed from the composition are not thermally cured.

<Composition (IV) for forming an energy-ray curable protective film>

A preferable composition for forming a protective film includes, for example, the energy ray curable component (a), the acrylic resin (b) without the energy ray curable group, and the inorganic filler (d). Composition (IV) (in this specification, it may simply be referred to as “composition (IV)”), etc. can be mentioned.

[Energy Ray Curing Ingredient (a)]

The energy ray-curable component (a) is a component that hardens by irradiation of an energy ray. It provides film-forming properties and flexibility to the protective film-forming film, and is also a component for forming a hard protective film after curing. The protective film forming film forms a protective film with good properties by containing the energy ray curable component (a).

In the protective film forming film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

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 80,000 to 2,000,000, and a compound (a2) having an energy ray curable group and a molecular weight of 100 to 80,000. there is. The polymer (a1) may be at least partially crosslinked with a crosslinking agent, or may be uncrosslinked.

(Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000)

Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, a group that reacts with the functional group, and a double layer of energy ray curing property. An acrylic resin (a1-1) formed by reacting an energy ray curable compound (a12) having an energy ray curable group such as a bond can be mentioned.

Examples of the functional groups capable of reacting with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, substituted amino groups (groups having a structure in which one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms), epoxy groups, etc. You can. However, from the viewpoint of preventing corrosion of circuits such as wafers and chips, it is preferable that the functional group is a group other than a carboxyl group.

Among these, it is preferable that the 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 copolymerizing 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 ( It may be a copolymerization of non-acrylic monomer).

Additionally, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method can be adopted.

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. ) Hydroxyalkyl (meth)acrylate such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols that do not have a (meth)acryloyl skeleton) such as vinyl alcohol and allyl alcohol can be 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 above ethylenically unsaturated dicarboxylic acids; and (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate.

The acrylic monomer having the above functional group is preferably a hydroxyl group-containing monomer.

The acrylic monomer having the functional group that constitutes the acrylic polymer (a11) may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of acrylic monomers that do not have the above functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (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, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (( (meth)lauryl acrylate), (meth)tridecyl acrylate, tetradecyl (meth)acrylate ((meth)myristyl acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate) , (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain-like structure of 1 to 18 carbon atoms, such as heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. You can.

In addition, acrylic monomers that do not have the above functional group include, for example, alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. Contains (meth)acrylic acid ester; (meth)acrylic acid esters having an aromatic group, including aryl (meth)acrylic acid such as phenyl (meth)acrylate; Non-crosslinkable (meth)acrylamide and its derivatives; Also included are (meth)acrylic acid esters having a non-crosslinkable tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

The acrylic monomer without the functional group that constitutes the acrylic polymer (a11) may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; Vinyl acetate; Styrene, etc. can be mentioned.

The number of non-acrylic monomers constituting the acrylic polymer (a11) may be one, two or more, and in the case of two or more, their combination and ratio can be arbitrarily selected.

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

The number of the acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one, two or more types may be used, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

The ratio of the content of acrylic resin (a1-1) in the protective film forming film to the total mass of the protective film forming film is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass. It is especially preferable that it is mass %.

·Energy ray curable compound (a12)

The energy ray-curable compound (a12) preferably has one or two or more groups 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). It is more preferable to have an isocyanate group as the group. For example, 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), which has a hydroxyl group as the functional group.

The number of energy ray curable groups in one molecule of the energy ray curable compound (a12) is not particularly limited and can be appropriately selected, for example, taking into account physical properties such as shrinkage required for the target protective film. .

For example, the energy ray curable compound (a12) preferably has 1 to 5 energy ray curable groups per molecule, and more preferably has 1 to 3 groups.

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;

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

An acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate, etc. can be mentioned.

Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one type, or two or more types may be used. When two or more types are used, their combination and ratio 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 20. It is preferable that it is 120 mol%, it is more preferable that it is 35-100 mol%, and it is especially preferable that it is 50-100 mol%. When the content ratio is within this range, the adhesive force of the cured product of the protective film forming film becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional (having one group per molecule) compound, the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) In the case of a polyfunctional compound (having two or more of the above groups per molecule), the upper limit of the above content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.

In this specification, “weight average molecular weight” is a polystyrene conversion value measured by gel permeation chromatography (GPC) method, unless otherwise specified.

The polymer (a1) contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

(Compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80,000)

The energy ray curable group in the compound (a2) having a molecular weight of 100 to 80000 having an energy ray curable group includes a group containing an energy ray curable double bond, and preferred examples include a (meth)acryloyl group, a vinyl group, etc. can be mentioned.

The compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low molecular weight compounds having an energy ray curable group, epoxy resins having an energy ray curable group, and phenol resins having an energy ray curable group.

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

Examples of the acrylate-based compound include polyfunctional monomers or oligomers, and polyfunctional acrylate-based compounds having two or three or more (meth)acryloyl groups in one molecule are preferable.

Examples of the multifunctional acrylate-based compounds include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di( Meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth) Acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypoly Propoxy)phenyl]propane, tricyclodecanedimethyloldi(meth)acrylate (aka: tricyclodecanedimethyloldi(meth)acrylate), 1,10-decanedioldi(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 Rate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4- ((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxy Bifunctional (meth)acrylates such as propane ((meth)acrylates having two (meth)acryloyl groups in one molecule);

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, ditrimethylolpropane 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 ((meth)acrylates having three or more (meth)acryloyl groups in one molecule);

and polyfunctional (meth)acrylate oligomers such as polyfunctional urethane (meth)acrylate oligomers ((meth)acrylate oligomers having two or three or more (meth)acryloyl groups in one molecule).

Among the compounds (a2), for example, those described in paragraph 0043 of Japanese Patent Application Laid-Open No. 2013-194102 can be used as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group. This resin also corresponds to the resin constituting the thermosetting component described later, but is treated as the compound (a2) in composition (IV).

The weight average molecular weight of the compound (a2) is preferably 100 to 30,000, and more preferably 300 to 10,000.

The compound (a2) contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

The protective film-forming film preferably contains the above-mentioned compound (a2) as the energy ray-curable component (a), and contains a polyfunctional acrylate-based compound having two or three or more (meth)acryloyl groups in one molecule. It is more preferable that it contains a polyfunctional urethane (meth)acrylate oligomer. The cured product (protective film) of the protective film forming film containing the energy ray curable component (a) by irradiation with energy rays has good protective ability, flexibility, and particularly excellent properties.

The energy ray-curable component (a) may or may not contain a polymer having a structural unit derived from 4-(meth)acryloylmorpholine, but it is preferable not to include it.

When the composition (IV) and the protective film-forming film contain the energy ray-curable component (a), the content of the energy ray-curable component (a) in the composition (IV) and the protective film-forming film is 100% the content of the acrylic resin (b). With respect to parts by mass, it is preferably 100 to 310 parts by mass, more preferably 130 to 280 parts by mass, for example, 130 to 200 parts by mass or 210 to 280 parts by mass may be used.

In the composition (IV), the content ratio of the energy ray curable component (a) to the total mass of all components other than the solvent (i.e., the energy ray curable component (a) to the total mass of the protective film forming film in the protective film forming film ) Content ratio) is preferably 12 to 31 mass%, more preferably 14 to 28 mass%, and more preferably 16 to 25 mass%. When the content ratio of the energy ray-curable component (a) (i.e., the content ratio of the energy ray-curable component (a)) is more than the lower limit, the energy ray curability of the protective film forming film becomes better. When the content ratio of the energy ray curable component (a) (i.e., the content ratio of the energy ray curable component (a)) is below the upper limit, it is easy to prepare the desired protective film forming film.

[Acrylic resin (b) without energy ray curable group]

The protective film forming film preferably contains acrylic resin (b) (in this specification, it may simply be referred to as “acrylic resin (b)”) which does not have an energy ray curable group.

The acrylic resin (b) is a component that imparts film-forming properties to the protective film-forming film.

The acrylic resin (b) may be any known material. For example, it may be a homopolymer of one type of acrylic monomer, or it may be a copolymer of two or more types of acrylic monomers, or may be a mixture of one or two or more types of acrylic monomers, and one type of acrylic monomer. Alternatively, it may be a copolymer of two or more types of monomers other than acrylic monomers (non-acrylic monomers).

The acrylic resin (b) preferably has a structural unit derived from 4-(meth)acryloylmorpholine. That is, the acrylic resin (b) is preferably a polymer of 4-(meth)acryloylmorpholine. When the acrylic resin (b) has a structural unit derived from 4-(meth)acryloylmorpholine, it has excellent adhesion to the above-mentioned wafer or chip and increases the effect of suppressing peeling of the protective film from the wafer or chip. .

The acrylic resin (b) preferably has a structural unit derived from 4-(meth)acryloylmorpholine and other structural units. That is, the acrylic resin (b) is preferably a copolymer of 4-(meth)acryloylmorpholine and other monomers or oligomers.

In the acrylic resin (b), the ratio of the amount of structural units derived from 4-(meth)acryloylmorpholine to the total mass of structural units is preferably 10 to 30% by mass, and 13 to 30% by mass. It is more preferable that it is %, and it may be either 18-30 mass % or 23-30 mass %.

The acrylic resin (b) may be at least partially crosslinked with a crosslinking agent, or may be uncrosslinked.

Examples of the acrylic monomer constituting the acrylic resin (b) include alkyl (meth)acrylate, (meth)acrylic acid ester without a functional group and having a cyclic skeleton, (meth)acrylic acid ester containing a glycidyl group, (meth)acrylic acid esters such as hydroxyl group-containing (meth)acrylic acid ester, substituted amino group-containing (meth)acrylic acid ester, carboxyl group-containing (meth)acrylic acid ester, and amino group-containing (meth)acrylic acid ester; (meth)acrylamide; (meth)acrylamide derivatives such as 4-(meth)acryloylmorpholine, etc. can be mentioned. Here, “substituted amino group” means a group having a structure in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. Here, “functional group” means a group (reactive functional group) that can react with other groups such as glycidyl group, hydroxyl group, substituted amino group, carboxyl group, and amino group.

In this specification, “(meth)acrylic acid” is a concept that includes both “acrylic acid” and “methacrylic acid.” The same applies to terms similar to (meth)acrylic acid, for example, “(meth)acrylate” is a concept that includes both “acrylate” and “methacrylate”, and “(meth)acryloyl group” " is a concept that includes both "acryloyl group" and "methacryloyl group".

In this specification, when a structure in which one or more hydrogen atoms is substituted with a group other than a hydrogen atom is assumed in a specific compound, the compound having this substituted structure is referred to as a “derivative” of the specific compound described above.

In this specification, the term “group” includes not only an atomic group formed by combining a plurality of atoms, but also a single atom.

Examples of (meth)acrylic acid alkyl esters that do not have the above functional group and cyclic skeleton include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. ) n-butyl acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (meth)dodecyl acrylate ((meth)lauryl acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate The alkyl group constituting the alkyl ester, such as ((meth)acrylic acid palmityl), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl ((meth)stearyl (meth)acrylic acid), has a chain-like structure of 1 to 18 carbon atoms ( Meth)acrylic acid alkyl ester, etc. are mentioned.

Examples of (meth)acrylic acid esters that do not have the above functional group and have a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

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

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

(meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester.

Examples of the glycidyl group-containing (meth)acrylic acid ester include glycidyl (meth)acrylate.

Examples of the hydroxyl group-containing (meth)acrylic acid ester include either an alkyl (meth)acrylic acid ester that does not have the functional group and a cyclic skeleton, and a (meth)acrylic acid ester that does not have the functional group and has a cyclic skeleton. In this case, examples include those having a structure in which one or two or more hydrogen atoms are substituted with hydroxyl groups. Preferred hydroxyl group-containing (meth)acrylic acid esters include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylic acid, 2-hydroxypropyl (meth)acrylic acid, and 3-hydroxy (meth)acrylic acid. Roxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylate.

Examples of the non-acrylic monomer constituting the acrylic resin (b) include olefins such as ethylene and norbornene; Vinyl acetate; Styrene, etc. can be mentioned.

Examples of the acrylic resin (b) that is at least partially crosslinked with a crosslinking agent include those in which functional groups in the acrylic resin (b) have reacted with the crosslinking agent.

The functional group may be appropriately selected depending on the type of crosslinking agent, etc., and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, the functional group includes a hydroxyl group, a carboxyl group, an amino group, etc. Among these, a hydroxyl group with high reactivity with an isocyanate group is preferable. In addition, when the crosslinking agent is an epoxy-based compound, the functional group includes a carboxyl group and an amino group, and among these, a carboxyl group that has high reactivity with an epoxy group is preferable. However, from the viewpoint of preventing corrosion of the wafer or chip circuit, it is preferable that the functional group is a group other than a carboxyl group.

Examples of the acrylic resin (b) having the above functional group include those obtained by polymerizing a monomer having at least the above functional group.

More specifically, the acrylic resin (b) having the functional group includes, for example, the glycidyl group-containing (meth)acrylic acid ester, the hydroxyl group-containing (meth)acrylic acid ester, and the substituted amino group-containing (meth)acrylic acid. From the group consisting of esters, the carboxyl group-containing (meth)acrylic acid esters, the amino group-containing (meth)acrylic acid esters, and monomers having a structure in which one or two or more hydrogen atoms in the biacrylic monomer are substituted with the functional groups. Examples include those obtained by polymerizing one or two or more selected monomers.

In the acrylic resin (b), the ratio (content) of the amount of structural units derived from monomers having functional groups to the total mass of structural units constituting the same is preferably 1 to 20% by mass, and 2 to 10% by mass. It is more preferable that it is mass %. When the ratio is within this range, the degree of crosslinking in the acrylic resin (b) becomes a more preferable range.

The weight average molecular weight (Mw) of the acrylic resin (b) is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 40,000 or more since bleed-out during the reflow process is further suppressed. The weight average molecular weight (Mw) of the acrylic resin (b) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000, since the film-forming properties of the composition (IV) become better.

The composition (IV) and the acrylic resin (b) contained in the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In composition (IV), the ratio of the content of acrylic resin (b) to the total mass of all components other than the solvent (i.e., the content of acrylic resin (b) to the total mass of the protective film-forming film in the protective film-forming film) ratio) is preferably 8% by mass or more, more preferably 10% by mass or more, and may be, for example, either 12% by mass or more and 14% by mass or more.

In composition (IV), the ratio of the content of acrylic resin (b) to the total mass of all components other than the solvent (i.e., the content of acrylic resin (b) to the total mass of the protective film-forming film in the protective film-forming film) The upper limit of the ratio) is not particularly limited. Since the protective film exhibits the characteristic of suppressing bleed out due to the reflow process and other characteristics in a balanced manner, the upper limit may be 27% by mass or less, preferably 25% by mass or less, and 23% by mass or less. It is more preferable, and it is still more preferable that it is 21 mass % or less.

In composition (IV), the ratio of the content of acrylic resin (b) to the total mass of all components other than the solvent (i.e., the content of acrylic resin (b) to the total mass of the protective film-forming film in the protective film-forming film) ratio) can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower and upper limits.

For example, in one embodiment, the ratio is preferably 8 to 27 mass%, more preferably 10 to 25 mass%, and may be either 12 to 23 mass% or 14 to 21 mass%. .

When the composition (IV) and the protective film-forming film contain the energy-ray curable component (a) and the acrylic resin (b), the content of the energy-ray curable component (a) in the composition (IV) and the protective film-forming film is the acrylic resin. The content of resin (b) is preferably 70 to 310 parts by mass, more preferably 80 to 280 parts by mass, and more preferably 85 to 250 parts by mass.

In the composition (IV), the ratio of the total content of the energy radiation curable component (a) and the acrylic resin (b) to the total mass of all components other than the solvent (i.e., the total mass of the protective film-forming film in the protective film-forming film) The ratio of the total content of the energy ray curable component (a) and the acrylic resin (b) is preferably 10 to 60% by mass, for example, either 20 to 50% by mass or 30 to 45% by mass. It's okay too. When the ratio is within this range, the effect of using the energy ray-curable component (a) and the acrylic resin (b) becomes higher.

[Other ingredients]

The composition (IV) and the protective film forming film may contain other components that do not correspond to either the energy ray curable component (a) or the acrylic resin (b) within a range that does not impair the effect of the present invention.

The other components include, for example, a photopolymerization initiator (c); inorganic filler (d); Coupling agent (e); Cross-linking agent (f); Colorant (g); thermosetting component (h); universal additive (z); Polymer (b0) that does not have an energy ray curable group and does not correspond to acrylic resin (b) (in this specification, it may be referred to as “another polymer (b0) that does not have an energy ray curable group” or “polymer (b0)” ), etc.

(Photopolymerization initiator (c))

When the composition (IV) and the protective film forming film contain a photopolymerization initiator (c), the polymerization (curing) reaction of the energy ray-curable component (a) can be carried out efficiently.

The photopolymerization initiator includes, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. phosphorus compounds; Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-1-(4- (4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl Acetophenone compounds such as -1-butanone; 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; Quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone can be mentioned.

Additionally, examples of the photopolymerization initiator include photosensitizers such as amines.

The photopolymerization initiator (c) contained in the composition (IV) and the protective film forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected. For example, a highly reactive photopolymerization initiator in the liquid phase at room temperature, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, can be used alone to efficiently crosslink the protective film forming film. The gel fraction can be increased. 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, 1-hydroxycyclohexyl-phenylketone, etc. A low-reactivity photopolymerization initiator can be used in combination with a highly reactive photopolymerization initiator such as 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone to efficiently form a protective film. Crosslinking becomes possible and the gel fraction can be increased.

When using a photopolymerization initiator (c), the content of the photopolymerization initiator (c) in the composition (IV) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable component (a), It is more preferable that it is 1 to 10 parts by mass, and it is especially preferable that it is 2 to 5 parts by mass.

(Inorganic filler (d))

When the composition (IV) and the protective film-forming film contain an inorganic filler (d), by adjusting the amount of the inorganic filler (d) in the composition (IV) and the protective film-forming film, the cured product of the protective film-forming film (e.g., The thermal expansion coefficient of the protective film) can be more easily adjusted. For example, by optimizing the thermal expansion coefficient of the protective film with respect to the object on which the protective film is formed, the reliability of the package obtained using the protective film forming film is further improved. Additionally, by using a protective film-forming film containing the inorganic filler (d), the moisture absorption rate of the cured product (eg, protective film) of the protective film-forming film can be reduced or heat dissipation can be improved.

Examples of the inorganic filler (d) include powders of inorganic materials such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, and boron nitride; Beads made by spheroidizing these inorganic materials; surface modifications of these inorganic materials; single crystal fibers of these inorganic materials; Glass fiber, etc. can be mentioned.

Among these, it is preferable that the inorganic filler (d) is silica or alumina.

The inorganic filler (d) contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In composition (IV), the ratio of the content of the inorganic filler (d) to the total mass of all components other than the solvent (i.e., the content of the inorganic filler (d) to the total mass of the protective film-forming film in the protective film-forming film) ratio) is preferably 35 to 75% by mass, for example, may be either 45 to 70% by mass or 50 to 65% by mass. When the ratio is within this range, the effect of using the inorganic filler (d) becomes higher without impairing the characteristics of the protective film forming film.

(Coupling agent (e))

When the composition (IV) and the protective film-forming film contain a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesion of the protective film-forming film to the adherend is improved. Additionally, the cured product of the protective film forming film (eg, protective film) does not impair heat resistance and improves water resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the acrylic resin (b), the energy ray-curable component (a), etc., and is more preferably a silane coupling agent.

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 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, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, etc. are mentioned.

The coupling agent (e) contained in the composition (IV) and the protective film forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be selected arbitrarily.

When using the coupling agent (e), in the composition (IV) and the protective film forming film, the content of the coupling agent (e) is 100 parts by mass relative to the total content of the energy ray curable component (a) and the acrylic resin (b). , it is preferably 0.03 to 20 parts by mass. When the content of the coupling agent (e) is more than the above lower limit, the dispersibility of the inorganic filler (d) in the resin is improved, the adhesion of the protective film forming film to the adherend is improved, etc., due to the use of the coupling agent (e). The effect is more significantly obtained. When the content of the coupling agent (e) is below the upper limit, the generation of outgassing is further suppressed.

(Cross-linking agent (f))

When using an acrylic resin (b) having functional groups such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxyl group, and isocyanate group that can be combined with other compounds, the composition (IV) and the protective film forming film are: It may contain a crosslinking agent (f). The crosslinking agent (f) is a component for crosslinking the functional group in the acrylic resin (b) by bonding it with another compound. By crosslinking in this way, the initial adhesion and cohesion of the protective film forming film can be adjusted.

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

Examples of the organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively abbreviated as “aromatic polyvalent isocyanate compounds, etc.”) ; trimers, isocyanurates, and adducts of the aromatic polyvalent isocyanate compounds; and a terminal isocyanate urethane prepolymer obtained by reacting the above aromatic polyvalent isocyanate compound with a polyol compound. The “adduct body” refers to the aromatic polyvalent isocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyvalent isocyanate compound, and a low-molecular-weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. refers to the reactant of Examples of the adduct include xylylene diisocyanate adducts of trimethylolpropane, as described later. In addition, “terminal isocyanate urethane prepolymer” means a prepolymer that has a urethane bond and an isocyanate group at the terminal portion of the molecule.

More specifically, the organic polyvalent isocyanate compound includes, 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 are added to all or part of the hydroxyl group of a polyol such as trimethylolpropane; Lysine diisocyanate, etc. can be mentioned.

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

When using an organic polyvalent isocyanate compound as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the acrylic resin (b). When the crosslinking agent (f) has an isocyanate group and the acrylic resin (b) has a hydroxyl group, a crosslinking structure can be easily introduced into the protective film-forming film through the reaction between the crosslinking agent (f) and the acrylic resin (b).

The crosslinking agent (f) contained in the composition (IV) and the protective film forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be selected arbitrarily.

When using a cross-linking agent (f), the content of the cross-linking agent (f) in the composition (IV) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the acrylic resin (b). When the content of the crosslinking agent (f) is more than the lower limit, the effect of using the crosslinking agent (f) is more significantly obtained. When the content of the crosslinking agent (f) is below the upper limit, excessive use of the crosslinking agent (f) is suppressed.

(Colorant (g))

When the composition (IV) and the protective film-forming film contain a colorant (g), the light transmittance of the protective film-forming film can be adjusted by adjusting the content. And by adjusting the light transmittance in this way, for example, laser mark visibility can be adjusted when laser marking is performed on a protective film forming film or protective film. Additionally, the design of the protective film can be improved, or grinding marks on the back side of the wafer can be made less noticeable.

Examples of the colorant (g) include known ones such as inorganic pigments, organic pigments, and organic dyes.

The organic pigments and organic dyes include, for example, aminonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, squaryllium-based pigments, azurenium-based pigments, polymethine-based pigments, and naphthoquinone-based 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, anthrax. Quinone-based dyes, naphthol-based dyes, azomethine-based dyes, benzimidazolone-based dyes, pyranthrone-based dyes, and srene-based dyes can be mentioned.

Examples of the inorganic pigment include carbon black, cobalt pigment, iron pigment, chromium pigment, titanium pigment, vanadium pigment, zirconium pigment, molybdenum pigment, ruthenium pigment, platinum pigment, and ITO (indium pigment). Tin oxide (tin oxide)-based pigments, ATO (antimony tin oxide)-based pigments, etc. can be mentioned.

The coloring agent (g) contained in the composition (IV) and the protective film forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be selected arbitrarily.

When using the colorant (g), the content of the colorant (g) in the composition (IV) and the protective film forming film may be appropriately adjusted depending on the purpose. For example, in the case of improving the visibility of the laser mark of the protective film forming film or protective film, or the design of the protective film, or making grinding marks on the back side of the wafer less noticeable, in composition (IV), as described above, The ratio of the content of the colorant (g) to the total mass of all components other than the solvent (that is, the ratio of the content of the colorant (g) to the total mass of the protective film-forming film in the protective film-forming film) is 0.05 to 12% by mass. It is preferable, it is more preferable that it is 0.05-9 mass %, and it is especially preferable that it is 0.1-7 mass %. When the ratio is above the lower limit, the effect of using the colorant (g) is more significantly obtained. When the ratio is below the upper limit, excessive use of the colorant (g) is suppressed.

(Thermosetting component (h))

When the composition (IV) and the protective film-forming film contain the energy ray-curable component (a) and the thermosetting component (h), the adhesive force of the protective film-forming film to the adherend is improved by heating, and the hardness of the protective film-forming film is improved. The strength of the cargo (e.g. shield) is also improved.

Examples of the thermosetting component (h) include epoxy-based thermosetting resin, polyimide resin, and unsaturated polyester resin, and epoxy-based thermosetting resin is preferred.

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

The epoxy-based thermosetting resin contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

·Epoxy resin (h1)

Known epoxy resins (h1) include, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolac epoxy resins, and dicyclopentadiene. Bifunctional or higher epoxy compounds such as epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and phenylene skeleton epoxy resin can be mentioned.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a chip with a protective film formed using a composite sheet for forming a protective film is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. These compounds are obtained, for example, by adding (meth)acrylic acid or a derivative thereof to an epoxy group.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin. The unsaturated hydrocarbon group is an unsaturated group that has polymerizability, and specific examples include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth)acrylamide group, etc. , acryloyl group is preferred.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30,000, more preferably 300 to 10,000, from the viewpoint of the curability of the protective film forming film and the strength and heat resistance of the protective film. It is particularly preferable that it is 3000.

The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g/eq, and more preferably 150 to 950 g/eq.

The composition (IV) and the epoxy resin (h1) contained in the protective film forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

·Heat curing agent (h2)

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

Examples of the thermosetting agent (h2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. 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 anhydrized. Preferably, a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrized is preferred. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resin, biphenol, novolac-type phenol resin, dicyclopentadiene-type phenol resin, and aralkyl-type phenol resin. You can.

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

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

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

Examples of the unsaturated hydrocarbon group in the thermosetting agent (h2) include the same unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.

When using a phenol-based curing agent as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature because the peelability of the protective film from the support sheet is improved.

Among the thermosetting agents (h2), for example, the number average molecular weight of the resin components such as polyfunctional phenol resin, novolak-type phenol resin, dicyclopentadiene-type phenol resin, and aralkyl-type phenol resin is preferably 300 to 30,000. , it is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Among the thermosetting agents (h2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably, for example, 60 to 500.

The number of thermosetting agents (h2) contained in the composition (IV) and the protective film forming film may be one, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

When using a thermosetting component (h), the content of the thermosetting agent (h2) in the composition (IV) and the protective film forming film is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (h1). . When the content of the thermosetting agent (h2) is more than the lower limit, curing of the protective film forming film becomes more likely to proceed. When the content of the thermosetting agent (h2) is below the upper limit, the moisture absorption rate of the protective film-forming film is reduced, and the reliability of the package obtained using the chip with the protective film is further improved.

When using a thermosetting component (h), in the composition (IV) and the protective film forming film, the content of the thermosetting component (h) (for example, the total content of the epoxy resin (h1) and the thermosetting agent (h2)) is acrylic. It is preferably 5 to 120 parts by mass with respect to 100 parts by mass of the resin (b) content. When the content of the thermosetting component (h) is within this range, for example, the adhesive force between the cured product of the protective film forming film and the support sheet is suppressed, and the peelability of the support sheet is improved.

(General purpose additive (z))

The general-purpose additive (z) may be any known additive, may be selected arbitrarily depending on the purpose, and is not particularly limited. Preferred general-purpose additives (z) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, and ultraviolet absorbers.

The general-purpose additive (z) contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

When using the general-purpose additive (z), the content of the general-purpose additive (z) in the composition (IV) and the protective film forming film is not particularly limited and may be appropriately selected depending on the purpose.

For example, when the general-purpose additive (z) is an ultraviolet absorber, in composition (IV), the ratio of the content of the general-purpose additive (z) (ultraviolet absorber) to the total mass of all components other than the solvent (i.e., protective film) The ratio of the content of the general-purpose additive (z) (ultraviolet absorber) to the total mass of the protective film forming film in the formed film is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and 0.5% by mass. It is preferable that it is -1.5 mass %. When the ratio is above the lower limit, the effect of using the general-purpose additive (z) is more significantly obtained. When the ratio is below the upper limit, excessive use of the general-purpose additive (z) is suppressed.

(Other polymer (b0) that does not have an energy radiation curable group)

Another polymer (b0) that does not have an energy-ray curable group provides film-forming properties to the protective film-forming film.

The polymer (b0) is not particularly limited as long as it does not correspond to the acrylic resin (b).

The polymer (b0) may be at least partially crosslinked with a crosslinking agent, or may be uncrosslinked.

Examples of the polymer (b0) include acrylic resins with a weight average molecular weight exceeding 1,100,000 and acrylic resins with a dispersion degree of 3.0 or less (in this specification, these acrylic resins may be referred to as “other acrylic resins”); Polymers other than acrylic resins that do not have an energy ray curable group, etc. can be mentioned.

Examples of the other acrylic resins include those similar to acrylic resin (b), except that the weight average molecular weight is greater than 1,100,000 or the dispersion degree is 3.0 or less.

Examples of polymers other than acrylic resins that do not have an energy-ray curable group include urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.

The weight average molecular weight (Mw) of the polymer other than the acrylic resin that does not have an energy ray curable group is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000, since the film-forming properties of the composition (IV) become better. .

The polymer (b0) contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

In the composition (IV) and the protective film forming film, the content of polymer (b0) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 mass part or less, based on 100 parts by mass of the acrylic resin (b). It is more preferable that it is 0 part by mass or less, that is, it is especially preferable that composition (IV) and the protective film forming film do not contain polymer (b0). When the content of polymer (b0) is below the upper limit, the effect of suppressing peeling of the protective film from the wafer or chip is further increased.

[menstruum]

Composition (IV) preferably further contains a solvent. Composition (IV) containing a solvent improves handling properties.

The solvent is not particularly limited, but preferred examples include 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; Amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone can be mentioned.

The solvent contained in composition (IV) may be one type, two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected.

A more preferable solvent contained in composition (IV) includes, for example, methyl ethyl ketone because it allows the components contained in composition (IV) to be more uniformly mixed.

The solvent content of composition (IV) is not particularly limited and may be appropriately selected depending on the type of components other than the solvent.

＜＜Production method of composition for forming a protective film＞＞

A composition for forming an energy-ray curable protective film, such as composition (IV), is obtained by mixing each component for forming the composition.

The order of addition when mixing each component is not particularly limited, and two or more types of components may be added simultaneously.

The method of mixing each component at the time of mixing is not particularly limited, and includes mixing by rotating a stirrer or a stirring blade, etc.; Method of mixing using a mixer; It may be appropriately selected from known methods, such as a method of mixing by applying ultrasonic waves.

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 adjusted appropriately, but the temperature is preferably 15 to 30°C.

1 is a cross-sectional view schematically showing an example of the protective film forming film of this embodiment. Meanwhile, in the drawings used in the following description, the main parts may be enlarged for convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component are not limited to being the same as the actual ones. No.

The protective film forming film 13 shown here has a first release film 151 on one side (sometimes referred to as “first side” in this specification) 13a, and the first side A second release film 152 is provided on the other surface 13b (sometimes referred to as “second surface” in this specification) opposite to 13a.

This protective film forming film 13 is preferably stored in roll form, for example.

The protective film forming film 13 has the above-described characteristics.

The protective film forming film 13 can be formed using the composition for forming a protective film described above.

The first release film 151 and the second release film 152 may both be known.

The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other, for example, the peeling forces required when peeling from the protective film forming film 13 are different from each other.

In the protective film forming film 13 shown in FIG. 1, the exposed surface created by removing either the first peeling film 151 or the second peeling film 152 becomes the attaching surface to the back side of the wafer (not shown). . And the exposed surface created by removing the other of the first peeling film 151 and the second peeling film 152 becomes the attaching surface of the support sheet or dicing sheet described later.

In Fig. 1, an example is shown in which a release film is formed on both surfaces (the first side 13a and the second side 13b) of the protective film forming film 13. However, the release film is formed on the protective film forming film 13. It may be formed on only one side, that is, only the first side 13a or only the second side 13b.

The protective film forming film of this embodiment can be affixed to the back side of the wafer without being used together with the support sheet described later. In that case, a release film may be formed on the surface opposite to the surface of the protective film forming film attached to the wafer, and this release film may be removed at an appropriate timing.

On the other hand, the protective film forming film of this embodiment can be used in combination with a support sheet described later to form a composite sheet for forming a protective film that can perform both formation of a protective film and dicing. Hereinafter, such a composite sheet for forming a protective film will be described.

◇Composite sheet for forming a protective film

The composite sheet for forming a protective film according to one embodiment of the present invention includes a support sheet and a protective film forming film formed on one side of the support sheet, and the protective film forming film is according to the above-described embodiment of the present invention. It is a protective film forming film.

The composite sheet for forming a protective film of the present embodiment is provided with the protective film forming film, so that when the protective film forming film is cured with energy rays, the change rate of the indentation depth of the protective film forming film is set to a preferable range, making the protective film forming film preferable. By hardening, peeling of the protective film is suppressed.

In this specification, as long as the laminated structure of the support sheet and the cured product of the protective film forming film is maintained even after the protective film forming film is cured, this laminated structure is referred to as a “composite sheet for forming a protective film.”

Hereinafter, each layer constituting the composite sheet for forming a protective film will be described in detail.

◎Support sheet

The support sheet may be made of one layer (single layer), or may be made of multiple layers of two or more layers. When the support sheet is made of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

The support sheet is preferably transparent, and may be colored depending on the purpose.

In this embodiment where the protective film forming film has energy ray curability, it is preferable that the support sheet transmits the energy ray.

Examples of the support sheet include a base material and an adhesive layer formed on one side of the base material; Consisting of materials only; etc. can be mentioned. When the support sheet is provided with an adhesive layer, the adhesive layer is disposed between the base material and the protective film forming film in the composite sheet for forming a protective film.

When a support sheet provided with a base material and an adhesive layer is used, the adhesion and peelability between the support sheet and the protective film forming film can be easily adjusted in the composite sheet for forming a protective film.

When a support sheet consisting of only a base material is used, a composite sheet for forming a protective film can be manufactured at low cost.

Examples of the composite sheet for forming a protective film of the present embodiment will be described below for each type of such support sheet with reference to the drawings.

Figure 2 is a cross-sectional view schematically showing an example of the composite sheet for forming a protective film of the present embodiment.

Meanwhile, in the drawings after FIG. 2, the same components as those shown in the already described drawings are given the same reference numerals as in the described drawings, and their detailed descriptions are omitted.

The composite sheet 101 for forming a protective film shown here is formed on a support sheet 10 and one side (sometimes referred to as “first side” in this specification) 10a of the support sheet 10. It is comprised by providing a protective film forming film 13.

The support sheet 10 is comprised of a base material 11 and an adhesive layer 12 formed on one side (first side) 11a of the base material 11. In the composite sheet 101 for forming a protective film, the adhesive layer 12 is disposed between the base material 11 and the protective film forming film 13.

That is, the composite sheet 101 for forming a protective film is formed by stacking a base material 11, an adhesive layer 12, and a protective film forming film 13 in this order in their thickness direction.

The first surface 10a of the support sheet 10 is a surface 12a (sometimes referred to as “first surface” in this specification) on the side opposite to the substrate 11 side of the adhesive layer 12. same.

The composite sheet 101 for forming a protective film further includes an adhesive layer 16 for a jig and a release film 15 on the protective film forming film 13.

In the composite sheet 101 for forming a protective film, a protective film forming film 13 is laminated on the entire or almost entire surface of the first surface 12a of the adhesive layer 12, and the adhesive of the protective film forming film 13 The jig adhesive layer 16 is laminated on a part of the surface 13a (sometimes referred to as the “first surface” in this specification) opposite to the layer 12 side, that is, the area near the periphery. It is done. In addition, of the first surface 13a of the protective film forming film 13, the area on which the jig adhesive layer 16 is not laminated and the side of the jig adhesive layer 16 opposite to the protective film forming film 13 side. A release film 15 is laminated on the surface 16a (sometimes referred to as the “first surface” in this specification). A support sheet 10 is formed on a surface 13b (sometimes referred to as “second surface” in this specification) opposite to the first surface 13a of the protective film forming film 13.

Not limited to the case of the composite sheet 101 for forming a protective film, in the composite sheet for forming a protective film of the present embodiment, the release film (for example, the release film 15 shown in FIG. 1) is of any configuration, The composite sheet for forming a protective film of this embodiment may or may not be provided with a release film.

The jig adhesive layer 16 is used to fix the composite sheet 101 for forming a protective film to a jig such as a ring frame.

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or a multi-layer structure including a sheet serving as a core material and a layer containing an adhesive component formed on both sides of the sheet. You can stay.

The composite sheet 101 for forming a protective film has the release film 15 removed, the back side of the wafer is attached to the first side 13a of the protective film forming film 13, and the adhesive layer 16 for a jig is attached. The first surface 16a of is attached to a jig such as a ring frame and used.

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

The composite sheet 102 for forming a protective film shown here has a different shape and size of the protective film forming film, except that the jig adhesive layer is laminated on the first side of the adhesive layer rather than the first side of the protective film forming film. , is the same as the composite sheet 101 for forming a protective film shown in FIG. 2 .

More specifically, in the composite sheet 102 for forming a protective film, the protective film forming film 23 is a portion of the first surface 12a of the adhesive layer 12, that is, in the width direction of the adhesive layer 12. They are stacked in the center area in the left and right direction in FIG. 3. In addition, the jig is used so that the protective film forming film 23 is surrounded in a non-contact manner from the outside in the width direction in the area of the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated. Adhesive layers 16 are laminated. And, the surface 23a of the protective film forming film 23 opposite to the adhesive layer 12 side (in this specification, it may be referred to as the “first surface”) and the jig adhesive layer 16. A release film 15 is laminated on the first surface 16a. A support sheet 10 is formed on a surface 23b (sometimes referred to as “second surface” in this specification) opposite to the first surface 23a of the protective film forming film 23.

Figure 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film of the present embodiment.

The composite sheet 103 for forming a protective film shown here is the same as the composite sheet 102 for forming a protective film shown in FIG. 3 except that it does not include the adhesive layer 16 for a jig.

Fig. 5 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film of the present embodiment.

The composite sheet 104 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in FIG. 2 except that it is provided with a support sheet 20 instead of the support sheet 10.

The support sheet 20 consists only of the base material 11.

That is, the composite sheet 104 for forming a protective film is formed by stacking a base material 11 and a protective film forming film 13 in their thickness direction.

The surface (first surface) 20a of the support sheet 20 on the protective film forming film 13 side is the same as the first surface 11a of the substrate 11.

The base material 11 has adhesiveness at least on its first surface 11a.

The composite sheet for forming a protective film of the present embodiment is not limited to that shown in Figs. 2 to 5, and may have some configurations of those shown in Figs. 2 to 5 changed or deleted within a range that does not impair the effect of the present invention. However, another configuration may be added to what has been described so far.

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

○Description

The base material is in the form of a sheet or a film, and its constituent materials include, for example, various resins.

Examples of the resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); Polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (copolymers obtained using ethylene as a monomer) ; Vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymer (resins obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, and wholly aromatic polyesters in which all structural units have aromatic cyclic groups; 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. can be mentioned.

Additionally, examples of the resin include polymer alloys such as mixtures of the polyester and other resins. It is preferable that the polymer alloy of polyester and other resins contains a relatively small amount of resins other than polyester.

In addition, examples of the resin include crosslinked resins obtained by crosslinking one or two or more of the resins exemplified so far; Modified resins such as ionomers using one or two or more of the above resins exemplified so far can also be mentioned.

The resin constituting the base material may be one type, two or more types, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

The substrate may be composed of one layer (single layer), or may be composed of two or more layers. 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. No.

The thickness of the base material is preferably 50 to 300 μm, and more preferably 60 to 100 μm. When the thickness of the base material is within this range, the flexibility of the composite sheet for forming a protective film and the adhesion suitability to the wafer are further improved.

Here, “thickness of the base material” means the thickness of the entire base material, and for example, the thickness of a base material consisting of multiple layers means the total thickness of all layers constituting the base material.

In addition to the main constituent materials such as the above resins, the base material may contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

The substrate is preferably transparent, may be colored depending on the purpose, or may have other layers deposited on it.

In this embodiment in which the protective film forming film has energy ray curability, it is preferable that the base material transmits energy rays.

The base material is roughened by sand blasting, solvent treatment, etc. to adjust its adhesion with the layer formed thereon (for example, an adhesive layer, a protective film forming film, or the other layers); Oxidation treatments such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; Lipophilic treatment; Hydrophilic treatment or the like may be applied to the surface. Additionally, the surface of the substrate may be primer-treated.

The base material may have adhesiveness on at least one side by containing a specific range of components (for example, resin, etc.).

The base material can be manufactured by known methods. For example, a base material containing a resin can be manufactured by molding a resin composition containing the resin.

○Adhesive layer

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

Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin.

In this specification, “adhesive resin” includes both adhesive resin and adhesive resin. For example, the adhesive resins include not only those that have adhesiveness in themselves, but also resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness in the presence of a trigger such as heat or water. etc. are also included.

The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. 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 specifically limited. It doesn't work.

The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.

Here, “thickness of the adhesive layer” means the thickness of the entire adhesive layer, and for example, the thickness of the adhesive layer consisting of multiple layers means the total thickness of all layers constituting the adhesive layer.

The adhesive layer is preferably transparent, and may be colored depending on the purpose.

In this embodiment in which the protective film forming film has energy ray curability, it is preferable that the pressure-sensitive adhesive layer transmits energy rays.

The adhesive layer may be either energy ray curable or non-energy ray curable. The energy radiation-curable adhesive layer can control its physical properties before and after curing. For example, by curing the energy ray-curable adhesive layer before picking up the chip with the protective film, which will be described later, the chip with the protective film can be picked up more easily. When the adhesive layer is non-energy ray curable, light stability is high and storage stability is excellent.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer can be formed in the target area by coating the adhesive composition on the surface on which the adhesive layer is to be formed and drying it as necessary. The content ratio of components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the components in the adhesive layer.

Coating and drying of the adhesive composition can be performed, for example, in the same manner as in the case of coating and drying of the composition for forming a protective film described above.

When forming an adhesive layer on a substrate, for example, the adhesive composition may be applied on the substrate and dried as necessary. Additionally, for example, a pressure-sensitive adhesive composition is applied onto a release film and dried as necessary to form a pressure-sensitive adhesive layer on the release film, and the exposed surface of this pressure-sensitive adhesive layer is bonded to one surface of the base material, thereby forming a pressure-sensitive adhesive layer on the base material. An adhesive layer may be laminated. In this case, the release film can be removed at any timing during the manufacturing process or use process of the composite sheet for forming a protective film.

When the adhesive layer is energy ray curable, the energy ray curable adhesive composition may be, for example, non-energy ray curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”). and an adhesive composition (I-1) containing an energy ray curable compound; Contains energy ray curable adhesive resin (I-2a) (hereinafter sometimes abbreviated as “adhesive resin (I-2a)”) in which an unsaturated group is introduced into the side chain of non-energy ray curable adhesive resin (I-1a). Adhesive composition (I-2); and the adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.

When the pressure-sensitive adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable pressure-sensitive adhesive composition include the pressure-sensitive adhesive composition (I-4) containing the non-energy ray-curable adhesive resin (I-1a).

[Non-energy radiation curable adhesive resin (I-1a)]

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

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate ester.

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

The acrylic polymer preferably has structural units derived from functional group-containing monomers in addition to structural units derived from (meth)acrylic acid alkyl esters.

Examples of the functional group-containing monomer include, for example, the functional group reacting with a cross-linking agent to be described later, thereby becoming a starting point for cross-linking, or the functional group reacting with a functional group such as an isocyanate group or glycidyl group in an unsaturated group-containing compound to be described later, to form an acrylic polymer. Examples include those that enable the introduction of an unsaturated group into the side chain.

Examples of the functional group-containing monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.

The acrylic polymer may have structural units derived from other monomers in addition to structural units derived from (meth)acrylic acid alkyl esters and structural units derived from functional group-containing monomers.

The other monomers mentioned above are not particularly limited as long as they can be copolymerized with (meth)acrylic acid alkyl esters, etc.

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

The adhesive composition (I-1), adhesive composition (I-2), adhesive composition (I-3), and adhesive composition (I-4) (hereinafter, encompassing these adhesive compositions, “Adhesive composition (I-1) ) to (I-4)”), the structural units of the acrylic resin such as the acrylic polymer may be one type, two or more types, and in the case of two or more types, their combination and ratio are You can choose arbitrarily.

In the acrylic polymer, the ratio of the amount of structural units derived from functional group-containing monomers to the total mass of structural units is preferably 1 to 35% by mass.

The adhesive resin (I-1a) contained in the adhesive composition (I-1) or the adhesive composition (I-4) may be one type, two or more types, and in the case of two or more types, their combination and ratio may be arbitrary. You can choose.

In the adhesive layer formed from the adhesive composition (I-1) or the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive layer is 5 to 99% by mass. It is preferable, and for example, it may be any of 25 to 95 mass %, 45 to 95 mass %, and 65 to 95 mass %.

[Energy Ray Curable 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 that, in addition to the energy-ray polymerizable unsaturated group, has a group that can be bonded to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a).

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

Groups that can be bonded to functional groups in the adhesive resin (I-1a) include, for example, isocyanate groups and glycidyl groups that can bond to hydroxyl groups or amino groups, and hydroxyl and amino groups that can bond to carboxyl groups or epoxy groups.

Examples of the unsaturated group-containing compound include (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, and glycidyl (meth)acrylate.

The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be one type, two or more types, and if two or more types are used, their combination and ratio can be arbitrarily selected. .

In the adhesive layer formed from the adhesive composition (I-2) or (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive layer is preferably 5 to 99% by mass. do.

[Energy ray curable compound]

Examples of the energy ray curable compound contained in the adhesive composition (I-1) or (I-3) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation of an energy ray.

Among energy-ray curable compounds, monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Polyhydric (meth)acrylates such as 1,4-butylene glycol di(meth)acrylate and 1,6-hexanediol (meth)acrylate; Urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; Epoxy (meth)acrylate, etc. can be mentioned.

Among energy-ray curable compounds, examples of oligomers include oligomers that are polymers of the monomers exemplified above.

The energy ray curable compound contained in the adhesive composition (I-1) or (I-3) may be one type or two or more types, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

In the adhesive layer formed from the adhesive composition (I-1) or (I-3), the ratio of the content of the energy ray curable compound to the total mass of the adhesive layer is preferably 1 to 95% by mass.

[Cross-linking agent]

When using the above-described acrylic polymer as the adhesive resin (I-1a), which has structural units derived from functional group-containing monomers in addition to structural units derived from (meth)acrylic acid alkyl esters, the adhesive composition (I-1) or (I -4) It is preferable to further contain a cross-linking agent.

In addition, when using as the adhesive resin (I-2a), for example, the acrylic polymer having the same structural unit derived from a functional group-containing monomer as that in the adhesive resin (I-1a), the adhesive composition (I- 2) or (I-3) may further contain a cross-linking agent.

For example, the crosslinking agent reacts with the functional group to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a).

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

The crosslinking agent contained in the adhesive compositions (I-1) to (I-4) may be one type, two or more types, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

In the adhesive composition (I-1) or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the adhesive resin (I-1a), for example, 1 It may be any one of -40 parts by mass, 5-35 parts by mass, and 10-30 parts by mass.

The content of the crosslinking agent in the adhesive composition (I-2) or (I-3) is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a).

[Photopolymerization initiator]

Adhesive compositions (I-1), (I-2), and (I-3) (hereinafter, collectively, these adhesive compositions are abbreviated as “adhesive compositions (I-1) to (I-3)”) Additionally, a photopolymerization initiator may be contained. The curing reaction of the adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator sufficiently proceeds even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include the same photopolymerization initiator (c) described above.

The photopolymerization initiator contained in the adhesive compositions (I-1) to (I-3) may be one type, two or more types, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray curable compound.

The content of the photopolymerization initiator in the adhesive composition (I-2) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the adhesive resin (I-2a).

The content of the photopolymerization initiator in the adhesive composition (I-3) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total mass of the adhesive resin (I-2a) and the energy ray curable compound.

[Other additives]

The adhesive compositions (I-1) to (I-4) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effect of the present invention.

The above other additives include, for example, antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts). ) and other known additives.

On the other hand, the reaction retardant refers to, for example, the reaction of the adhesive composition (I-1) to (I-4) during storage by the action of the catalyst mixed in the adhesive composition (I-1) to (I-4). It is a component that suppresses the progress of an unintended crosslinking reaction. Examples of reaction retarders include those that form a chelate complex by chelating the catalyst, and more specifically, those that have two or more carbonyl groups (-C(=O)-) in one molecule. there is.

The number of other additives contained in the adhesive compositions (I-1) to (I-4) may be one, two or more, and in the case of two or more, their combination and ratio may be selected arbitrarily.

The content of other additives in the adhesive compositions (I-1) to (I-4) is not particularly limited and may be appropriately selected depending on the type.

[menstruum]

The adhesive compositions (I-1) to (I-4) may contain a solvent. By containing a solvent, the adhesive compositions (I-1) to (I-4) improve the coating suitability on the surface to be coated.

The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; Ester (carboxylic acid ester) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as cyclohexane and n-hexane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as 1-propanol and 2-propanol can be mentioned.

The solvent contained in the adhesive compositions (I-1) to (I-4) may be one type, two or more types, and in the case of two or more types, their combination and ratio may be selected arbitrarily.

The solvent content of the adhesive compositions (I-1) to (I-4) is not particularly limited and may be adjusted appropriately.

○Method for producing adhesive composition

Adhesive compositions such as adhesive compositions (I-1) to (I-4) are obtained by mixing the adhesive and, if necessary, components for constituting the adhesive composition, such as components other than the adhesive.

For example, the adhesive composition can be prepared in the same manner as the composition for forming a protective film described above, except that the types of ingredients are different.

◇Method of manufacturing composite sheet for forming protective film

The composite sheet for forming a protective film can be manufactured by stacking each of the above-described layers in a corresponding positional relationship and adjusting the shapes of some or all layers as needed. The method of forming each layer is the same as described above.

For example, when manufacturing a support sheet and laminating an adhesive layer on a base material, the above-described adhesive composition may be applied on the base material and dried as necessary.

Alternatively, a pressure-sensitive adhesive composition may be applied onto the release film, dried as necessary, thereby forming an adhesive layer on the release film, and the exposed surface of this adhesive layer may be bonded to one surface of the substrate to form the adhesive on the substrate. Layers can be stacked. At this time, it is preferable to apply the adhesive composition to the peeling treated surface of the peeling film.

So far, the case of laminating an adhesive layer on a base material has been taken as an example, but the above-described method can also be applied, for example, in the case of laminating a layer other than the adhesive layer on a base material.

On the other hand, for example, when a protective film-forming film is additionally laminated on the adhesive layer laminated on the substrate, it is possible to directly form the protective film-forming film by coating the protective film-forming composition on the adhesive layer. Layers other than the protective film forming film can also be laminated on the adhesive layer in the same manner using a composition for forming this layer. In this way, a new layer (hereinafter abbreviated as “second layer”) is formed on one of the layers (hereinafter abbreviated as “first layer”) laminated on the substrate, and the two consecutive layers are formed. When forming a laminated structure (in other words, a laminated structure of a first layer and a second layer), a method of coating a composition for forming the second layer on the first layer and drying it as necessary It can be applied.

However, the second layer is formed in advance on the release film using a composition for forming the second layer, and the exposed surface of the formed second layer on the opposite side from the side in contact with the release film is exposed to the first layer. It is preferable to form a continuous two-layer laminated structure by bonding with cotton. At this time, it is preferable to apply the composition to the peeling treated surface of the peeling film. The release film may be removed as needed after forming the laminated structure.

Here, the case of laminating a protective film-forming film on an adhesive layer is given as an example, but the target laminate structure can be selected arbitrarily, such as the case of laminating a layer (film) other than a protective film-forming film on the adhesive layer. .

In this way, all layers other than the base material constituting the composite sheet for forming a protective film are formed in advance on a release film and can be laminated by bonding them to the surface of the target layer, so this process is adopted as necessary. A composite sheet for forming a protective film can be manufactured by appropriately selecting the layers.

On the other hand, the composite sheet for forming a protective film is usually stored with a release film laminated to the surface of the outermost layer (for example, a protective film forming film) on the opposite side to the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is applied onto this peeling film (preferably the peeling treated surface thereof) and dried as necessary, thereby forming a top layer on the peeling film. A layer constituting the surface layer is formed, and the remaining layers are laminated on the exposed surface opposite to the side in contact with the release film of this layer by any of the above-described methods and bonded together without removing the release film. By leaving it as is, a composite sheet for forming a protective film on which a release film is formed is obtained.

The composite sheet for forming a protective film may be in the form of a sheet, and is preferably in the form of a roll.

◇Kit

The kit according to one embodiment of the present invention is used to support a first laminate in which a first release film and a protective film-forming film are laminated in this order, a work to which the protective film-forming film is attached, and the protective film-forming film. A kit including a support sheet, wherein the protective film forming film is the protective film forming film according to one embodiment of the present invention described above.

An example of the kit 1 of this embodiment will be described below with reference to the drawings.

Fig. 6 is a cross-sectional view schematically showing an example of the kit 1 of this embodiment.

The kit 1 of this embodiment includes a first laminate 5 in which the first release film 151, the protective film forming film 13, and the second release film 152 are laminated in this order, and the protective film forming film. It is provided with a support sheet 10 used to support the work to be attached to (13) and the protective film forming film 13, and the support sheet 10 is a support sheet according to the embodiment of the present invention described above. .

The protective film forming film 13 shown here has a first release film 151 on one side (sometimes referred to as “first side” in this specification) 13a, and the first side A second release film 152 is provided on the other surface 13b (sometimes referred to as “second surface” in this specification) opposite to 13a.

By using the kit 1 provided with the support sheet 10 and the protective film forming film, a protective film comprising a chip and a protective film formed on the back side of the chip is formed by the method of manufacturing a chip with a protective film, which will be described later. Chips can be manufactured.

This protective film forming film 13 is preferably stored in roll form, for example. That is, it is preferable that the first laminate is roll-shaped.

The protective film forming film 13 can be formed using the composition for forming a protective film described above.

The first release film 151 and the second release film 152 may both be known.

The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other, for example, the peeling forces required when peeling from the protective film forming film 13 are different from each other.

In the protective film forming film 13 shown in FIG. 6, the exposed surface created by removing either the first peeling film 151 or the second peeling film 152 becomes the attaching surface to the back side of the work (not shown). . Then, the exposed surface created by removing the other side of the first peeling film 151 and the second peeling film 152 becomes the attaching surface of the support sheet.

In Figure 6, an example is shown in which the release film is formed on both surfaces (the first side 13a and the second side 13b) of the protective film forming film 13, but the release film is formed on the protective film forming film 13. It may be formed on only one side, that is, only the first side 13a or only the second side 13b.

The kit 1 of this embodiment uses the protective film forming film 13 and the support sheet 10 in combination, so that both the attachment of the protective film formation film to the work and the subsequent attachment of the support sheet can be performed in an in-line process. Here, “in-line process” is “a process performed within a device that connects multiple devices (multiple units) performing one or more processes, or within the same device, and includes multiple processes and the conveyance that connects the processes. It refers to the process of “transferring workpieces one by one between one process and the next process.”

◇Method of manufacturing a chip with a protective film (method of using the protective film forming film, composite sheet for forming a protective film, and kit)

The protective film forming film, the composite sheet for forming a protective film, and the kit can be used to manufacture a chip on which the protective film is formed.

That is, the method of manufacturing a chip with a protective film according to the present embodiment is a method of manufacturing a chip with a protective film including a chip and a protective film formed on the back side of the chip, wherein one embodiment of the present invention described above is applied to the back side of the wafer. By attaching a protective film-forming film according to the shape, a first laminated film composed of the protective film-forming film and the wafer stacked in the thickness direction thereof is produced, or the above-described work of the present invention is applied to the back side of the wafer. By attaching the protective film forming film in the protective film forming composite sheet according to the embodiment, the first laminated composite sheet is formed by stacking the support sheet, protective film forming film, and wafer in this order in their thickness direction. A manufacturing process (sometimes referred to as a “pasting process” in this specification) and energy ray curing of the protective film forming film in the first laminated film or the first laminated composite sheet to form the protective film, A second laminated film is manufactured in which the protective film and the wafer are stacked in their thickness direction, or the support sheet, protective film, and wafer are stacked in this order in their thickness direction. A process of producing a second laminated composite sheet (in this specification, it may be referred to as a “curing process”), and a dicing sheet is formed on the protective film side of the second laminated film, By dividing the wafer in the laminated film and cutting the protective film, a third laminated film is produced in which a plurality of chips formed with the protective film are fixed on the dicing sheet, or a third laminated film in the second laminated composite sheet is produced. A process of dividing the wafer and cutting the protective film to produce a third laminated composite sheet in which a plurality of chips formed with the protective film are fixed on the support sheet (referred to as “splitting process” in this specification) (in some cases) and a process of picking up the chips with the protective film in the third laminated film by separating them from the dicing sheet, or by separating the chips with the protective film in the third laminated composite sheet from the support sheet. (In this specification, it may be referred to as a “pickup process”).

Hereinafter, referring to the drawings, a method for manufacturing a chip with a protective film (this method) in which a protective film forming film that does not constitute a composite sheet for forming a protective film (i.e., the protective film forming film in the kit) is attached to the back side of the wafer In the specification, it may be referred to as “manufacturing method 1”), and a method of manufacturing a chip with a protective film formed in the case of attaching a protective film forming film in a protective film forming composite sheet to the back side of the wafer (in this specification, (sometimes referred to as “manufacturing method 2”) will be explained sequentially.

＜＜Manufacturing method 1＞＞

Figure 7 is a cross-sectional view schematically explaining manufacturing method 1. Here, manufacturing method 1 will be described taking as an example the case where the protective film forming film 13 shown in FIG. 1, and more specifically, the kit shown in FIG. 6, is used.

In the above sticking process of manufacturing method 1, as shown in FIG. 7(a), the above-described protective film forming film 13 is attached to the back surface 9b of the wafer 9, thereby forming the protective film forming film 13 and A first laminated film 601 composed of wafers 9 stacked in the thickness direction is produced. The first side 13a of the protective film forming film 13 is attached to the back side 9b of the wafer 9. A second release film 152 is formed on the second surface 13b of the protective film forming film 13.

Here, the first release film 151 is removed from the protective film forming film 13 shown in FIG. 1, and the first surface 13a of the protective film forming film 13 is attached to the back surface 9b of the wafer 9. Although the case is shown, the second peeling film 152 is removed from the protective film forming film 13 shown in FIG. 1, and the second surface 13b of the protective film forming film 13 is attached to the back surface 9b of the wafer 9. ) may be attached.

Attaching the protective film forming film 13 to the wafer 9 can be performed by a known method. For example, the protective film forming film 13 may be attached to the wafer 9 while heating.

Next, in the curing step of manufacturing method 1, the protective film forming film 13 in the first laminated film 601 is cured with energy rays to form a protective film 13', as shown in FIG. 7(b). The second laminated film 602 is manufactured by stacking the protective film 13' and the wafer 9 in the thickness direction. The symbol 13a' represents a surface of the protective film 13' that was the first surface 13a of the protective film forming film 13 (in this specification, it may be referred to as the “first surface”). The symbol 13b' represents a surface of the protective film 13' that was the second surface 13b of the protective film forming film 13 (in this specification, it may be referred to as the “second surface”).

In the curing process, from the outside of the first laminated film 601 on the protective film forming film 13 side, beyond the second peeling film 152 with respect to the protective film forming film 13 (second peeling film 152) By irradiating energy lines through (through), a protective film 13' is formed.

In the curing process, the second peeling film 152 is removed from the protective film forming film 13 in the first laminated film 601 to expose the second surface 13b of the protective film forming film 13, The protective film 13' may be formed by irradiating the protective film forming film 13 with energy rays.

The energy ray irradiation conditions in the curing process are the same as described above.

The protective film forming film 13 shown in FIG. 7(a) may be laser marked by irradiating the laser beyond the second release film 152 (through the second release film 152), or may be laser marked as shown in FIG. 7(b). The protective film 13' shown in ) may be laser marked by irradiating the laser beyond the second peeling film 152 (through the second peeling film 152).

Next, in the division step of manufacturing method 1, the second release film 152 is first removed from the protective film 13' in the second laminated film 602. And, as shown in FIG. 7(c), on the second surface 13b' of the protective film 13' newly exposed by this, one surface of the dicing sheet 8 (in this specification, "first surface") Attach (8a) (sometimes referred to as “myeon”).

The dicing sheet 8 shown here is comprised of a base material 81 and an adhesive layer 82 formed on one side 81a of the base material 81, and the adhesive layer in the dicing sheet 8 (82) is attached to the protective film 13'. The surface 82a (sometimes referred to as “first surface” in this specification) of the adhesive layer 82 on the protective film 13′ side is the same as the first surface 8a of the dicing sheet 8. do.

The dicing sheet 8 may be a known one. For example, the base material 81 may be the same as the base material in the above-described composite sheet for forming a protective film, and the adhesive layer 82 may be the same as the adhesive layer in the composite sheet for forming a protective film described above. That is, the dicing sheet 8 can be replaced with the support sheet 10.

Here, the case where the dicing sheet 8 provided with the base material 81 and the adhesive layer 82 is used is shown, but in the above dividing process, a dicing sheet other than this may be used, for example, using only the base material. You may use a dicing sheet that is made.

Next, in the division step, as shown in FIG. 7(d), the dicing sheet 8 is formed on the protective film 13' side of the second laminated film 602, and the second laminated film 602 is The wafer 9 in (602) is divided and the protective film 13' is cut. The wafer 9 is divided into individual pieces to form a plurality of chips 90.

The division of the wafer 9 and the cutting of the protective film 13' may be performed by known methods. For example, the wafer 9 is divided by dicing such as blade dicing, laser dicing by laser irradiation, or water dicing by spraying water containing an abrasive, and the protective film 13' is formed. Cutting can be performed continuously.

The protective film 13' is cut along the outer circumference of the chip 90, regardless of the cutting method.

In this way, by dividing the wafer 9 and cutting the protective film 13', the chip 90 and the cut protective film (in this specification, simply referred to as "protective film") are formed on the back surface 90b of the chip 90. A chip 901 on which a plurality of protective films including 130' is formed is obtained. The symbol 130b' represents the surface of the protective film 130' after cutting, which was the second surface 13b' of the protective film 13' (in this specification, it may be referred to as the "second surface").

In the division step of manufacturing method 1, the third laminated film 603 is produced by fixing the plurality of chips 901 with the protective film formed on the dicing sheet 8 as described above.

Next, in the above-mentioned pickup process of manufacturing method 1, as shown in FIG. 7(e), the chip 901 with the protective film in the third laminated film 603 is picked up by separating it from the dicing sheet 8.

In the pick-up process, between the second surface 130b' of the protective film 130' in the chip 901 on which the protective film is formed and the first surface 82a of the adhesive layer 82 in the dicing sheet 8. Delamination occurs.

Here, the case where the chip 901 with the protective film formed is separated in the direction of arrow P using the separation means 7 such as a vacuum collet is shown. Meanwhile, the cross-sectional representation of the separating means 7 is omitted here.

The chip 901 on which the protective film is formed can be picked up by a known method.

When the adhesive layer 82 is energy ray curable, in the pickup process, the adhesive layer 82 is cured by irradiating an energy ray to the adhesive layer 82 to form a cured product (not shown). , it is desirable to separate the chip 901 on which the protective film is formed from the dicing sheet 8. In this case, in the pick-up process, peeling occurs between the protective film 130' in the chip 901 on which the protective film is formed and the cured product of the adhesive layer 82 in the dicing sheet 8.

In this case, the cured product of the adhesive layer 82 becomes less likely to be deformed compared to before curing, making it easier to pick up the chip 901 on which the protective film is formed.

For example, the conditions for irradiating energy rays to the adhesive layer 82 in the pick-up process may be the same as the conditions for irradiating energy rays to the protective film forming film 13 in the curing process.

In this specification, as long as the laminated structure of the substrate and the cured product of the energy ray-curable adhesive layer is maintained even after the energy ray-curable adhesive layer is energy ray-cured, this laminated structure is referred to as a “dicing sheet.”

On the other hand, in the case where the adhesive layer 82 is non-energy ray curable, the chip 901 with the protective film formed thereon can be separated from the adhesive layer 82 as is, and curing of the adhesive layer 82 is not necessary, which is a simplified process. The chip 901 on which the protective film is formed can be picked up.

Even if the adhesive layer 82 is energy-ray curable, the chip 901 with the protective film can be picked up in a simplified process by picking up the chip 901 with the protective film formed without curing the adhesive layer 82.

In the pick-up process, the pick-up of the chips 901 with the protective film is performed on all chips 901 with the protective film.

In manufacturing method 1, the chip 901 on which the target protective film is formed is obtained by carrying out the above-mentioned pick-up process.

In the conventional energy ray curable protective film forming film, when the protective film forming film is irradiated with energy rays through the release film, there are cases where the protective film forming film is not sufficiently cured and the protective film becomes prone to peeling. In this way, when the protective film forming film is not properly cured, there is a risk that subsequent manufacturing of the semiconductor device may be hindered.

In manufacturing method 1, since the protective film-forming film according to one embodiment of the present invention described above is used, the change rate of the indentation depth of the protective film-forming film is set to a preferable range when curing the protective film-forming film with energy rays, thereby forming the protective film-forming film. can be cured preferably, and peeling of the protective film can be suppressed.

＜＜Manufacturing method 2＞＞

Figure 8 is a cross-sectional view schematically illustrating manufacturing method 2. Here, manufacturing method 2 will be described taking the case where the composite sheet 101 for forming a protective film shown in FIG. 2 is used as an example.

In the above sticking process of manufacturing method 2, as shown in FIG. 8(a), the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the back surface 9b of the wafer 9, The first laminated composite sheet 501 is manufactured by stacking the support sheet 10, the protective film forming film 13, and the wafer 9 in this order in the thickness direction. In this case as well, as in the case of manufacturing method 1, the first side 13a of the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the back surface 9b of the wafer 9. .

The protective film forming film 13 in the protective film forming composite sheet 101 can be attached to the wafer 9 by a known method. For example, the protective film forming film 13 may be attached to the wafer 9 while heating.

Next, in the curing step of manufacturing method 2, the protective film forming film 13 in the first laminated composite sheet 501 is cured with energy rays to form a protective film 13', as shown in FIG. 8(b). , the second laminated composite sheet 502 is manufactured by stacking the support sheet 10, the protective film 13', and the wafer 9 in this order in their thickness direction.

In the curing process, from the outside of the first laminated composite sheet 501 on the support sheet 10 side, the protective film forming film 13 passes through the support sheet 10 (through the support sheet 10). By irradiating energy lines, a protective film 13' is formed.

The curing process can be performed in the same manner as the curing process in Manufacturing Method 1, except that the first laminated composite sheet 501 is used instead of the first laminated film 601.

The second laminated composite sheet 502 obtained in the curing process has the same structure as the laminate of the second laminated film 602 and the dicing sheet 8 in the dividing process in manufacturing method 1. When the dicing sheet 8 is the same as the support sheet 10, the second laminated composite sheet 502 is identical to the above laminate.

Next, in the division step of manufacturing method 2, as shown in FIG. 8(c), the wafer 9 in the second laminated composite sheet 502 is divided and the protective film 13' is cut. The wafer 9 is divided into individual pieces to form a plurality of chips 90.

The dividing process is similar to the dividing process in manufacturing method 1, except that the second laminated composite sheet 502 is used instead of the laminate of the second laminated film 602 and the dicing sheet 8. It can be done in the same way as in the case.

Also in manufacturing method 2, the protective film 13' is cut along the outer periphery of the chip 90 regardless of the cutting method.

In this way, by dividing the wafer 9 and cutting the protective film 13', a plurality of wafers are formed including the chip 90 and the cut protective film 130' formed on the back surface 90b of the chip 90. A chip 901 with a protective film formed thereon is obtained.

The chip 901 with a protective film obtained in the division step in manufacturing method 2 is the same as the chip 901 with a protective film obtained in the division step in manufacturing method 1.

The protective film forming film 13 shown in FIG. 8(a) may be laser marked by irradiating a laser beyond the support sheet 10 (through the support sheet 10), or the protective film shown in FIG. 8(b) may be applied. For (13'), laser marking may be performed by irradiating the laser beyond the support sheet 10 (through the support sheet 10).

In the division step of manufacturing method 2, the third laminated composite sheet 503 is manufactured by fixing the plurality of chips 901 with the protective film formed on the support sheet 10 as described above.

The third laminated composite sheet 503 has the same structure as the third laminated film 603 obtained in the splitting process in Manufacturing Method 1. When the dicing sheet 8 is the same as the support sheet 10, the third laminated composite sheet 503 is the same as the third laminated film 603.

Next, in the pickup process of manufacturing method 2, as shown in FIG. 8(d), the chip 901 with the protective film in the third laminated composite sheet 503 is picked up by separating it from the support sheet 10.

In the pick-up process, separation occurs between the second surface 130b' of the protective film 130' in the chip 901 on which the protective film is formed and the first surface 12a of the adhesive layer 12 in the support sheet 10. occurs.

The pickup process can be performed in the same manner as the pickup process in Manufacturing Method 1, except that the third laminated composite sheet 503 is used instead of the third laminated film 603.

For example, when the pressure-sensitive adhesive layer 12 is energy-ray curable, in the pickup process, the pressure-sensitive adhesive layer 12 is cured by irradiating energy rays to the pressure-sensitive adhesive layer 12 to form a cured product (not shown). After forming, it is preferable to separate the chip 901 on which the protective film is formed from the support sheet 10. In this case, in the pick-up process, separation occurs between the protective film 130' in the chip 901 on which the protective film is formed and the cured product of the adhesive layer 12 in the support sheet 10.

In this case, since the cured product of the adhesive layer 12 is less likely to be deformed compared to before curing, the chip 901 with the protective film formed can be picked up more easily.

On the other hand, in the case where the adhesive layer 12 is non-energy ray curable, the chip 901 with the protective film formed thereon can be separated from the adhesive layer 12 as is, and curing of the adhesive layer 12 is not necessary, which is a simplified process. The chip 901 on which the protective film is formed can be picked up.

Even if the adhesive layer 12 is energy-ray curable, the chip 901 with the protective film can be picked up in a simplified process by picking up the chip 901 with the protective film formed without curing the adhesive layer 12.

In manufacturing method 2, the chip 901 on which the target protective film is formed is obtained by carrying out the above-mentioned pick-up process. The chip 901 with a protective film obtained in manufacturing method 2 is the same as the chip 901 with a protective film obtained in manufacturing method 1.

In the conventional composite sheet for forming a protective film including an energy ray-curable protective film forming film, when the protective film forming film is irradiated with energy rays beyond the support sheet 10, the protective film forming film is not sufficiently cured and the protective film becomes prone to peeling. There was a problem. In this way, when the protective film forming film is not properly cured, there is a risk that subsequent manufacturing of the semiconductor device may be hindered.

In manufacturing method 2, since the above-described composite sheet for forming a protective film including the protective film forming film according to one embodiment of the present invention described above is used, when curing the protective film forming film with energy rays, the indentation depth of the protective film forming film By setting the change rate within a desirable range, the protective film forming film can be cured suitably and peeling of the protective film can be suppressed.

So far, the manufacturing method 2 when using the composite sheet 101 for forming a protective film shown in FIG. 2 has been described, but in manufacturing method 2, the composite sheet 102 for forming a protective film shown in FIGS. 3 to 5 and the protective film are used. You may use a composite sheet for forming a protective film of this embodiment other than the composite sheet for forming a protective film 101, such as the composite sheet for forming a protective film 103 or the composite sheet 104 for forming a protective film.

◇Manufacturing method of substrate device (method of using chip with protective film formed)

After obtaining a chip with a protective film formed by the above-described manufacturing method, the manufacturing method of the conventional face-down type substrate device is the same as that of the conventional face-down type substrate device, except that the chip with this protective film is used instead of the chip with the conventional protective film. With this method, a substrate device can be manufactured.

For example, a reflow process in which the protruding electrodes on the chip with the protective film are melted by heating the circuit board on which the chip with the protective film obtained using the protective film forming film is mounted using a reflow furnace equipped with a halogen heater. A method of manufacturing a substrate device that strengthens the electrical connection between a protruding electrode and a connection pad on a circuit board can be mentioned.

The substrate device of the present embodiment uses the above-described kit including the above-described protective film-forming film or the above-described composite sheet for forming a protective film, so that the protective film-forming film can be cured suitably, and peeling of the protective film is suppressed.

◇Use of protective film forming film

The use of the protective film forming film according to one embodiment of the present invention is the use of the protective film forming film to form a protective film on the surface (i.e., back side) opposite to the circuit surface of a semiconductor wafer or semiconductor chip, wherein the protective film forming film This is a protective film forming film according to one embodiment of the present invention described above.

The use of the protective film-forming film of the present embodiment is provided with the protective film-forming film, so that when the protective film-forming film is cured by energy rays, the change rate of the indentation depth of the protective film-forming film is set to a desirable range, so that the protective film-forming film is preferably formed. It can be hardened and peeling of the protective film is suppressed.

Use of the protective film forming film of the present invention has the following aspects.

<11> Use of a protective film forming film to form a protective film on the surface opposite to the circuit surface of a semiconductor wafer or semiconductor chip,

The protective film forming film is an energy ray curable protective film forming film,

Use of a protective film forming film wherein the rate of change in indentation depth measured by the method for measuring the rate of change in indentation depth of the protective film forming film below is 60% or more.

＜Method for measuring the rate of change of indentation depth＞

The protective film-forming film is irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2 to produce a cured protective film-forming film.

For the protective film forming film before and after curing, the indentation depth (μm) is measured using an ultra-micro hardness meter under the following conditions.

Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛

Measurement mode: load-unload test

Maximum load: 10mN

Hold time when reaching maximum load: 5 seconds

Load speed: 0.14mN/sec

Temperature: 23℃

Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing is calculated by the following formula (1), and this is taken as the rate of change of the indentation depth of the protective film-forming film.

Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One)

<12> The protective film forming film contains an acrylic resin (b) without an energy ray curable group, and the acrylic resin (b) has a structural unit derived from 4-(meth)acryloylmorpholine, <11 Use of the protective film forming film described in ＞.

<13> Use of the protective film forming film according to <11> or <12> to form a protective film on a surface opposite to the circuit surface of a semiconductor wafer or semiconductor chip in the production of a chip with a protective film.

<14> Use of the protective film forming film according to <11> or <12> to form a protective film on a surface opposite to the circuit surface of a semiconductor wafer or semiconductor chip in the manufacture of a face-down type substrate device.

Example

Hereinafter, the present invention will be described in more detail through specific examples. However, the present invention is in no way limited to the examples shown below.

＜Raw materials for manufacturing resin＞

The official names of the raw materials for producing the resin abbreviated in this Example and Comparative Example are shown below.

BA: n-butyl acrylate

MA: Methyl acrylate

ACrMO: 4-acryloylmorpholine

HEA: 2-hydroxyethyl acrylate

2EHA: 2-ethylhexyl acrylate

MMA: Methyl methacrylate

＜Making raw materials for the composition for forming a protective film＞

The raw materials used in the production of the composition for forming a protective film are shown below.

[Energy Ray Curing Ingredient (a)]

(a)-1: ε-caprolactone modified tris-(2-acryloxyethyl)isocyanurate (“A-9300-1CL” manufactured by Shinnakamura Kagaku Kogyo Co., Ltd., trifunctional ultraviolet curable compound)

(a)-2: Urethane acrylate (“Quick cure 8100EA70” manufactured by KJ Chemicals)

[Acrylic resin (b) without energy ray curable group]

(b)-1: Acrylic resin (weight average molecular weight (700000), glass transition temperature) which is a copolymer of BA (33 parts by mass), MA (27 parts by mass), ACrMO (25 parts by mass), and HEA (15 parts by mass) 2℃)

[Photopolymerization initiator (c)]

(c)-1: 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one (“Omnirad (registered trademark) 379” manufactured by IGM Resins) )

(c)-2: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (manufactured by IGM Resins) Omnirad (registered trademark) 127D”)

(c)-3: 1-Hydroxy-cyclohexyl-phenyl-ketone (“Omnirad (registered trademark) 184” manufactured by IGM Resins)

[Inorganic filler (d)]

(d)-1: Silica filler (fused quartz filler, average particle diameter 8㎛)

[Colorant (g)]

(g)-1: Organic black pigment (“6377 Black” manufactured by Dainichi Seika Kogyo Co., Ltd.)

[General purpose additive (z)]

(z)-1: Hydroxyphenyltriazine-based ultraviolet absorber (“Tinuvin (registered trademark) 479” manufactured by BASF, solid at 25°C)

＜＜Manufacture of protective film forming film＞＞

[Example 1]

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

Energy ray curable component (a)-1 (12.4 parts by mass), energy ray curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) without an energy ray curable group, photopolymerization Initiator (c)-1 (0.1 parts by mass), photopolymerization initiator (c)-2 (0.5 parts by mass), inorganic filler (d)-1 (58.4 parts by mass), colorant (g)-1 (3.0 parts by mass), and the general-purpose additive (z)-1 (0.8 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to form a composition for forming an energy ray-curable protective film in which the total concentration of all components other than the solvent is 55% by mass. (IV)-1 was obtained. Meanwhile, the blending amounts of components other than the solvent shown here are all blending amounts of the target substance without a solvent, and are the same in the following composition (IV) for forming a protective film.

<Manufacture of protective film forming film>

Using a release film (second release film, "SP-PET382150" manufactured by Lintec, thickness 38 ㎛) in which one side of the polyethylene terephthalate film was subjected to a release treatment by silicone treatment, the protective film obtained above was applied to the release treatment side. Composition (IV)-1 for forming was applied and dried at 100°C for 2 minutes to prepare an energy-ray curable protective film forming film with a thickness of 25 μm.

Additionally, the peeling treated surface of the peeling film (first peeling film, “SP-PET381031” manufactured by Lintech, thickness 38 μm) is bonded to the exposed surface of the obtained protective film forming film on the side not provided with the second peeling film. , a protective film forming film was obtained with a peeling film comprising a protective film forming film, a first peeling film formed on one side of the protective film forming film, and a second peeling film formed on the other side of the protective film forming film.

[Example 2]

<Preparation of composition (IV)-2 for forming a protective film>

Energy ray curable component (a)-1 (12.4 parts by mass), energy ray curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) without an energy ray curable group, photopolymerization Initiator (c)-2 (0.6 parts by mass), inorganic filler (d)-1 (58.4 parts by mass), colorant (g)-1 (3.0 parts by mass), and general-purpose additive (z)-1 (0.8 parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain composition (IV)-2 for forming an energy ray curable protective film having a total concentration of all components other than the solvent of 55% by mass.

<Manufacture of protective film forming film>

A protective film forming film of Example 2 was manufactured in the same manner as in Example 1, except that Composition (IV)-2 for forming a protective film was used instead of Composition (IV)-1 for forming a protective film.

[Example 3]

<Preparation of composition (IV)-3 for forming a protective film>

Energy ray curable component (a)-1 (12.4 parts by mass), energy ray curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) without an energy ray curable group, photopolymerization Initiator (c)-1 (0.1 parts by mass), photopolymerization initiator (c)-2 (0.5 parts by mass), inorganic filler (d)-1 (59.2 parts by mass), and colorant (g)-1 (3.0 parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain composition (IV)-3 for forming an energy ray curable protective film having a total concentration of all components other than the solvent of 55% by mass.

<Manufacture of protective film forming film>

A protective film forming film of Example 3 was manufactured in the same manner as in Example 1, except that Composition (IV)-3 for forming a protective film was used instead of Composition (IV)-1 for forming a protective film.

[Comparative Example 1]

<Preparation of composition (X)-1 for forming a protective film>

Energy ray curable component (a)-1 (12.4 parts by mass), energy ray curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) without an energy ray curable group, photopolymerization Initiator (c)-2 (0.1 parts by mass), inorganic filler (d)-1 (58.9 parts by mass), colorant (g)-1 (3.0 parts by mass), and general-purpose additive (z)-1 (0.8 parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain composition (X)-1 for forming an energy ray curable protective film having a total concentration of all components other than the solvent of 55% by mass.

<Manufacture of protective film forming film>

A protective film forming film of Comparative Example 1 was produced in the same manner as in Example 1, except that Composition (X)-1 for forming a protective film was used instead of Composition (IV)-1 for forming a protective film.

[Comparative Example 2]

<Preparation of composition (X)-2 for forming a protective film>

Energy ray curable component (a)-1 (12.4 parts by mass), energy ray curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) without an energy ray curable group, photopolymerization Initiator (c)-3 (0.1 parts by mass), inorganic filler (d)-1 (58.9 parts by mass), colorant (g)-1 (3.0 parts by mass), and general-purpose additive (z)-1 (0.8 parts by mass) was dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain composition (X)-2 for forming an energy ray curable protective film having a total concentration of all components other than the solvent of 55% by mass.

<Manufacture of protective film forming film>

A protective film forming film of Comparative Example 2 was prepared in the same manner as in Example 1, except that Composition (X)-2 for forming a protective film was used instead of Composition (IV)-1 for forming a protective film.

[Comparative Example 3]

<Preparation of composition (X)-3 for forming a protective film>

Energy ray curable component (a)-1 (12.4 parts by mass), energy ray curable component (a)-2 (10.1 parts by mass), acrylic resin (b)-1 (14.7 parts by mass) without an energy ray curable group, photopolymerization Initiator (c)-1 (0.1 parts by mass), photopolymerization initiator (c)-2 (0.5 parts by mass), inorganic filler (d)-1 (54.2 parts by mass), colorant (g)-1 (3.0 parts by mass), and general-purpose additive (z)-1 (5.0 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to form a composition for forming an energy ray-curable protective film wherein the total concentration of all components other than the solvent is 55% by mass. (X)-3 was obtained.

<Manufacture of protective film forming film>

A protective film forming film of Comparative Example 3 was prepared in the same manner as in Example 1, except that Composition (X)-3 for forming a protective film was used instead of Composition (IV)-1 for forming a protective film.

＜＜Evaluation of protective film forming film＞＞

＜Measurement of the indentation depth and rate of change of the protective film forming film＞

The protective film-forming film obtained above was irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2, and a cured protective film-forming film was produced.

For the protective film forming film before and after curing, the indentation depth (μm) was measured using an ultra-micro hardness meter (“Shimadzu Dynamic Ultra-micro hardness meter DUH-211” manufactured by Shimadzu Seisakusho) under the following conditions.

Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛

Measurement mode: load-unload test

Maximum load: 10mN

Hold time when reaching maximum load: 5 seconds

Load speed: 0.14mN/sec

Temperature: 23℃

Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing was calculated using the following formula (1), and this was used as the rate of change of the indentation depth of the protective film-forming film.

Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One)

The results of the indentation depth and change rate of the protective film forming film are shown in Tables 1 and 2.

＜Measurement of peel strength of protective film forming film＞

The second peeling film was removed from the protective film forming film on which the peeling film obtained above was formed. The exposed surface of the protective film forming film is affixed to the polished surface of a 6-inch silicon wafer (thickness 350 ㎛, #2000 polishing) under conditions of 70°C and 0.3 MPa, and the second release film, protective film forming film, and wafer are attached to this surface. In this order, a first laminated sheet was produced by stacking them in the thickness direction (above sticking process).

After the first laminated sheet was left standing for 20 minutes, it was irradiated with UV from the second release film side at an illuminance of 220 mW/cm2 and a light amount of 500 mJ/cm2, and the second release film, protective film, and wafer were peeled off in this order. A second laminated sheet configured to be laminated in the thickness direction was produced (above curing process). Next, the second release film was peeled from the second laminated sheet, the protective film and the wafer were divided into 1/4 using a ceramic cutter, and a third laminated sheet with a size of 1/4 of the second laminated sheet was produced ( above division process).

A dicing tape (“ADWILL D-833W” manufactured by Lintec) is attached to the exposed surface of the protective film in the third laminated sheet, and from the dicing tape side, using a cutter knife, 10 cuts are applied to the protective film and the dicing tape. The incision was made in a rectangular shape with a width of mm. Next, using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Seisakusho), the dicing tape and protective film were peeled from the wafer under the conditions of a peeling angle of 90°, a measurement temperature of 23°C, and a tensile speed of 50 mm/sec. A tensile test was performed, and the load at this time was measured, and was taken as the peeling force (peel strength of the protective film forming film) of the cured protective film forming film (protective film) and the wafer. The peeling strength of the protective film forming film was evaluated based on the following criteria.

A: The peeling strength was 3.5 to 10 N/10 mm.

B: Peel strength was less than 3.5 N/10 mm or more than 10 N/10 mm.

The evaluation results of the peel strength of the protective film forming film are shown in Tables 1 and 2.

[Manufacture of support sheet with peeling film formed]

100 parts by mass (solid content) of polymer component, 10 parts by mass (solid content) of tolylene diisocyanate-based crosslinking agent (“BHS-8515” manufactured by Tosoh Corporation), and 7.5 mass parts of hexamethylene diisocyanate-based crosslinking agent (“Coronate HL” manufactured by Tosoh Corporation) The portion (solid content) was dissolved or dispersed in methyl ethyl ketone, and the solid content concentration was adjusted to 30% by mass to obtain an adhesive composition.

Meanwhile, the polymer component is an acrylic polymer with a weight average molecular weight of 600,000 and a glass transition temperature of -11°C obtained by copolymerizing 80 parts by mass of 2-ethylhexyl methacrylate (2EHMA) and 20 parts by mass of 2-hydroxylethyl acrylate (HEA). It is a copolymer.

The above adhesive composition was applied to the peeled surface of the release film (“SP-PET382150” manufactured by Lintec, thickness 38 μm) using a knife coater and dried at 110°C for 2 minutes to form an adhesive layer (thickness of 5 μm after drying). Separately, on the exposed surface (surface on the side opposite to the side with the release film), a polypropylene film (thickness 80 ㎛, "Funk Rare (registered trademark) LPD #80" manufactured by Gunze) as a base material is applied to the glossy surface. The glossy side with a surface roughness of 0.1 μm and the matte side with a surface roughness of 0.3 μm were bonded together to obtain a support sheet on which a release film consisting of base material/adhesive layer/release film was formed.

[Production of composite sheet for forming a protective film]

The release film was removed from the support sheet on which the release film obtained above was formed. Additionally, the first peeling film was removed from the protective film forming film obtained above. Then, the exposed surface of the adhesive layer formed by removing the peeling film is bonded to the exposed surface of the protective film forming film formed by removing the first peeling film, thereby forming a base material, an adhesive layer, a protective film forming film, and a second peeling film. A composite sheet for forming a protective film was produced by stacking the films in this order in their thickness direction.

＜Reliability test of protective film forming film＞

The second release film was removed from the obtained composite sheet for forming a protective film. The composite sheet for forming a protective film with the protective film forming film exposed is attached to the polished surface of a 6-inch silicon wafer (thickness 350 ㎛, #2000 polished) under conditions of 70°C and 0.3 MPa, and the support sheet, the protective film forming film, and A first laminated composite sheet was produced in which wafers were stacked in this order in their thickness direction (above sticking process).

After the first laminated composite sheet was left to stand for 20 minutes, it was irradiated with UV from the support sheet side at an illuminance of 220 mW/cm2 and a light quantity of 500 mJ/cm2, and the support sheet, protective film, and wafer were irradiated in this order in their thickness direction. A second laminated composite sheet was produced by lamination (above curing process). Next, using a dicing device (“DFD6362” manufactured by Disco), the silicon wafer is divided under the following conditions, the protective film is cut, and a 3 mm × 3 mm chip with a protective film is fixed on the support sheet. A laminated composite sheet was produced (splitting process above).

Dicing speed: 30㎜/sec

Blade rotation speed: 50000rpm

Blade height: 60㎛

Blade Product Number: Z05-SD2000-N1-90 CC (manufactured by Disco)

The chips with the protective film in the third laminated composite sheet were picked up by separating them from the support sheet (above pickup process).

Next, the chip with the protective film formed was moved to a metal basket and dried in an oven (“SPH-201” manufactured by ESPEC) at 125°C for 24 hours.

The chip with the protective film formed was taken out of the oven, left to stand in a moist heat environment at 85°C/85%RH for 168 hours, and subjected to moist heat treatment. After the chip with the wet heat treatment and the protective film formed on it is taken out from the constant temperature and humidity chamber, it is reflowed in a reflow furnace (“STR-2010M” manufactured by Senju Kinzoku Kogyo Co., Ltd.) at a speed of 0.22 m/min for 10 minutes under conditions of a maximum temperature of 260°C. Heat treatment was performed for one minute.

Next, the heat-treated chip on which the protective film was formed is subjected to a temperature cycle consisting of a low-temperature treatment (i) followed by a high-temperature treatment (ii) with a small cold-heat shock device (“TSE-11-A” manufactured by ESPEC), The temperature cycle was repeated 1000 times. Meanwhile, the low-temperature treatment (i) exposes the heat-treated chip with the protective film obtained above to a low temperature of -40°C for a holding time of 10 minutes, and the high-temperature treatment (ii) exposes the protective film after the low-temperature treatment (i). The formed chip is exposed to a high temperature of 125°C, holding time: 10 minutes. The temperature cycle was performed in accordance with JEDEC Condition C.

Next, peeling of the protective film from the chip was confirmed using an ultrasonic microscope (“D9600 C-SAM” manufactured by Sonoscan), and the reliability of the protective film forming film was evaluated based on the following criteria.

A: No chips were identified where the protective film had peeled off, and the reliability was excellent.

B: Since a chip with peeling of the protective film was confirmed, reliability was poor.

The results of the reliability evaluation of the protective film forming film are shown in Tables 1 and 2.

On the other hand, the description "-" in the column of contained components in Tables 1 and 2 means that the protective film forming film does not contain that component.

As is clear from the above results, the protective film forming films of Examples 1 to 3 had a large change rate in indentation depth before and after curing, a high peel strength, and excellent adhesion reliability.

The protective film forming film of Comparative Example 1 had a small change rate in indentation depth before and after curing, a low peel strength, and poor adhesion reliability.

The protective film forming film of Comparative Example 2 had a small change rate in indentation depth before and after curing, a low peel strength, and poor adhesion reliability.

The protective film forming film of Comparative Example 3 had a small change rate in indentation depth before and after curing, low peel strength, and poor adhesion reliability.

The present invention can be used in the manufacture of various substrate devices, including semiconductor devices.

10, 20… Support sheets, 10a, 20a… One side of the support sheet (first side),
11… List, 12… Adhesive layer, 13, 23... Energy ray curable protective film forming film, 13'... Shield, 13b'... The other side of the shield (side 2), 130'... protective film after cutting,
101, 102, 103, 104… Composite sheet for forming a protective film,
501… First laminated composite sheet, 502... Second laminated composite sheet, 503... third laminated composite sheet,
601… First laminated film, 602... Second laminated film, 603... third laminated film,
8… Dicing sheet, 9… Wafer, 9b… The back side of the wafer, 90… Chip, 90b… The other side of the chip, 901... Chip with protective film

Claims (5)

As an energy ray curable protective film forming film,
A protective film forming film having a change rate of 60% or more in the indentation depth as measured by the following method for measuring the change rate of the indentation depth of the protective film forming film:
＜Method for measuring the rate of change of indentation depth＞
The protective film-forming film is irradiated with ultraviolet rays with a wavelength of 365 nm under conditions of an illumination intensity of 220 mW/cm2 and a light quantity of 500 mJ/cm2 to produce a cured protective film-forming film;
For the protective film forming film before and after curing, the indentation depth (μm) is measured using an ultra-micro hardness meter under the following conditions;
Indenter: Triangular pyramid, tip curvature radius less than 0.1㎛
Measurement mode: load-unload test
Maximum load: 10mN
Hold time when reaching maximum load: 5 seconds
Load speed: 0.14mN/sec
Temperature: 23℃
Next, the difference between the indentation depth of the protective film-forming film after curing and the indentation depth of the protective film-forming film before curing is calculated by the following formula (1), and this is taken as the rate of change of the indentation depth of the protective film-forming film;
Rate of change in indentation depth [%] = {(Indentation depth of the protective film-forming film before curing - Indentation depth of the protective film-forming film after curing)/Indentation depth of the protective film-forming film before curing｝×100... (One). According to claim 1,
A protective film-forming film, wherein the protective film-forming film contains an acrylic resin (b) that does not have an energy ray-curable group, and the acrylic resin (b) has a structural unit derived from 4-(meth)acryloylmorpholine. A composite sheet for forming a protective film comprising a support sheet and a protective film forming film formed on one side of the support sheet,
A composite sheet for forming a protective film, wherein the protective film forming film is the protective film forming film of claim 1 or 2. A kit comprising a first laminate in which a first release film and a protective film-forming film are laminated in this order, a work to which the protective film-forming film is attached, and a support sheet used to support the protective film-forming film,
A kit wherein the protective film forming film is the protective film forming film of claim 1 or 2. Use of a protective film forming film to form a protective film on a surface opposite to the circuit surface of a semiconductor wafer or semiconductor chip,
Use of a protective film forming film, wherein the protective film forming film is the protective film forming film of claim 1 or 2.

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