KR20220133785A - Protective membrane forming film - Google Patents

Abstract

The present invention relates to a film for forming a protective film. In the film for forming a protective film, in coordinates defined by a CIE1976L^*a^*b^* color system, when a color of a printing part has lightness L^*_p, chromaticity a^*_p, and chromaticity b^*_p and in the coordinates defined by the CIE1976L^*a^*b^* color system, when a color of a non-printing part has lightness L^*_N, chromaticity a^*_N, and chromaticity b^*_N, a color difference ΔE^*_(ab) between the printing part and the non-printing part is 8 or more. Therefore, in case of hardening of the film for forming a protective film or in a reflow process, even when a line width of printing is narrow, the film for forming a protective film from which sufficient printing visibility is obtained can be provided.

Description

Film for forming a protective film {PROTECTIVE MEMBRANE FORMING FILM}

The present invention relates to a film for forming a protective film that is affixed on the back surface of a semiconductor wafer or a semiconductor chip and used to form a protective film, and a sheet for forming a protective film comprising the same.

In recent years, manufacturing a semiconductor device by the mounting method called a face-down system is implemented. In this method, when a semiconductor chip having a circuit surface on which electrodes such as bumps are formed is mounted, the circuit surface side of the semiconductor chip is joined to a chip mounting portion such as a lead frame. Therefore, it becomes a structure in which the back surface side of the semiconductor chip in which the circuit is not formed is exposed.

For this reason, in order to protect a semiconductor chip, the protective film which consists of a hard organic material is formed in the back surface side of a semiconductor chip in many cases. This protective film is formed using the film for semiconductor back surface or a dicing tape integrated wafer back surface protective film as disclosed in patent document 1, for example.

The protective film may also be used as a member for information display of a workpiece (eg, a semiconductor wafer) or a workpiece (eg, a semiconductor chip) provided with the protective film. That is, by forming irregularities and shading on the surface of the protective film, printing may be performed in which information about a workpiece or a workpiece can be displayed visually. This printing process is normally performed by irradiating a laser to the surface of a protective film. In the case of a semiconductor chip, attributes of the chip such as the manufacturer's name or logo, product name, part number, and standard of the chip are printed.

In this regard, in the film for semiconductor back surface in Patent Document 1, the light transmittance at a wavelength of 532 nm or 1064 nm is 20% or less. Thereby, while enabling the printing process by irradiation of a laser beam, the adverse effect by a laser beam on a semiconductor element is prevented. It is calculated|required to improve the visibility of information based on the unevenness|corrugation formed on the surface of a protective film by printing process (in this specification, it is also referred to as "printing visibility."). It is taught by patent document 2 that printing visibility improves by making the average particle diameter of the filler mix|blended with the film for protective film formation into 0.4 micrometer or less. However, in recent years, as size reduction of a semiconductor device progresses, the tendency for print visibility to fall has become remarkable.

Japanese Patent Laid-Open No. 2012-28396 International Publication No. WO2015/146936

The present inventors considered the fall factor of printing visibility.

Generally, the film for protective film formation contains thermosetting or energy-ray-curable resin, additives, such as a hardening|curing agent, a coloring agent, and a filler. Laser printing may be performed before hardening of the film for protective film formation, and laser printing may be performed with respect to the protective film of the hardening|curing agent obtained by hardening the film for protective film formation. Then, the printed information is sequentially checked, moved between each process, and finally transferred to the mounting process. At this time, if the print visibility is insufficient, the attributes of the chip may not be recognized or misunderstood, resulting in problems in movement between processes or in the mounting process.

In addition, the semiconductor chip having the protective film subjected to laser printing is exposed to the reflow step in the mounting step. The reflow process is a process for connecting the substrate and the semiconductor chip by melting the protruding solder formed on the substrate for mounting the chip or the protruding solder formed on the semiconductor chip. At this time, the semiconductor chip is heated to around 260°C. By the reflow process, a semiconductor chip is connected to a board|substrate and is commercialized. However, the visibility of printing may fall after a reflow process. The information printed on the chip is not only used in the assembly process of the semiconductor device, but also displays the quality of the semiconductor device, and also has a function of improving the designability. For this reason, also in a commercialized semiconductor device, it is calculated|required that printing visibility is maintained.

On the other hand, in semiconductor devices, miniaturization and high performance are constantly being demanded. As a result, the size of the semiconductor chip is being reduced in size to several millimeters in width and length, and by extension, to 1 mm or less in width and length. With miniaturization, the area in which laser printing can be performed is also narrowed, and printing is also reduced, and the line width of characters and graphics to be printed may be 30 mu m or less.

As a result of this fact, the present inventors have narrowed the line|wire width of printing, The heating at the time of hardening the film for protective film formation, or heating at the time of reflow, the line|wire width further narrows, The possibility that printing visibility is brought about I was crazy about thinking. When hardening the film for protective film formation, since the resin component contained in the film for protective film formation temporarily raises fluidity|liquidity, there exists a possibility of narrowing the line|wire width of a laser printing part. Moreover, even if it is a protective film after hardening, when it exposes to high temperature of about 260 degreeC, it is thought that a protective film will soften partially, and a laser printing part will deform|transform, and the fall of printing visibility will be caused.

Therefore, an object of this invention is to provide the film for protective film formation from which sufficient printing visibility is obtained even when the line|wire width of printing is narrow.

As a result of intensive studies to solve the above problems, the present inventors have found that sufficient printing visibility is obtained even when the line width of printing becomes narrow by making the color difference between the printing part and the non-printing part more than a predetermined value, and completing the present invention. reached That is, the summary of this invention which solves the said subject is as follows.

(1) A film for forming a protective film that is laser-printed on the surface,

In the coordinates specified by the CIE1976L ^* a ^* b ^* color space system, the color of the printing part is set to lightness L ^* _p , chromaticity a ^* _p , and chromaticity b ^* _p , and at the coordinates specified by the CIE1976L ^* a ^* b ^* color space system , when the color of the non-printing part is lightness L ^* _N , chromaticity a ^* _N , and chromaticity b ^* _N ,

The film for protective film formation whose color difference (DELTA)E ^* _ab of the printing part and the non-printing part defined by following formula (A) is 8 or more.

ΔE ^* _ab = [(L ^* _p - L ^* _N ) ² + (a ^* _p - a ^* _N ) ² + (b ^* _p - b ^* _N ) ² ] ^1/2 … (A)

(2) The film for protective film formation as described in (1) whose brightness difference (DELTA)L ^* of the printing part and the non-printing part defined by following formula (B) is 8 or more.

ΔL ^* = [(L ^* _p - L ^* _N ) ² ] ^1/2 … (B)

(3) The film for protective film formation as described in (1) or (2) with which the brightness L ^* _p of the said printing part and the brightness L ^* _N of a non-printing part satisfy|fill L ^* _p >L ^* _N .

(4) The color of the said printing part and the color of the non-printing part are the protective film formation film in any one of the indexes (1)-(3) measured after laser printing, after heating and hardening the film for protective film formation at 130 degreeC .

(5) The color of the printing part and the color of the non-printing part are the indexes measured after laser printing, curing the protective film forming film by heating at 180° C., and further heating at 260° C. for 10.8 minutes three times ( 1) The film for protective film formation in any one of (3).

(6) The film for protective film formation in any one of (1)-(5) in which the said printing part contains the part of 50 micrometers or less of line|wire width.

(7) the film for forming a protective film according to any one of (1) to (6);

A sheet for forming a protective film comprising a supporting sheet.

ADVANTAGE OF THE INVENTION According to this invention, at the time of hardening of the film for protective film formation, or a reflow process. WHEREIN: Even when the line|wire width of printing is narrow, the film for protective film formation from which sufficient printing visibility is obtained can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
It is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
3 : is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
4 : is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
5 : is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
6 : is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
7 : is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
8 : is a schematic diagram which shows an example of the protective film formation sheet which concerns on this embodiment.
It is a schematic diagram which shows an example of the manufacturing process of the protective film formation sheet which concerns on this embodiment.

Film for forming a protective film

The film for forming a protective film is a curable film used to form a protective film on a workpiece such as a semiconductor wafer or a workpiece obtained by processing the workpiece (eg, a semiconductor chip).

The film for protective film formation which concerns on this embodiment is finally affixed to workpiece|works, such as a semiconductor chip, and is used as a protective film by which laser printing was carried out on the surface. The surface of the film for protective film formation of this embodiment changes in quality by irradiation of a laser beam, and has the printing part in which characters, a figure, etc. were formed, and the non-printing part to which the laser beam is not irradiated.

In the film for forming a protective film according to the present embodiment, in the coordinates defined by the CIE1976L ^* a ^* b ^* color space system, the color of the printing part is the brightness L ^* _p , the chromaticity a ^* _p , the chromaticity b ^* _p , and CIE1976L ^* In the coordinates stipulated by the a ^* b ^* color space system, when the color of the non-printing part is lightness L ^* _N , chromaticity a ^* _N , and chromaticity b ^* _N , the color difference ΔE ^* _ab between the printing part and the non-printing part is 8 or more, , preferably 10 or more, more preferably 15 or more. The upper limit of the color difference ΔE ^* _ab is not particularly limited, but considering designability, it is preferably 120 or less, more preferably 90 or less, and more preferably 80 or less. If the color difference ΔE ^* _ab is 8 or more, printing visibility is maintained even when exposed to heating for curing or reflow of the film for forming a protective film in a narrow printing width.

In addition, the color difference ΔE ^* _ab is defined by the following formula (A).

ΔE ^* _ab = [(L ^* _p - L ^* _N ) ² + (a ^* _p - a ^* _N ) ² + (b ^* _p - b ^* _N ) ² ] ^1/2 … (A)

The film for protective film formation which concerns on this embodiment WHEREIN: It is preferable that it is 8 or more, and, as for the brightness difference (DELTA)L ^* of a printing part and a non-printing part, it is more preferable that it is 10 or more. Although the upper limit of the brightness difference ΔL ^* is not particularly limited, when designability is considered, it is preferably 85 or less, more preferably 70 or less, and more preferably 60 or less. If the brightness difference ΔL ^* is 8 or more, printing visibility is maintained even when exposed to heating for curing or reflow of the film for forming a protective film in a narrow printing width.

In addition, the brightness difference ΔL ^* is defined by the following formula (B).

ΔL ^* = [(L ^* _p - L ^* _N ) ² ] ^1/2 … (B)

The film for protective film formation which concerns on this embodiment WHEREIN: It is more preferable that the brightness L ^* _p of a printing part and the brightness L ^* _N of a non-printing part satisfy|fill L ^* _p >L ^* _N , L ^* _p >1.5*L ^* More preferably _N. That is, when the brightness L ^* _p of the printing part is higher than the brightness L ^* _N of the non-printing part, the printing appears as if it is floating on a dark background, so that the printing visibility is excellent.

It is sufficient that the color difference ΔE ^* _ab in the present embodiment is within the above range immediately after laser printing, but preferably, it is within the above range in all steps after laser printing. The same is true for the lightness difference ΔL ^* .

When laser printing is performed on an uncured film for forming a protective film, the color difference ΔE is in an uncured state, in a state in which the protective film is cured to form a protective film, and in a state after exposing the chip on which the protective film is formed to reflow conditions. It is preferable that ^* _ab and the lightness difference ΔL ^* are in the above range. In addition, when the protective film is subjected to laser printing after curing the film for forming a protective film to form a protective film, the color difference ΔE ^* _ab and It is preferable that the lightness difference ΔL ^* is in the above range.

The film for protective film formation may be either thermosetting or energy-beam sclerosis|hardenability. When the film for protective film formation is thermosetting, thermosetting conditions vary. In the present embodiment, when evaluating the color difference ΔE ^* _ab and the lightness difference ΔL ^* in a state in which the film for forming a protective film is cured to form a protective film, the protective film for forming a protective film is heated and cured at 180° C. for a sufficient time. color difference ΔE ^* _ab and lightness difference ΔL ^* are evaluated for

When a chip having a protective film is mounted on a substrate, solder is melted in a reflow step to connect the chip and the substrate. The heating conditions in the reflow process are not specifically limited. In the present embodiment, when evaluating the color difference ΔE ^* _ab and the lightness difference ΔL ^* in the state after exposure to reflow conditions, heating for 10.8 minutes at 260° C. The color difference ΔE ^* _ab and the lightness difference ΔL ^* are evaluated for the protective film after performing 3 times.

ADVANTAGE OF THE INVENTION According to this invention, even when the line|wire width of printing is narrow, sufficient printing visibility is acquired at the time of hardening of the film for protective film formation, or even after going through a reflow process. When the line width of printing is narrow, in the case of hardening of the film for protective film formation or a reflow process. WHEREIN: In particular, the printing part with a narrow line width narrows further, and printing visibility falls. However, according to the film for forming a protective film of the present embodiment, since there is a sufficient color difference between the printing portion and the non-printing portion, sufficient printing visibility is obtained even after the film for protective film formation is cured or the line width of the printing becomes narrow after the reflow step. lose Therefore, the film for protective film formation which concerns on this embodiment is used especially preferably, when a printing part has a part 50 micrometers or less in width.

The film for protective film formation which concerns on this embodiment may have a peeling film in one surface, and may have a peeling film in both surfaces. When it has a peeling film in both surfaces, the peeling film may be the same in both surfaces, and may differ. The film for protective film formation which concerns on this embodiment can provide as a long film wound in roll shape by having a peeling film. Although it does not specifically limit as a peeling film, The thing similar to the peeling film used for the sheet|seat for protective film formation mentioned later can be used.

The film for protective film formation which concerns on this embodiment is hardened|cured and turns into a protective film. This protective film is for protecting the back surface (surface opposite to the electrode formation surface) of a semiconductor wafer or a semiconductor chip. The film for protective film formation is soft and can be affixed to a sticking object easily.

Below, a non-limiting example is shown about the material and manufacturing method of the film for protective film formation which concern on this embodiment.

The film for forming a protective film may be any of thermosetting and energy ray curability, as long as the color difference ΔE ^* _ab of the printed portion and the non-printed portion satisfies the above in the coordinates specified by the CIE1976L ^* a ^* b ^* color space system. The film for protective film formation finally becomes a protective film with high impact resistance through hardening. According to this protective film, generation|occurrence|production of the crack in the semiconductor chip after a dicing process can be prevented, for example, and the semiconductor chip with a protective film in the state accommodated in the carrier tape can be detected favorably.

The film for forming a protective film is formed using a composition for a film for forming a thermosetting protective film or a composition for a film for forming an energy ray-curable protective film (hereinafter, collectively referred to as “composition for film for forming a protective film”), which will be described later. can do.

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

Although the thickness of the film for protective film formation is not specifically limited, It is preferable that it is 1-100 micrometers, It is more preferable that it is 5-75 micrometers, It is especially preferable that it is 5-50 micrometers. When the thickness of the film for protective film formation is more than the said lower limit, when irradiating a laser with respect to a protective film or the film for protective film formation and performing laser printing, the prevention effect of the damage of the semiconductor wafer accompanying laser penetration becomes high. Moreover, the protective ability of a protective film improves. On the other hand, when the thickness of the film for protective film formation is below the said upper limit, the grade of the shrinkage at the time of hardening of the said film reduces, and the effect which reduces the curvature of the semiconductor chip with a protective film becomes high. Moreover, at the time of a temperature cycle test, generation|occurrence|production of the stress resulting from the difference of the linear expansion coefficient of a protective film and a semiconductor wafer is suppressed, and the effect which suppresses peeling of a protective film from a semiconductor wafer becomes high.

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

Hereinafter, when the film for forming a protective film according to the present embodiment is a film for forming a thermosetting protective film formed from a film composition for forming a thermosetting protective film, and a film for forming an energy ray-curable protective film formed from a film composition for forming an energy ray-curable protective film case is explained.

· Film for forming a thermosetting protective film

As a film for thermosetting protective film formation, the thing containing the polymer component (A) and thermosetting component (B) mentioned later is mentioned, for example. The polymer component (A) is a component that can be regarded as formed by a polymerization reaction of a polymerizable compound. Moreover, a thermosetting component (B) makes heat|fever as a trigger of reaction, and is a component which can harden (polymerize) and react. In addition, in this invention, a polycondensation reaction is also contained in a polymerization reaction.

<<The composition for films for forming a thermosetting protective film>>

The film for thermosetting protective film formation can be formed from the composition for films for thermosetting protective film formation containing the constituent material. For example, the film for thermosetting protective film formation can be formed in the target site|part by coating the composition for films for thermosetting protective film formation on the formation target surface of the film for thermosetting protective film formation, and drying as needed. The ratio of content of components which do not vaporize at normal temperature in the composition for films for thermosetting protective film formation becomes the same as the ratio of content of the said components of the film for thermosetting protective film formation normally.

In addition, in this specification, "normal temperature" means the temperature which does not cool or heat in particular, ie, normal temperature, For example, the temperature of 15-25 degreeC etc. are mentioned.

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

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

<Composition (1) for films for forming a protective film>

As a composition for films for thermosetting protective film formation, for example, the composition (1) for films for thermosetting protective film formation containing a polymer component (A) and a thermosetting component (B) (in this specification, "for film for protective film formation) composition (1)"), etc. are mentioned.

[Polymer component (A)]

A polymer component (A) is a polymer compound for providing film formability, flexibility, etc. to the film for thermosetting protective film formation.

The composition (1) for the film for forming a protective film and the polymer component (A) contained in the film for forming a thermosetting protective film may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. have.

As the polymer component (A), for example, an acrylic resin (for example, a resin having a (meth)acryloyl group), polyester, a urethane-based resin (for example, a resin having a urethane bond), an acrylic urethane resin, silicone-based resins (eg, resins having a siloxane bond), rubber-based resins (eg, resins having a rubber structure), phenoxy resins, and thermosetting polyimides, and acrylic resins are preferable.

As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.

It is preferable that it is 10000-200000, and, as for the weight average molecular weight (Mw) of acrylic resin, it is more preferable that it is 100000-1500000. When the weight average molecular weight of acrylic resin is more than the said lower limit, shape stability (time-dependent stability at the time of storage) of the film for thermosetting protective film formation improves. In addition, when the weight average molecular weight of the acrylic resin is below the upper limit, the film for forming a thermosetting protective film tends to follow the uneven surface of the adherend, and the occurrence of voids between the adherend and the film for forming a thermosetting protective film is more suppressed. .

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

It is preferable that it is -60-70 degreeC, and, as for the glass transition temperature (Tg) of acrylic resin, it is more preferable that it is -30-50 degreeC. When Tg of acrylic resin is more than the said lower limit, the adhesive force of a protective film and a support sheet is suppressed, and the peelability of a support sheet improves. Moreover, when Tg of acrylic resin is below the said upper limit, the adhesive force with the to-be-adhered body of the film for thermosetting protective film formation and a protective film improves.

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

As acrylic resin, For example, the polymer of 1 type or 2 or more types of (meth)acrylic acid ester; (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, a copolymer of at least 2 types of monomers selected from N-methylolacrylamide, etc. are mentioned.

As the (meth)acrylic acid ester constituting the acrylic resin, for example, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid isopropyl, (meth)acrylic acid n -Butyl, (meth) acrylate isobutyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylic acid 2- Ethylhexyl, (meth)acrylic acid isooctyl, (meth)acrylic acid n-octyl, (meth)acrylic acid n-nonyl, (meth)acrylic acid isononyl, (meth)acrylic acid decyl, (meth)acrylic acid undecyl, (meth) Dodecyl acrylate (also called (meth)acrylic acid lauryl), (meth)acrylic acid tridecyl, (meth)acrylic acid tetradecyl ((meth)acrylic acid myristyl), (meth)acrylic acid pentadecyl, (meth)acrylic acid hexadecyl An alkyl group constituting an alkyl ester, such as decyl (also called palmityl (meth)acrylate), heptadecyl (meth)acrylate, or octadecyl (meth)acrylate (also called stearyl (meth)acrylate), has 1 to (meth)acrylic acid alkylester having a chain structure of 18;

(meth)acrylic acid cycloalkyl esters, such as (meth)acrylic-acid isobornyl and (meth)acrylic-acid dicyclopentanyl;

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

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

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

(meth)acrylic acid imide;

glycidyl group-containing (meth)acrylic acid esters such as (meth)acrylic acid glycidyl;

(meth) acrylic acid hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters, such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylic acid;

Substituted amino group containing (meth)acrylic acid ester, such as (meth)acrylic-acid N-methylaminoethyl, etc. are mentioned. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

Among the above, n-butyl acrylate, methyl acrylate, glycidyl methacrylate, and 2-hydroxyethyl acrylate are preferable.

The acrylic resin is, for example, in addition to the (meth)acrylic acid ester, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. 1 type or 2 or more types selected What is formed by copolymerizing a monomer may be sufficient.

The number of monomers constituting the acrylic resin may be one, two or more, and in the case of two or more, their combination and ratio can be arbitrarily selected.

Acrylic resin may have a functional group which can couple|bond with other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, and an isocyanate group. The said functional group of acrylic resin may couple|bond with another compound through the crosslinking agent (F) mentioned later, and may couple|bond with another compound directly without passing through a crosslinking agent (F). When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the sheet for forming a protective film tends to be improved.

In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter, it may be simply abbreviated as “thermoplastic resin”) may be used in combination with the acrylic resin.

By using the above-mentioned thermoplastic resin, the peelability of the protective film from the supporting sheet is improved, the film for forming a thermosetting protective film tends to follow the uneven surface of the adherend, and voids or the like are generated between the adherend and the film for forming a thermosetting protective film. In some cases, this is more suppressed.

It is preferable that it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

It is preferable that it is -30-150 degreeC, and, as for the glass transition temperature (Tg) of the said thermoplastic resin, it is more preferable that it is -20-120 degreeC.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

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

The content of the polymer component (A) is, irrespective of the type of the polymer component (A), with respect to the total mass of all components other than the solvent constituting the composition (1) for the film for forming a protective film (that is, the film for forming a thermosetting protective film). with respect to the total mass of ), preferably 5 to 50 mass%, more preferably 10 to 40 mass%, particularly preferably 15 to 35 mass%.

A polymer component (A) may correspond also to a thermosetting component (B). In the present invention, when the composition (1) for films for forming a protective film contains a component corresponding to both such a polymer component (A) and a thermosetting component (B), the composition (1) for films for forming a protective film is , a polymer component (A) and a thermosetting component (B).

[thermosetting component (B)]

A thermosetting component (B) is a component for hardening the film for thermosetting protective film formation, and forming a hard protective film.

The composition (1) for the film for forming a protective film and the thermosetting component (B) contained in the film for forming a thermosetting protective film may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. have.

As a thermosetting component (B), an epoxy type thermosetting resin, a thermosetting polyimide, a polyurethane, unsaturated polyester, a silicone resin etc. are mentioned, for example, An epoxy type thermosetting resin is preferable.

(epoxy thermosetting resin)

An epoxy-type thermosetting resin consists of an epoxy resin (B1) and a thermosetting agent (B2).

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

・Epoxy resin (B1)

As an epoxy resin (B1), a well-known thing is mentioned, For example, polyfunctional type epoxy resin, a biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated substance, orthocresol novolak epoxy resin, dicyclopenta Bifunctional or more than bifunctional epoxy compounds, such as a diene type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type|mold epoxy resin, a bisphenol F type|mold epoxy resin, and a phenylene skeleton type|mold epoxy resin, are mentioned.

Among the above, a bisphenol A epoxy resin, a dicyclopentadiene epoxy resin, etc. are preferable.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. The epoxy resin which has an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than the epoxy resin which does not have an unsaturated hydrocarbon group. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the sheet|seat for protective film formation improves.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound formed by conversion into the group which has an unsaturated hydrocarbon group in part of the epoxy group of a polyfunctional epoxy resin is mentioned, for example. Such a compound is obtained, for example by making an epoxy group addition-react (meth)acrylic acid or its derivative(s).

In the present specification, "derivative" means that at least one hydrogen atom of the original compound is substituted with a group (substituent) other than a hydrogen atom.

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

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

Although the number average molecular weight of the epoxy resin (B1) is not particularly limited, from the viewpoint of the curability of the film for forming a thermosetting protective film and the strength and heat resistance of the protective film after curing, it is preferably 300 to 30000, more preferably 300 to 10000 It is preferable, and it is especially preferable that it is 300-3000.

In the present specification, "number average molecular weight" means a number average molecular weight expressed by a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method, unless otherwise specified.

It is preferable that it is 100-1100 g/eq, and, as for the epoxy equivalent of an epoxy resin (B1), it is more preferable that it is 150-1000 g/eq.

In this specification, "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing an epoxy group of 1 gram equivalent, and can be measured according to the method of JISK7236:2001.

An epoxy resin (B1) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combination and a ratio can be selected arbitrarily.

· Thermosetting agent (B2)

The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

As a thermosetting agent (B2), the compound which has at least 2 functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group in which an acid group is anhydride, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydrized is preferable, and phenol It is more preferable that they are a sexual hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak phenol resins, dicyclopentadiene phenol resins, aralkylphenol resins, and the like. can be heard

Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.

As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin and the like.

The said unsaturated hydrocarbon group in a thermosetting agent (B2) is the same thing as the unsaturated hydrocarbon group in the epoxy resin which has the above-mentioned unsaturated hydrocarbon group.

When using a phenol-type hardening|curing agent as a thermosetting agent (B2), it is preferable that the softening point or glass transition temperature of a thermosetting agent (B2) is high at the point which the peelability of a protective film from the support sheet improves.

The thermosetting agent (B2) is solid at room temperature, and does not exhibit curing activity with respect to the epoxy resin (B1), on the other hand, is dissolved by heating, and a thermosetting agent showing curing activity with respect to the epoxy resin (B1) ( Hereinafter, it may be abbreviated as "thermal active latent epoxy resin curing agent").

In addition, in this specification, "normal temperature" means the temperature which does not cool or heat in particular, ie, normal temperature, For example, the temperature of 15-25 degreeC etc. are mentioned.

The thermally active latent epoxy resin curing agent is stably dispersed in the epoxy resin (B1) in the film for forming a thermosetting protective film at room temperature, but is compatible with the epoxy resin (B1) by heating, and the epoxy resin (B1) react By using the said thermally active latent epoxy resin hardening|curing agent, the storage stability of the sheet|seat for protective film formation improves remarkably. For example, the movement of this hardening|curing agent from the film for protective film formation to the adjacent support sheet is suppressed, and the thermosetting fall of the film for thermosetting protective film formation is suppressed effectively. And since the thermosetting degree by heating of the film for thermosetting protective film formation becomes higher, the pick-up property of the semiconductor chip with a protective film mentioned later improves more.

As said thermally active latent epoxy resin hardening|curing agent, an onium salt, dibasic acid hydrazide, dicyandiamide, the amine adduct of a hardening|curing agent, etc. are mentioned, for example.

Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resins, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins is preferably 300 to 30000. And, it is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Although the molecular weight of non-resin components, such as a biphenol and dicyandiamide, is not specifically limited among thermosetting agents (B2), For example, it is preferable that it is 60-500.

A thermosetting agent (B2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combination and a ratio can be selected arbitrarily.

In the composition (1) for films for forming a protective film and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (B1), 1 It is more preferable that it is -200 mass parts. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of the film for thermosetting protective film formation advances more easily. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption of the film for thermosetting protective film formation is reduced, and the reliability of the package obtained using the sheet|seat for protective film formation improves more.

In the composition (1) for films for forming a protective film and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is a polymer component ( It is preferable that it is 1-100 mass parts with respect to 100 mass parts of content of A), It is more preferable that it is 1.5-85 mass parts, It is especially preferable that it is 2-70 mass parts. When the said content of a thermosetting component (B) is such a range, the adhesive force of a protective film and a support sheet is suppressed, and the peelability of a support sheet improves.

As another aspect, in the composition (1) for a film for forming a protective film and the film for forming a thermosetting protective film, the content of the thermosetting component (B) is the total mass of all components other than the solvent of the composition (1) for the film for forming a protective film. With respect to (that is, with respect to the gross mass of the film for thermosetting protective film formation), 1-90 mass % is preferable, 10-80 mass % is more preferable, 30-70 mass % is still more preferable.

[curing accelerator (C)]

The composition (1) for films for protective film formation and the film for thermosetting protective film formation may contain the hardening accelerator (C). A hardening accelerator (C) is a component for adjusting the cure rate of the composition (1) for films for protective film formation.

As a preferable hardening accelerator (C), For example, tertiary amines, such as triethylenediamine, benzyl dimethylamine, a triethanolamine, dimethylamino ethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 imidazoles such as -hydroxymethylimidazole (imidazole in which at least one hydrogen atom is substituted with a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine (phosphine in which at least one hydrogen atom is substituted with an organic group); Tetraphenyl boron salts, such as a tetraphenyl phosphonium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. are mentioned.

Among the above, 2-phenyl-4,5-dihydroxymethylimidazole is preferable.

The composition (1) for the film for forming a protective film and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. have.

When a curing accelerator (C) is used, in the composition (1) for films for forming a protective film and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is 100 parts by mass of the content of the thermosetting component (B), It is preferable that it is 0.01-10 mass parts, and it is more preferable that it is 0.1-5 mass parts. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) is acquired more notably. Moreover, when the content of the curing accelerator (C) is below the upper limit, for example, the highly polar curing accelerator (C) moves to the adhesive interface side with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of suppressing segregation by doing this increases, and the reliability of the package obtained using the sheet|seat for protective film formation improves more.

[Filling material (D)]

The composition (1) for films for protective film formation and the film for thermosetting protective film formation may contain the filler (D). When the film for forming a thermosetting protective film contains the filler (D), the protective film obtained by curing the film for forming a thermosetting protective film is easy to adjust the coefficient of thermal expansion, and by optimizing this coefficient of thermal expansion for the object to be formed of the protective film, The reliability of the package obtained by using the sheet is further improved. Moreover, when the film for thermosetting protective film formation contains a filler (D), the moisture absorption of a protective film can be reduced, or heat dissipation can also be improved.

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

As a preferable inorganic filler, For example, powders, such as a silica, alumina, a talc, a calcium carbonate, a titanium white, bengala, a silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; Surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned. Among these, the inorganic filler is preferably silica or alumina.

It is preferable that the average particle diameter of a filler (D) shall be 0.1-10 micrometers. By making the particle diameter of a filler (D) into the said range, the smoothness of the film for protective film formation can be maintained and filling property can also be improved.

The composition (1) for the film for forming a protective film and the filler (D) which the film for forming a thermosetting protective film contains may be one type, or two or more types, and in the case of two or more types, their combination and ratio can be arbitrarily selected. .

When a filler (D) is used, in the composition (1) for a film for forming a protective film, the content of the filler (D) with respect to the total content (total mass) of all components other than the solvent (that is, of the film for forming a thermosetting protective film It is preferable that it is 5-80 mass %, and, as for content of a filler (D), it is more preferable that it is 7-60 mass %. When content of a filler (D) is such a range, adjustment of the said thermal expansion coefficient becomes easier.

[Coupling agent (E)]

The composition (1) for films for protective film formation and the film for thermosetting protective film formation may contain the coupling agent (E). By using as a coupling agent (E) what has a functional group which can react with an inorganic compound or an organic compound, the adhesiveness and adhesiveness with respect to the to-be-adhered body of the film for thermosetting protective film formation can be improved. Moreover, water resistance improves the protective film obtained by hardening|curing the film for thermosetting protective film formation by using a coupling agent (E), without inhibiting heat resistance.

It is preferable that it is a compound which has a functional group which can react with the functional group which a polymer component (A), a thermosetting component (B), etc. have, and, as for a coupling agent (E), it is more preferable that it is a silane coupling agent.

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

The composition (1) for the film for forming a protective film and the coupling agent (E) contained in the film for forming a thermosetting protective film may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. have.

When using a coupling agent (E), the composition (1) for films for protective film formation, and the film for thermosetting protective film formation WHEREIN: Content of a coupling agent (E) is the total of a polymer component (A) and a thermosetting component (B). It is preferable that it is 0.03-20 mass parts with respect to content 100 mass parts, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.1-5 mass parts. When the content of the coupling agent (E) is equal to or higher than the lower limit, the improvement of the dispersibility of the filler (D) to the resin, the improvement of the adhesiveness of the film for forming a thermosetting protective film to the adherend, etc., using the coupling agent (E) The effect is obtained more conspicuously. Moreover, generation|occurrence|production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]

As the polymer component (A), when using a polymer component (A) having a functional group such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxy group, and isocyanate group capable of bonding to other compounds, such as the above-mentioned acrylic resin, a protective film is formed The composition (1) for films for use and the film for thermosetting protective film formation may contain the crosslinking agent (F) for bonding the said functional group with another compound further and making it bridge|crosslink. By crosslinking using a crosslinking agent (F), the initial adhesive force and cohesive force of the film for thermosetting protective film formation can be adjusted.

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

As said organic polyhydric isocyanate compound, For example, an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyhydric isocyanate compound (Hereinafter, these compounds may be abbreviated as "aromatic polyvalent isocyanate compound etc." together); a trimer, an isocyanurate body, and an adduct body, such as the said aromatic polyhydric isocyanate compound; The terminal isocyanate urethane prepolymer etc. which are obtained by making the said aromatic polyhydric isocyanate compound etc. react with a polyol compound are mentioned. The "adduct body" is the aromatic polyhydric isocyanate compound, aliphatic polyvalent isocyanate compound, or alicyclic polyvalent isocyanate compound, and low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reactant, and examples thereof include an adduct of xylylene diisocyanate of trimethylolpropane, which will be described later, and the like. In addition, "terminal isocyanate urethane prepolymer" means a prepolymer which has a urethane bond and an isocyanate group at the terminal part of a molecule|numerator.

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

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

When using an organic polyvalent isocyanate compound as a crosslinking agent (F), as a polymer component (A), it is preferable to use a hydroxyl-containing polymer. When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced into the film for forming a thermosetting protective film by reaction of the crosslinking agent (F) with the polymer component (A).

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

When a crosslinking agent (F) is used, in the composition (1) for films for forming a protective film, the content of the crosslinking agent (F) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the polymer component (A), , It is more preferable that it is 0.1-10 mass parts, and it is especially preferable that it is 0.5-5 mass parts. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is acquired more notably. In addition, when the content of the crosslinking agent (F) is below the upper limit, the adhesive force of the film for forming a thermosetting protective film and the support sheet and the adhesive force of the film for forming a thermosetting protective film with a semiconductor wafer or semiconductor chip are suppressed from excessively decreasing. do. In this invention, even if it does not use a crosslinking agent (F), the effect of this invention is fully acquired.

[Energy-ray-curable resin (G)]

The composition (1) for films for protective film formation may contain the energy-beam curable resin (G). Since the film for thermosetting protective film formation contains energy-beam curable resin (G), a characteristic can be changed by irradiation of an energy-beam.

Energy-beam curable resin (G) is obtained by superposing|polymerizing (hardening) an energy-beam curable compound.

As said energy-beam-curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, for example, The acrylate type compound which has a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di ( chain aliphatic skeleton-containing (meth)acrylates such as meth)acrylate; Cyclic aliphatic skeleton containing (meth)acrylates, such as dicyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylate; Urethane (meth)acrylate oligomer; epoxy-modified (meth)acrylate; Polyether (meth)acrylates other than the said polyalkylene glycol (meth)acrylate; Itaconic acid oligomer etc. are mentioned.

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said energy-beam curable compound, it is more preferable that it is 300-10000.

The number of the said energy-ray-curable compound used for superposition|polymerization may be one, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

The number of energy-beam curable resin (G) which the composition (1) for films for protective film formation contains may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

In the composition (1) for protective film formation, content of energy ray-curable resin (G) is 1-95 mass % with respect to the total mass of all components other than the solvent of the composition (1) for protective film formation It is preferable that it is 2-90 mass %, It is more preferable, It is especially preferable that it is 3-85 mass %.

[Photoinitiator (H)]

When the composition (1) for films for protective film formation contains energy-beam curable resin (G), in order to advance the polymerization reaction of energy-beam curable resin (G) efficiently, you may contain the photoinitiator (H). .

As a photoinitiator (H) in the composition (1) for films for protective film formation, the thing similar to the photoinitiator in the adhesive composition (i) mentioned later is mentioned.

The number of photoinitiators (H) which the composition (1) for films for protective film formation contains may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

Composition (1) for protective film formation WHEREIN: It is preferable that content of a photoinitiator (H) is 0.1-20 mass parts with respect to content 100 mass parts of energy-beam curable resin (G), It is 1-10 mass parts It is more preferable, and it is especially preferable that it is 2-5 mass parts.

[Colorant (I)]

The composition (1) for a film for forming a protective film is, in the coordinates defined by the CIE1976L ^* a ^* b ^* color space system, the color difference ΔE ^* _ab of the printed portion and the non-printed portion from the viewpoint of obtaining a film for forming a protective film that satisfies the above, It is preferable to contain a coloring agent (I).

The colorant (I) is not particularly limited as long as it is possible to obtain a film for forming a protective film in which the color difference ΔE ^* _ab of the printed portion and the non-printed portion in the coordinates specified by the CIE1976L ^* a ^* b ^* color space system can be obtained. Examples For example, well-known things, such as an inorganic type pigment, an organic type pigment, and organic type dye, can be used.

Examples of the organic pigments and organic dyes include aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squarylium pigments, azulenium pigments, polymethine pigments, and naphthoquinone pigments. Pigment, pyrylium pigment, phthalocyanine pigment, naphthalocyanine pigment, naphtholactam pigment, azo pigment, condensed azo pigment, indigo pigment, perinone pigment, perylene pigment, dioxazine pigment, quinacridone pigment , isoindolinone dye, quinophthalone dye, pyrrole dye, thioindigo dye, metal complex dye (metal complex dye), dithiol metal complex dye, indole phenol dye, triallylmethane dye, and anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazolone dyes, pyranthrone dyes and threne dyes.

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

One type may be sufficient as the coloring agent (I) which the composition (1) for films for protective film formation contains, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

The content of the colorant (I) in the film for forming a thermosetting protective film is a film for forming a protective film in which the color difference ΔE ^* _ab of the printed portion and the non-printed portion satisfies the above in the coordinates defined by the CIE1976L ^* a ^* b ^* color space system. Although it will not specifically limit as long as it can obtain, with respect to the total content (total mass) of all components other than a solvent, Preferably it is 0.2 mass % or more, More preferably, it is 0.5 mass % or more, More preferably, it is 1.5 mass %. More than that. Although the upper limit of content of the colorant (I) in the film for thermosetting protective film formation is not specifically limited, From a viewpoint of suppressing the excessive fall of the light transmittance of the film for thermosetting protective film formation, the total content of all components other than a solvent (total mass), Preferably it is 10 mass % or less, and can also be set as 5 mass % or less.

[Universal Additive (J)]

The composition (1) for films for protective film formation and the film for thermosetting protective film formation may contain the general-purpose additive (J) within the range which does not impair the effect of this invention.

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

The composition (1) for the film for forming a protective film and the general-purpose additive (J) contained in the film for forming a thermosetting protective film may be one type, two or more types, and when two or more types, combinations and ratios thereof can be arbitrarily selected. have.

Content of the composition (1) for films for protective film formation and the general-purpose additive (J) of the film for thermosetting protective film formation is not specifically limited, What is necessary is just to select suitably according to the objective.

[Solvent (K)]

It is preferable that the composition (1) for films for protective film formation contains a solvent (K) further. The composition (1) for films for protective film formation containing a solvent (K) becomes favorable in handleability.

Although the said solvent (K) is not specifically limited, As a preferable thing, For example, Hydrocarbons, such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; Ester, such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

One type may be sufficient as the solvent (K) which the composition (1) for films for protective film formation contains, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

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

The content of the solvent is preferably an amount in which the solid content concentration of the composition for a protective film formation is 10-80 mass%, and 20 to 70 mass% with respect to the total mass of the composition for a film for forming a protective film. It is more preferable, and it is still more preferable that it is the quantity used as 30-65 mass %.

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

The composition for films for thermosetting protective film formation as the composition (1) for films for protective film formation is obtained by mix|blending each component for comprising this.

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

When using a solvent, you may use by mixing a solvent with any compounding component other than a solvent and diluting this compounding component beforehand, without diluting any compounding component other than a solvent beforehand, a solvent is mixed with these compounding components. You may use by mixing.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; How to mix using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not specifically limited as long as each compounding component does not deteriorate, What is necessary is just to adjust suitably, It is preferable that the temperature is 15-30 degreeC.

Film for forming energy ray-curable protective film

The film for energy ray-curable protective film formation contains an energy-beam sclerosing|hardenable component (a).

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

In addition, in this specification, an "energy beam" means having an energy proton in an electromagnetic wave or a charged particle beam, and an ultraviolet-ray, an electron beam, etc. are mentioned as an example. Ultraviolet rays can be irradiated by using a high pressure mercury lamp, a fusion lamp, a xenon lamp, etc. as an ultraviolet source, for example. The electron beam can irradiate what was generated by an electron beam accelerator etc.

In addition, in this specification, "energy-beam sclerosis|hardenability" means the property hardened|cured by irradiating an energy beam, and "non-energy-beam sclerosis|hardenability" means the property which does not harden even if it irradiates an energy beam.

<<The composition for films for forming an energy ray-curable protective film>>

The film for energy ray-curable protective film formation can be formed from the composition for films for energy ray-curable protective film formation containing the constituent material. For example, by coating a composition for a film for forming an energy ray-curable protective film on the formation target surface of the film for forming an energy ray-curable protective film, and drying as necessary, a film for forming an energy ray-curable protective film is formed on the target site. can The ratio of content of the components which are not vaporized at normal temperature in the composition for films for energy ray-curable protective film formation becomes the same as the ratio of content of the said components of the film for energy-beam curable protective film formation normally. Here, "room temperature" is the same as described above.

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

The drying conditions of the composition for a film for forming an energy ray-curable protective film are not particularly limited, but the composition for a film for forming an energy ray-curable protective film is preferably heat-dried when it contains a solvent to be described later, in this case, yes For example, it is preferable to dry under the conditions for 10 second - 5 minutes at 70-130 degreeC.

<Composition (2) for films for forming a protective film>

As a composition for films for energy ray-curable protective film formation, for example, the composition (2) for films for energy ray-curable protective film formation containing the following energy ray-curable component (a) (in this specification, simply "for protective film formation) It may be abbreviated as "composition for films (2)"), etc. are mentioned.

[Energy-ray-curable component (a)]

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

As the energy ray curable component (a), for example, a polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80000 to 2000000, and a compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80000 can be heard As for the said polymer (a1), the thing which is not bridge|crosslinked may be sufficient as that at least one part was bridge|crosslinked with a crosslinking agent.

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

Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80000 to 2000000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of other compounds, a group reactive with the functional group, and energy and an acrylic resin (a1-1) formed by addition reaction of an energy ray-curable compound (a12) having an energy ray-curable group such as a ray-curable double bond.

The functional group capable of reacting with the group of another compound in the acrylic polymer (a11) is, for example, a hydroxyl group, a carboxy group, an amino group, or a substituted amino group (one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms) group), an epoxy group, and the like. However, it is preferable that the said functional group is groups other than a carboxy group from the point of preventing corrosion of circuits, such as a semiconductor wafer and a semiconductor chip.

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

- Acrylic polymer having a functional group (a11)

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

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

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

As said hydroxyl-containing monomer, For example, (meth)acrylic acid hydroxymethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, ( (meth)acrylic acid hydroxyalkyl, such as 2-hydroxybutyl meth)acrylic acid, 3-hydroxybutyl (meth)acrylic acid, and 4-hydroxybutyl (meth)acrylic acid; and non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (that is, unsaturated alcohol having no (meth)acryloyl skeleton) and the like.

As said carboxyl group-containing monomer, For example, ethylenically unsaturated monocarboxylic acids, such as (meth)acrylic acid and a crotonic acid (namely, monocarboxylic acid which has an ethylenically unsaturated bond); ethylenically unsaturated dicarboxylic acids (ie, dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydride of the said ethylenically unsaturated dicarboxylic acid; (meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

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

In addition, in this specification, let "(meth)acrylic acid" be a concept including both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acrylate" is a concept including both "acrylate" and "methacrylate", and "(meth)acryloyl group" "" is a concept including both "acryloyl group" and "methacryloyl group".

The number of the acryl-type monomers which comprise the said acrylic polymer (a11) and which has the said functional group may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and ratio can be selected arbitrarily.

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

Moreover, as an acryl-type monomer which does not have the said functional group, For example, alkoxy, such as (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl, (meth)acrylate ethoxyethyl, Alkyl group containing (meth)acrylic acid ester; (meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as (meth)acrylic acid phenyl; Non-crosslinkable (meth)acrylamide and its derivative(s); (meth)acrylic acid ester etc. which have non-crosslinkable tertiary amino groups, such as (meth)acrylic-acid N,N- dimethylaminoethyl, and (meth)acrylic-acid N,N- dimethylaminopropyl, etc. are mentioned.

The number of the acrylic monomers which do not have the said functional group which comprises the said acrylic polymer (a11) may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and ratio can be selected arbitrarily.

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

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

In the acrylic polymer (a11), the proportion (content) of the structural units derived from the acrylic monomer having a functional group is 0.1 to 50 mass% with respect to the total mass of the structural units constituting the acrylic polymer (a11). It is preferable that it is 1-40 mass %, It is more preferable, It is especially preferable that it is 3-30 mass %. When the ratio is within such a 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) may increase the amount of the protective film. The degree of curing can be easily adjusted to a desired range.

The number of the said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

· Energy ray-curable compound (a12)

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

It is preferable to have 1-5 pieces of the said energy-beam hardenable groups in 1 molecule, and, as for the said energy-beam-curable compound (a12), it is more preferable to have 1-2 pieces.

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

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

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

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

The number of the said energy-beam curable compound (a12) which comprises the said acrylic resin (a1-1) may be 1 type, and 2 or more types may be sufficient as them, and when 2 or more types, those combinations and a ratio can be selected arbitrarily.

It is preferable that it is 1-40 mass %, and, as for content of acrylic resin (a1-1), it is more preferable that it is 2-30 mass % with respect to the gross mass of components other than the solvent of the composition for films for protective film formation (2). And it is especially preferable that it is 3-20 mass %.

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 It is preferable that it is 120 mol%, It is more preferable that it is 35-100 mol%, It is especially preferable that it is 50-100 mol%. When the ratio of the content is within such a range, the adhesive force of the protective film after curing becomes larger. Further, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the ratio of the content is 100 mol%, but the energy ray-curable compound (a12) is In the case of a polyfunctional (having two or more groups in one molecule) compound, the upper limit of the ratio of the content may exceed 100 mol%. Here, "derived" means that the chemical structure changes in order to polymerize.

It is preferable that it is 100000-200000, and, as for the weight average molecular weight (Mw) of the said polymer (a1), it is more preferable that it is 300000-1500000. Here, the "weight average molecular weight" is as described above.

When the polymer (a1) is at least partially crosslinked with a crosslinking agent, the polymer (a1) does not correspond to any of the above-mentioned monomers described as constituting the acrylic polymer (a11). Further, a monomer having a group reactive with the crosslinking agent is polymerized and may be crosslinked in a group reactive with the crosslinking agent, or may be crosslinked in a group reactive with the functional group derived from the energy ray-curable compound (a12) do.

The number of the polymer (a1) contained in the composition (2) for a film for forming a protective film and the film for forming an energy ray-curable protective film may be one type, or two or more types, and in the case of two or more types, combinations and ratios thereof are arbitrarily You can choose.

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

Examples of the energy-ray-curable group that the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80000 has includes a group containing an energy-ray-curable double bond, and preferably a (meth)acryloyl group, a vinyl group and the like.

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

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

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di( Meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth) Acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypoly Propoxy) phenyl] propane, tricyclodecane dimethanol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-no Nandol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 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, neo bifunctional (meth)acrylates such as pentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane;

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

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

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

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

The number of compounds (a2) contained in the composition (2) for films for forming a protective film and the film for forming an energy ray-curable protective film may be one or two or more, and in the case of two or more, combinations and ratios thereof are arbitrarily You can choose.

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

When the composition (2) for films for protective film formation and the film for energy ray-curable protective film formation contain the compound (a2) as the energy ray-curable component (a), the polymer (b) having no energy ray-curable group further It is also preferable to contain

As for the said polymer (b), the thing which is not bridge|crosslinked may be sufficient as that at least one part was bridge|crosslinked with a crosslinking agent.

As a polymer (b) which does not have an energy-ray-curable group, an acrylic polymer, a phenoxy resin, a urethane resin, polyester, a rubber-type resin, an acrylic urethane resin etc. are mentioned, for example.

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

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl ester, (meth)acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid ester, hydroxyl group-containing (meth)acrylic acid ester, substituted amino group containing (meth)acrylic acid ester, etc. are mentioned. Here, the "substituted amino group" is as described above.

As said (meth)acrylic acid alkylester, (meth)acrylic acid alkylester etc. whose alkyl group which comprises an alkylester has a C1-C18 chain structure are preferable, For example, (meth)acrylate methyl, ( ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylate isobutyl, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl , (meth) acrylate pentyl, (meth) acrylic acid hexyl, (meth) acrylic acid heptyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylate isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl , (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate undecyl, (meth) acrylate dodecyl (also called (meth) acrylate lauryl), (meth) acrylate tridecyl, (meth) acrylic acid Tetradecyl (also called (meth) acrylate myristyl), (meth) acrylate pentadecyl, (meth) acrylate hexadecyl (also called (meth) acrylate palmityl), (meth) acrylate heptadecyl, (meth) acrylate octadecyl ((meth)stearyl acrylate) etc. are mentioned.

As (meth)acrylic acid ester which has the said cyclic skeleton, For example, (meth)acrylic acid cycloalkyl esters, such as (meth)acrylic acid isobornyl and (meth)acrylic acid dicyclopentanyl;

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

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

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

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

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

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

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

As a polymer (b) which does not have the said energy-beam curable group which at least one part was bridge|crosslinked with a crosslinking agent, what the reactive functional group in the said polymer (b) reacted with a crosslinking agent is mentioned, for example.

The reactive functional group may be appropriately selected according to the type of the crosslinking agent, and is not particularly limited. For example, when a crosslinking agent is a polyisocyanate compound, a hydroxyl group, a carboxy group, an amino group etc. are mentioned as said reactive functional group, Among these, a hydroxyl group with high reactivity with an isocyanate group is preferable. Moreover, when a crosslinking agent is an epoxy compound, a carboxy group, an amino group, an amide group etc. are mentioned as said reactive functional group, Among these, a carboxy group with high reactivity with an epoxy group is preferable. However, it is preferable that the said reactive functional group is a group other than a carboxy group from the point of preventing corrosion of the circuit of a semiconductor wafer or a semiconductor chip.

As a polymer (b) which has the said reactive functional group and does not have an energy-beam curable group, what was obtained by superposing|polymerizing the monomer which has the said reactive functional group at least is mentioned, for example. In the case of the acrylic polymer (b-1), one or both of the acrylic monomers and non-acrylic monomers exemplified as monomers constituting the acrylic polymer (b-1) may be those having the reactive functional group. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester. WHEREIN: The thing obtained by superposing|polymerizing the monomer which 1 or 2 or more hydrogen atoms are substituted with the said reactive functional group is mentioned.

In the said polymer (b) which has a reactive functional group, the ratio (content) of the structural unit derived from the monomer which has a reactive functional group is 1-20 mass % with respect to the total mass of the structural unit which comprises the said polymer (b). It is preferable that it is, and it is more preferable that it is 2-10 mass %. When the said ratio is such a range, in the said polymer (b), the degree of crosslinking becomes a more preferable range.

It is preferable that the weight average molecular weight (Mw) of the polymer (b) which does not have an energy ray-curable group is 10000-200000, and it is 100000-1500000 from the point which the film-formability of the composition (2) for films for protective film formation becomes more favorable. more preferably. Here, the "weight average molecular weight" is as described above.

The number of polymers (b) which does not have an energy-ray-curable group which the composition (2) for films for protective film formation and the film for energy-beam-curable protective film formation contain may be one, or two or more types may be sufficient, and, when 2 or more types, they Combinations and ratios of can be arbitrarily selected.

As a composition (2) for films for protective film formation, the thing containing any one or both of the said polymer (a1) and the said compound (a2) is mentioned. In addition, when the composition (2) for films for forming a protective film contains the compound (a2), it is preferable to further contain a polymer (b) not having an energy ray-curable group, and in this case, the polymer ( It is also preferable to contain a1). Moreover, the composition (2) for films for protective film formation does not contain the said compound (a2), but may contain the said polymer (a1) and the polymer (b) which does not have an energy-beam curable group together.

When the composition (2) for films for protective film formation contains the said polymer (a1), the said compound (a2), and the polymer (b) which does not have an energy-ray-curable group, in the composition (2) for films for protective film formation, The content of the compound (a2) is preferably from 10 to 400 parts by mass, more preferably from 30 to 350 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. desirable.

In the composition (2) for a film for forming a protective film, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group with respect to the total content (total mass) of components other than the solvent (i.e. , the total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group) of the film for forming an energy ray-curable protective film is preferably from 5 to 90 mass%, and from 10 to 80 mass% It is more preferable, and it is especially preferable that it is 20-70 mass %. When the said ratio of content of an energy-beam sclerosing|hardenable component is such a range, the energy-beam sclerosis|hardenability of the film for energy-beam curable protective film formation becomes more favorable.

As for content of the said energy-beam sclerosing|hardenable component (a), 1-80 mass % is preferable with respect to the gross mass of components other than the solvent in the composition (2) for films for protective film formation.

As for content of the said energy-beam curable component (a1), 1-80 mass % is preferable with respect to the gross mass of components other than a solvent in the composition (2) for films for protective film formation.

As for content of the said energy-beam sclerosing|hardenable component (a2), 1-80 mass % is preferable with respect to the gross mass of components other than the solvent in the composition (2) for films for protective film formation.

As for content of the polymer (b) which does not have the said energy-beam curable group, 1-80 mass % is preferable with respect to the gross mass of components other than a solvent in the composition (2) for films for protective film formation.

In addition, total content of the said component (a1), a component (a2), and a component (b) does not exceed 100 mass %.

The composition (2) for a film for forming a protective film is, in addition to the energy ray-curable component, according to the purpose, a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, a crosslinking agent, a colorant and a general-purpose additive selected from the group consisting of one type or You may contain 2 or more types. For example, by using the composition (2) for a film for forming a protective film containing the energy ray-curable component and the thermosetting component, the formed film for forming an energy ray-curable protective film has improved adhesion to an adherend by heating, and , the strength of the protective film formed from the film for forming an energy ray-curable protective film is also improved.

As said thermosetting component, a photoinitiator, a filler, a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose additive in the composition (2) for films for protective film formation, respectively, the thermosetting component (B) in the composition for films for protective film formation (1), respectively ), a photoinitiator (H), a filler (D), a coupling agent (E), a crosslinking agent (F), a colorant (I), and a general-purpose additive (J).

In the composition (2) for a film for forming a protective film, the thermosetting component, the photopolymerization initiator, the filler, the coupling agent, the crosslinking agent, the colorant and the general-purpose additive may be used individually by 1 type, respectively, may be used in combination of 2 or more types, When using 2 or more types together, those combination and ratio can be selected arbitrarily.

Content of the said thermosetting component, a photoinitiator, a filler, a coupling agent, a crosslinking agent, a coloring agent, and a general-purpose additive in the composition (2) for films for protective film formation may just adjust suitably according to the objective, and is not specifically limited.

It is preferable that the composition (2) for films for protective film formation further contains a solvent from the point which the handleability improves by dilution.

As a solvent which the composition (2) for films for protective film formation contains, the thing similar to the solvent in the composition (1) for films for protective film formation is mentioned, for example.

One type may be sufficient as the solvent which the composition (2) for films for protective film formation contains, and 2 or more types may be sufficient as it.

<<The manufacturing method of the composition for films for energy-beam-curable protective film formation>>

Compositions for films for energy ray-curable protective film formation, such as composition (2) for films for protective film formation, are obtained by mix|blending each component for comprising this.

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

When using a solvent, you may use by mixing a solvent with any compounding component other than a solvent and diluting this compounding component beforehand, without diluting any compounding component other than a solvent beforehand, a solvent is mixed with these compounding components. You may use by mixing.

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; How to mix using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not specifically limited as long as each compounding component does not deteriorate, What is necessary is just to adjust suitably, It is preferable that the temperature is 15-30 degreeC.

Control of the color of the film for forming a protective film

As for the film for protective film formation, the composition will not be specifically limited as color difference (DELTA)E ^* _ab of a printing part and a non-printing part is 8 or more. The film for protective film formation contains said various resin component, additives, such as a hardening|curing agent, a coloring agent (I), and a filler (D), The color of the film for protective film formation is determined by these kind and a compounding ratio. The color difference ΔE ^* _ab and the brightness difference ΔL ^* of the printing part and the non-printing part are the printing part whose component ratio fluctuates because the surface roughness of the irradiated part is changed by the irradiation of laser light, the components of the irradiated part are altered, or the components are volatilized, and the laser The difference in the color tone of the non-printing part not irradiated with light was digitized in the CIE1976L ^* a ^* b ^* color space system.

In the present specification, the color difference ΔE ^* _ab and the brightness difference ΔL ^* between the printed portion and the non-printed portion are calculated from the colors of the printed portion and the non-printed portion when laser printing is performed under the conditions described in Examples to be described later.

The color difference ΔE ^* _ab and the brightness difference ΔL ^* between the printing portion and the non-printing portion are controlled by the kind and compounding ratio of each component constituting the film for forming a protective film.

For example, by making the film surface for protective film formation into deep color in the state before laser printing, color difference (DELTA)E ^* _ab and brightness difference (DELTA)L ^* become large easily. This is because the surface roughness of the printed part by the laser increases and the whiteness increases due to diffuse reflection. In addition, the color difference tends to become large by designing a color tone in a complementary color relationship before and after laser printing rather than a color tone of the same color system. Moreover, when the colorant which volatilizes easily by laser beam irradiation is used, the quantity of the colorant in a printing part decreases, it becomes a color tone different from a non-printing part, and color difference (DELTA)E ^* _ab and lightness difference (DELTA)L ^* become large.

Sheet for forming a protective film

The sheet for protective film formation which concerns on this embodiment is equipped with the film for protective film formation mentioned above, and the support sheet mentioned later. Moreover, the said film for protective film formation may be equipped with the peeling film in the surface which is not equipped with the support sheet.

After removing the said peeling film, the sheet for protective film formation which concerns on this embodiment is affixed on the surface (back surface) on the opposite side to the surface in which the circuit in a semiconductor wafer is formed with the said film for protective film formation. After this, at a certain stage, the film for forming a protective film forms a protective film by curing. And the laminated body formed by laminating|stacking a support sheet, a protective film or protective film formation film, and a semiconductor wafer in this order is further dicing, and a support sheet, a protective film or protective film formation film, and a semiconductor chip are formed in this order. It is divided into pieces into the laminated body formed by lamination|stacking. The semiconductor chip is finally picked up from the support sheet in the state provided with the protective film on the back surface. Thus, the sheet for protective film formation which concerns on this embodiment is used in order to form a protective film on the back surface of a semiconductor chip.

In the present specification, in the sheet for forming a protective film, a protective film obtained by curing the film for forming a protective film by heating or irradiation with an energy ray is also referred to as a protective film forming sheet as long as the laminated structure of the supporting sheet and the protective film is maintained. Further, in the sheet for forming a protective film, for example, when the support sheet has an adhesive layer, the cured product of the adhesive layer also has a laminate structure such as a cured product of the adhesive layer and a film for forming a protective film or a protective film. As long as it is holding|maintained, it is called the sheet|seat for protective film formation.

Examples of the support sheet include those provided with a base material, and such a support sheet includes, for example, a sheet composed of only a base material, and other layers such as an adhesive layer, an intermediate layer, and a coating layer are laminated on the base material and a sheet formed by One layer (single layer) may be sufficient as said other layer, and two or more layers may be sufficient as multiple layers, In the case of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited. In addition, in this specification, it is not limited to the case of the said other layer, "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 "a plurality of layers are different from each other" means "at least one of the material and thickness of each layer is different from each other".

As described above, in the present embodiment, various types of sheets can be used as the support sheet. Hereinafter, the sheet for protective film formation which concerns on this embodiment for every kind of support sheet is demonstrated. In addition, in the drawings used in the following description, in order to make the characteristics of the present invention easy to understand, there are cases where the main parts are enlarged for convenience, and it is said that the dimensional ratio of each component is the same as in reality. can't

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically one Embodiment of the sheet|seat for protective film formation which concerns on this embodiment.

The sheet|seat 1A for protective film formation shown in FIG. 1 equips the adhesive layer 12 on the base material 11, and equips the adhesive layer 12 with the film 13 for protective film formation. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the sheet 1A for forming a protective film is a film for forming a protective film on one surface 10a of the support sheet 10 ( 13) has this stacked configuration. Moreover, the sheet|seat 1A for protective film formation is equipped with the peeling film 15 on the film 13 for protective film formation further.

In the sheet 1A for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the surface 12a of the pressure-sensitive adhesive layer 12 (in the pressure-sensitive adhesive layer 12) A film 13 for forming a protective film is laminated on the entire surface of the surface opposite to the surface in contact with the base 11), and on the surface 13a of the film 13 for forming a protective film (film 13 for forming a protective film) The adhesive layer 16 for a jig is laminated|stacked on a part of the surface on the opposite side to the surface in contact with the adhesive layer 12 in the adhesive layer for jig|tools among the surface 13a of the film 13 for protective film formation ( 16) the surface on which this is not laminated and the surface 16a of the adhesive layer 16 for a jig (upper surface, that is, on the opposite side to the surface in contact with the film 13 for forming a protective film in the adhesive layer 16 for a jig) The release film 15 is laminated|stacked on the side and side).

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

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

It is sectional drawing which shows typically other embodiment of the sheet|seat for protective film formation which concerns on this embodiment. In addition, in FIG. 2, the code|symbol similar to the case of FIG. 1 is attached|subjected to the component similar to that shown in FIG. 1, and the detailed description is abbreviate|omitted. This is also the same in the drawings after FIG. 3 .

The sheet 1B for forming a protective film shown in Fig. 2 is the same as the sheet 1A for forming a protective film shown in Fig. 1 except that the adhesive layer 16 for a jig is not provided. That is, in the sheet|seat 1B for protective film formation, the adhesive layer 12 is laminated|stacked on one surface 11a of the base material 11, and the surface 12a of the adhesive layer 12 (to the adhesive layer 12) The film 13 for protective film formation is laminated|stacked on the whole surface of the surface on the opposite side to the surface which contacts the base material 11 in the surface 13a (film 13 for protective film formation) of the film 13 for protective film formation. The release film 15 is laminated|stacked on the whole surface of the surface on the opposite side to the surface which contacts the adhesive layer 12 in ).

The sheet|seat 1B for protective film formation shown in FIG. 2 is in the state from which the peeling film 15 was removed, and among the surface 13a of the film 13 for protective film formation, in a part area|region on the central side, a semiconductor wafer (not shown) ) is affixed, and the area|region near the periphery which surrounds the semiconductor wafer of the film 13 for protective film formation is affixed to jigs, such as a ring frame, and is used.

3 : is sectional drawing which shows typically another embodiment of the sheet|seat for protective film formation which concerns on this embodiment.

The sheet|seat 1C for protective film formation shown in FIG. 3 is the same as that of the sheet|seat 1A for protective film formation shown in FIG. 1 except the point which is not equipped with the adhesive layer 12. That is, in 1 C of sheets for protective film formation, the support sheet 10 consists of the base material 11 only. And the film 13 for protective film formation is laminated|stacked on one surface 11a of the base material 11, and the surface 13a of the film 13 for protective film formation (substrate in the film 13 for protective film formation) The adhesive bond layer 16 for jig|tools is laminated|stacked on a part of the surface on the opposite side to the surface to contact, and the surface 13a of the surface 13a for protective film formation is the surface where the adhesive bond layer 16 for jigs is not laminated|stacked. and the surface 16a of the adhesive layer 16 for a jig (the upper surface, that is, the surface opposite to the surface in contact with the film 13 for forming a protective film in the adhesive layer 16 for a jig, and the side), peeled Films 15 are laminated.

The sheet|seat 1C for protective film formation shown in FIG. 3 is the state from which the peeling film 15 was removed similarly to the sheet|seat 1A for protective film formation shown in FIG. 1, The surface 13a of the film 13 for protective film formation ), the back surface of a semiconductor wafer (not shown) is affixed, and the upper surface among the surfaces 16a of the adhesive bond layer 16 for jigs is affixed to jigs, such as a ring frame, and is used.

4 : is sectional drawing which shows typically another embodiment of the sheet|seat for protective film formation which concerns on this embodiment.

The sheet|seat 1D for protective film formation shown in FIG. 4 is the same as 1C of sheet|seats for protective film formation shown in FIG. 3 except the point which is not equipped with the adhesive bond layer 16 for jig|tools. That is, in the sheet|seat 1D for protective film formation, the film 13 for protective film formation is laminated|stacked on one surface 11a of the base material 11, The surface 13a of the film 13 for protective film formation (protective film formation) The release film 15 is laminated|stacked on the whole surface of the surface on the opposite side to the surface in contact with the base material in the film 13 for use.

The sheet|seat 1D for protective film formation shown in FIG. 4 is the state from which the peeling film 15 was removed similarly to the sheet|seat 1B for protective film formation shown in FIG. 2, The surface 13a of the film 13 for protective film formation ), the back surface of a semiconductor wafer (not shown) is affixed to a partial region on the central side, and the region near the periphery surrounding the semiconductor wafer of the protective film formation film 13 is a jig such as a ring frame attached to and used.

5 : is sectional drawing which shows typically still another embodiment of the sheet|seat for protective film formation which concerns on this embodiment.

The sheet 1E for forming a protective film shown in FIG. 5 has a surface (hereinafter, sometimes referred to as the back surface of the base material) 11b on the opposite side to the side provided with the pressure-sensitive adhesive layer 12 in the base material 11 . It is the same as that of the sheet|seat 1A for protective film formation shown in FIG. 1 except the point provided with the coating layer 14 on it.

That is, in the sheet for forming a protective film 1E, the support sheet 10 is a laminate in which the coating layer 14, the substrate 11, and the pressure-sensitive adhesive layer 12 are laminated in this order, and the sheet for forming a protective film ( 1E) has the structure in which the film 13 for protective film formation was laminated|stacked on the one surface 10a of the support sheet 10. As shown in FIG. And the adhesive layer 12 is laminated|stacked on the one surface 11a of the base material 11, and the surface 12a of the adhesive layer 12 (the surface which contacts the base material 11 in the adhesive layer 12) The film 13 for protective film formation is laminated|stacked on the whole surface of the surface on the opposite side to the surface 13a of the film 13 for protective film formation (adhesive layer 12 in the film 13 for protective film formation) The adhesive bond layer 16 for jig|tools is laminated|stacked on a part of the surface on the opposite side to the surface to contact, and the surface 13a of the surface 13a for protective film formation is the surface where the adhesive bond layer 16 for jigs is not laminated|stacked. and the surface 16a of the adhesive layer 16 for a jig (the upper surface, that is, the surface opposite to the surface in contact with the film 13 for forming a protective film in the adhesive layer 16 for a jig, and the side), peeled Films 15 are laminated.

The sheet|seat 1E for protective film formation shown in FIG. 5 is the state from which the peeling film 15 was removed similarly to the sheet|seat 1A for protective film formation shown in FIG. 1, The surface 13a of the film 13 for protective film formation ), the back surface of a semiconductor wafer (not shown) is affixed, and the upper surface among the surfaces 16a of the adhesive bond layer 16 for jigs is affixed to jigs, such as a ring frame, and is used.

6 : is sectional drawing which shows typically still another embodiment of the sheet|seat for protective film formation which concerns on this embodiment.

The sheet|seat 1F for protective film formation shown here is the same thing as the sheet|seat 1E for protective film formation shown in FIG. 5 except the point which is not equipped with the adhesive bond layer 16 for jig|tools. That is, in the sheet|seat 1F for protective film formation, the adhesive layer 12 is laminated|stacked on one surface 11a of the base material 11, and the surface 12a of the adhesive layer 12 (to the adhesive layer 12) The film 13 for protective film formation is laminated|stacked on the whole surface of the surface on the opposite side to the surface which contacts the base material 11 in the surface 13a of the film 13 for protective film formation (in the film for protective film formation) The release film 15 is laminated|stacked on the whole surface of the surface on the opposite side to the surface in contact with the adhesive layer 12 of Moreover, the film back surface 11b (surface on the opposite side to the surface in contact with the adhesive layer 12 in the base material 11) of the film back surface 11b for protective film formation of the base material 11 is the sheet|seat 1E for protective film formation shown in FIG. ), and the coating layer 14 is laminated.

The sheet|seat 1F for protective film formation shown in FIG. 6 is the state from which the peeling film 15 was removed similarly to the sheet|seat 1B for protective film formation shown in FIG. 2, The surface 13a of the film 13 for protective film formation ), the back surface of a semiconductor wafer (not shown) is affixed to a partial region on the central side, and the region near the periphery surrounding the semiconductor wafer of the protective film formation film 13 is a jig such as a ring frame attached to and used.

7 : is sectional drawing which shows typically another embodiment of the sheet|seat for protective film formation which concerns on this embodiment.

The sheet|seat 1G for protective film formation shown here is the same thing as 1A of sheet|seats for protective film formation shown in FIG. 1 except the point from which the shape of the film for protective film formation differs. That is, the sheet|seat 1G for protective film formation equips the adhesive layer 12 on the base material 11, and equips the adhesive layer 12 with the film 23 for protective film formation. The support sheet 10 is a laminate of a base material 11 and an adhesive layer 12, and the sheet 1G for forming a protective film is a film for forming a protective film on one surface 10a of the support sheet 10 ( 23) has this stacked configuration. Moreover, the sheet|seat 1G for protective film formation is equipped with the peeling film 15 on the film 23 for protective film formation further. The film 23 for protective film formation is the same as the film 13 for protective film formation except the point from which a shape differs.

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

In the sheet 1G for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on one surface 11a of the base material 11, and the surface 12a of the pressure-sensitive adhesive layer 12 (in the pressure-sensitive adhesive layer 12) The film 23 for forming a protective film is laminated|stacked on a part of the surface on the opposite side to the surface in contact with the base material 11). And the surface 23a (upper surface, ie, the film 23 for protective film formation) of the surface on which the film 23 for protective film formation is not laminated|stacked among the surface 12a of the adhesive layer 12, and the film 23 for protective film formation ), the peeling film 15 is laminated|stacked on the surface on the opposite side to the surface which contacts the adhesive layer 12, and side).

In the sheet 1G for forming a protective film shown in FIG. 7 , in a state in which the release film 15 is removed, the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the film 23 for forming a protective film, and further , The surface on which the film 23 for protective film formation is not laminated|stacked among the surface 12a of the adhesive layer 12 is affixed to jigs, such as a ring frame, and is used.

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

The sheet|seat 1H for protective film formation shown here is the same thing as the sheet|seat 1G for protective film formation shown in FIG. 7 except the point which is not equipped with the adhesive layer 12. As shown in FIG. That is, in the sheet|seat 1H for protective film formation, a support sheet consists of the base material 11 only. Moreover, the film 23 for protective film formation is laminated|stacked on a part of one surface 11a of the base material 11, and the film 23 for protective film formation is not laminated|stacked among the surface 11a of the base material 11. On the surface 23a (the upper surface, ie, the surface opposite to the surface in contact with the base material 11 in the film 23 for protective film formation, and the side surface) of the surface and the film 23 for protective film formation, on the surface 23a, a peeling film (15) is laminated.

In the sheet 1H for forming a protective film shown in FIG. 8 , the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the film 23 for forming a protective film in a state in which the release film 15 is removed, and further , The surface on which the film 23 for protective film formation is not laminated among the surfaces 11a of the base material 11 is affixed to jigs, such as a ring frame, by the adhesive bond layer for jigs (not shown), and is used. Here, as an adhesive bond layer for jig|tools, the thing similar to the adhesive bond layer 16 for jig|tools shown in FIG. 1 etc. can be used.

Moreover, the sheet|seat for protective film formation can be affixed to jigs, such as a ring frame, using the adhesive bond layer for jig|tools even if a support sheet has any structure.

The sheet for forming a protective film according to the present embodiment is not limited to that shown in Figs. 1 to 8, and within a range that does not impair the effects of the present invention, some configurations of those shown in Figs. 1 to 8 are changed or deleted; , other configurations may be added in addition to those described above.

1, 2, 5, 6, and 7, the sheet for forming a protective film, in which the pressure-sensitive adhesive layer is formed in direct contact with the substrate, has been described. However, the sheet for forming a protective film according to the present embodiment. may have an intermediate layer formed between the substrate and the pressure-sensitive adhesive layer. That is, in the sheet|seat for protective film formation which concerns on this embodiment, the support sheet may have a laminated structure in which a base material, an intermediate|middle layer, and an adhesive layer are laminated|stacked in this order.

In addition, in Figs. 3, 4, and 8, as the sheet for forming a protective film, the film for forming a protective film has been described as being formed in direct contact with the base material. What the intermediate|middle layer was formed between the films for protective film formation may be sufficient.

Here, as an intermediate|middle layer, arbitrary things can be selected according to the objective, As a preferable thing, the thing which improves the adhesiveness of two adjacent layers is mentioned, for example.

Moreover, in the sheet|seat for protective film formation which concerns on this embodiment, layers other than the said intermediate|middle layer may be formed in arbitrary positions.

Hereinafter, each structure of the sheet|seat for protective film formation which concerns on this embodiment is demonstrated further in detail.

○ Support sheet

In this embodiment, the support sheet which comprises the sheet|seat for protective film formation will not be specifically limited if it can form the said film for protective film formation. Preferred support sheets include, for example, those made of only a base material commonly used in the field of the sheet for processing semiconductor wafers, as described above, a base material and a pressure-sensitive adhesive layer laminated, and a coating layer and a base material laminated one. and a coating layer, a base material, and a pressure-sensitive adhesive layer laminated in this order. Moreover, as a preferable support sheet, the thing in which the intermediate|middle layer was formed between two adjacent layers in the laminated structure exemplified above, such as one in which a base material, an intermediate|middle layer, and an adhesive layer are laminated|stacked, for example is mentioned.

That is, the support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When a support sheet consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

The thickness of the support sheet may be appropriately selected according to the purpose, but from the viewpoint of imparting sufficient flexibility to the sheet for forming a protective film and affixing it favorably to a semiconductor wafer, it is preferably 10 to 500 µm, and 20 to 350 µm It is more preferable that it is 30-200 micrometers, and it is still more preferable.

Here, "the thickness of the support sheet" means the total thickness of each layer constituting the support sheet, for example, in the case of a support sheet in which a base material and an adhesive layer are laminated, the thickness of the base material and the pressure-sensitive adhesive layer It means the total value of the thickness.

In addition, in this specification, "thickness" means the value shown by the average which measured the thickness by the contact-type thickness meter at arbitrary five points|points.

· write

In the present embodiment, the material of the substrate constituting the support sheet is preferably various resins, and specific examples thereof include polyethylene (low-density polyethylene, linear low-density polyethylene, high-density polyethylene, etc.), polypropylene, and ethylene/propylene. Copolymer, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene/acetic acid Vinyl copolymer, ionomer resin, ethylene/(meth)acrylic acid copolymer, ethylene/(meth)acrylic acid ester copolymer, polystyrene, polycarbonate, fluororesin, water additive, modified product, crosslinked product or copolymer of any of these resins water and the like.

The thickness of the base material can be appropriately selected according to the purpose.

When a support sheet is a thing by which other layers, such as a base material and an adhesive layer, are laminated|stacked, it is preferable that it is 15-300 micrometers, and, as for the thickness of a base material, it is more preferable that it is 20-200 micrometers. When the thickness of a base material is such a range, the flexibility of the sheet|seat for protective film formation, and the sticking property with respect to a semiconductor wafer or a semiconductor chip improve more.

The base material may consist of one layer (single layer), and may consist of multiple layers of two or more layers. When a base material consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

In addition, when a base material consists of multiple layers, what is necessary is just to make the thickness of the sum total of each layer become the thickness of the said preferable base material.

In order to improve adhesion with other layers such as a pressure-sensitive adhesive layer, a film for forming a protective film, and a coating layer formed thereon, the substrate is unevenly treated by sand blasting, solvent treatment, embossing treatment, etc. (matte treatment); The surface may be subjected to oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, or hot air treatment. Moreover, as for a base material, the thing to which the primer process was given may be sufficient as the surface.

· Adhesive layer

In this embodiment, a well-known thing can be used suitably for the adhesive layer which comprises the said support sheet.

An adhesive layer can be formed from the adhesive composition containing various components, such as an adhesive, for comprising this. The ratio of content of the components which are not vaporized at normal temperature in an adhesive composition becomes the same as the ratio of content of the said components of an adhesive layer normally. Here, "room temperature" is the same as described above.

Although the thickness of an adhesive layer can be suitably selected according to the objective, It is preferable that it is 1-100 micrometers, It is more preferable that it is 2-80 micrometers, It is still more preferable that it is 3-50 micrometers.

The adhesive layer may consist of one layer (single layer), and may consist of multiple layers of two or more layers. When an adhesive layer consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited.

When an adhesive layer consists of multiple layers, what is necessary is just to let the thickness of the sum total of each layer become the thickness of the said preferable adhesive layer.

Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resins, urethane-based resins, rubber-based resins, silicone-based resins, and vinyl ether-based resins. Curable resin etc. are mentioned.

Here, "energy-beam" and "energy-beam sclerosis|hardenability" are as described above.

As said energy-beam curable resin, what has polymeric groups, such as a (meth)acryloyl group and a vinyl group, is mentioned, for example.

It is preferable that it is an acrylic resin, and, as for the said adhesive resin, it is more preferable that it is a (meth)acrylic acid ester copolymer containing the structural unit derived from (meth)acrylic acid ester.

When the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with an energy ray, such as an energy ray-curable resin, it becomes energy ray-curable, and by irradiating an energy ray to reduce its adhesiveness, a protective film to be described later is formed Pick-up of the semiconductor chip becomes easy. Such an adhesive layer can be formed from various adhesive compositions containing the component superposed|polymerized by irradiation of an energy ray, for example.

<<Adhesive composition>>

Preferred ones in the pressure-sensitive adhesive composition include those containing a component that is polymerized by irradiation with energy rays, and as such a pressure-sensitive adhesive composition, for example, those containing an acrylic resin and an energy-beam polymerizable compound (hereinafter, It may be abbreviated as "adhesive composition (i)."); What contains the said acrylic resin (for example, it has a hydroxyl group and has a polymeric group in a side chain through a urethane bond) and an isocyanate type crosslinking agent which has a hydroxyl group and has a polymeric group in a side chain (the following) , it may be abbreviated as "adhesive composition (ii).") and the like.

[Adhesive composition (i)]

The adhesive composition (i) contains the said acrylic resin and an energy-beam polymeric compound as essential components.

Hereinafter, each component is demonstrated.

(Acrylic resin)

As a preferable thing in the said acrylic resin in the pressure-sensitive adhesive composition (i), for example, a (meth)acrylic acid ester as a monomer and a monomer other than the (meth)acrylic acid ester used as necessary are polymerized to obtain, (meth) ) an acrylic acid ester copolymer.

Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, ( Heptyl acrylate, (meth) acrylic acid n-octyl, (meth) acrylate isooctyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-nonyl, (meth) acrylate isononyl, (meth) acrylate decyl , (meth) acrylate undecyl, (meth) acrylate dodecyl (also called (meth) acrylate lauryl), (meth) acrylate tridecyl, (meth) acrylate tetradecyl ((meth) acrylate myristyl), (meth) Acrylic acid pentadecyl group, (meth)acrylic acid hexadecyl (also called (meth)acrylic acid palmityl), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl (also called (meth)acrylic acid stearyl), (meth)acrylic acid (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as isooctadecyl (also referred to as isostearyl (meth)acrylate), has a chain structure having 1 to 18 carbon atoms;

(meth)acrylic acid cycloalkyl esters, such as (meth)acrylic-acid isobornyl and (meth)acrylic-acid dicyclopentanyl;

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

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

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

(meth)acrylic acid imide;

glycidyl group-containing (meth)acrylic acid esters such as (meth)acrylic acid glycidyl;

(meth) acrylic acid hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters, such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylic acid, etc. are mentioned.

Among the above, methyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc. are preferable.

As a monomer other than the said (meth)acrylic acid ester, (meth)acrylic acid, itaconic acid, vinyl acetate, an acrylonitrile, styrene, N-methylolacrylamide etc. are mentioned, for example.

The number of various monomers, such as monomers other than the said (meth)acrylic acid ester and the said (meth)acrylic acid ester, constituting the acrylic resin may be one or two or more.

One type may be sufficient as the acrylic resin which adhesive composition (i) contains, and 2 or more types may be sufficient as it.

It is preferable that it is 40-99 mass % with respect to the gross mass of all components other than the solvent in an adhesive composition (i), and, as for content of the acrylic resin of an adhesive composition (i), it is more preferable that it is 50-91 mass %.

(energy ray polymerizable compound)

The energy-beam polymerizable compound in the pressure-sensitive adhesive composition (i) is a compound that is polymerized and cured by irradiation with an energy ray, and examples thereof include those having an energy ray-polymerizable group such as an energy ray-curable double bond in the molecule. have.

As said energy-beam polymeric compound, the low molecular-weight compound (monofunctional or polyfunctional monomer and oligomer) which has an energy-beam polymerizable group is mentioned, for example, More specifically, trimethylol propane tri(meth) is mentioned. Acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1 (meth)acrylates such as ,4-butylene glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate;

cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentadienedimethoxydi(meth)acrylate;

(meth)acrylics such as polyethylene glycol di(meth)acrylate, oligoester (meth)acrylate, urethane (meth)acrylate oligomer, epoxy-modified (meth)acrylate, polyether (meth)acrylate, itaconic acid oligomer rate-based compounds and the like.

It is preferable that molecular weight is 100-30000, and, as for the said energy-beam polymeric compound, it is more preferable that it is 300-10000.

One type may be sufficient as the energy-beam polymeric compound which adhesive composition (i) contains, and 2 or more types may be sufficient as it.

It is preferable that it is 1-125 mass parts with respect to 100 mass parts of content of the said acrylic resin, and, as for content of the energy-beam polymeric compound of an adhesive composition (i), it is more preferable that it is 10-125 mass parts.

(Photoinitiator)

The adhesive composition (i) may contain the photoinitiator other than the said acrylic resin and an energy-beam polymeric compound.

The said photoinitiator may be a well-known thing, Specifically, For example, 4-(2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, (alpha)-hydroxy- (alpha), α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl α-ketol compounds such as -propionyl)-benzyl]phenyl}-2-methyl-propan-1-one;

Acetophenone, dimethylaminoacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1- acetophenone-based compounds such as one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1;

benzoin ether compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, and anisoin methyl ether;

ketal compounds such as benzyl dimethyl ketal and acetophenone dimethyl ketal;

aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride;

1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl photoactive oxime compounds such as ]-1-(O-acetyloxime);

benzophenone compounds such as benzophenone, p-phenylbenzophenone, benzoylbenzoic acid, dichlorobenzophenone, 4,4'-diethylaminobenzophenone, and 3,3'-dimethyl-4-methoxybenzophenone;

anthraquinone-based compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 2-aminoanthraquinone;

Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, thioxanthone compounds such as 2,4-dichlorothioxanthone and 2,4-diisopropylthioxanthone;

p-dimethylaminobenzoic acid ester; camphor quinone; halogenated ketones; Acyl phosphine oxides, such as diphenyl (2,4,6- trimethylbenzoyl) phosphine oxide; acyl phosphonate, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], etc. are mentioned.

One type may be sufficient as the photoinitiator which adhesive composition (i) contains, and 2 or more types may be sufficient as it.

When using a photoinitiator, it is preferable that content of the photoinitiator of the adhesive composition (i) is 0.1-10 mass parts with respect to content 100 mass parts of the said energy-beam polymeric compound, It is more preferable that it is 1-5 mass parts do. When the said content of a photoinitiator is more than the said lower limit, the effect by using a photoinitiator is fully acquired. Moreover, when the said content of a photoinitiator is below the said upper limit, generation|occurrence|production of the by-product component from an excess photoinitiator is suppressed, and hardening of an adhesive layer advances more favorably.

(crosslinking agent)

The adhesive composition (i) may contain the crosslinking agent other than the said acrylic resin and an energy-beam polymeric compound further.

As said crosslinking agent, an organic polyhydric isocyanate compound, an organic polyvalent imine compound, etc. are mentioned, for example.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, an alicyclic polyvalent isocyanate compound, and a trimer, isocyanurate and adduct of these compounds, and the aromatic polyvalent isocyanate compound; The terminal isocyanate urethane prepolymer etc. which are obtained by making an aliphatic polyhydric isocyanate compound or an alicyclic polyhydric isocyanate compound and a polyol compound react are mentioned. The adduct is a reaction product of the aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound, or alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. it means.

As said organic polyhydric isocyanate compound, More specifically, For example, 2, 4- tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; compound which added any one or both of tolylene diisocyanate and hexamethylene diisocyanate to all or one part hydroxyl group of polyols, such as a trimethylol propane; Lysine diisocyanate etc. are mentioned.

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

When using an isocyanate compound as a crosslinking agent, it is preferable to use a hydroxyl-containing polymer as acrylic resin. When a crosslinking agent has an isocyanate group and acrylic resin has a hydroxyl group, a crosslinked structure can be easily introduce|transduced into an adhesive layer by reaction of these isocyanate groups and a hydroxyl group. One type may be sufficient as the crosslinking agent which adhesive composition (i) contains, and 2 or more types may be sufficient as it.

When using a crosslinking agent, it is preferable that it is 0.01-20 mass parts with respect to content of 100 mass parts of the said acrylic resin, and, as for content of the crosslinking agent in adhesive composition (i), it is more preferable that it is 0.1-16 mass parts.

(menstruum)

It is preferable that adhesive composition (i) contains a solvent other than the said acrylic resin and an energy-beam polymeric compound further.

Although the said solvent is not specifically limited, As a preferable thing, For example, Hydrocarbons, such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (also referred to as 2-methylpropan-1-ol), and 1-butanol; Ester, such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (ie, compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. One type may be sufficient as the solvent which adhesive composition (i) contains, and 2 or more types may be sufficient as it.

It is preferable that it is 40-90 mass % with respect to the gross mass of an adhesive composition, and, as for content of the solvent in case adhesive composition (i) contains a solvent, it is more preferable that it is 50-80 mass %.

(Other ingredients)

The pressure-sensitive adhesive composition (i) contains, in addition to the acrylic resin and the energy ray polymerizable compound, other components that do not correspond to the photopolymerization initiator, crosslinking agent and solvent, within the range that does not impair the effects of the present invention, there may be

The above-mentioned other components may be known, may be arbitrarily selected according to the purpose, and are not particularly limited, but preferably, for example, a colorant (dye, pigment), deterioration inhibitor, antistatic agent, flame retardant, silicone compound and various additives such as a chain transfer agent. One type may be sufficient as the said other component which adhesive composition (i) contains, and 2 or more types may be sufficient as it.

[Adhesive composition (ii)]

The adhesive composition (ii) has a hydroxyl group and has a polymeric group in a side chain acrylic resin (For example, it has a hydroxyl group and has a polymeric group in a side chain through a urethane bond), and an isocyanate type crosslinking agent as an essential ingredient.

When the pressure-sensitive adhesive composition (ii) is used, the acrylic resin has a polymerizable group in the side chain, so as in the case of the pressure-sensitive adhesive composition (i), an energy ray polymerizable compound is used and a polymerization reaction is carried out by irradiation with an energy ray. Furthermore, the peelability from the to-be-adhered body by the adhesive fall of the adhesive layer after polymerization reaction (hardening) improves, and the pick-up property of the semiconductor chip with a protective film improves.

In addition, in this specification, the description of "acrylic resin" in adhesive composition (ii) shall mean "acrylic resin which has a polymeric group in a side chain" unless otherwise indicated.

(Acrylic resin)

As acrylic resin which has the above-mentioned polymeric group in a side chain, hydroxyl-containing, such as a hydroxyl-free (meth)acrylic acid ester which does not have a hydroxyl group, and hydroxyl-containing (meth)acrylic acid ester which has a hydroxyl group, as a monomer, for example. What was obtained by making the isocyanate group of the compound which has an isocyanate group and a polymeric group react with the hydroxyl group of the hydroxyl-containing copolymer obtained by copolymerizing a compound, and forming a urethane bond is mentioned.

As said hydroxyl-free (meth)acrylic acid ester, things other than hydroxyl-containing (meth)acrylic acid ester among (meth)acrylic acid esters in an adhesive composition (i) are mentioned, for example.

Moreover, as said hydroxyl-containing compound, the thing similar to the hydroxyl-containing (meth)acrylic acid ester in adhesive composition (i) is mentioned.

Each of the hydroxyl group-free (meth)acrylic acid ester and the hydroxyl group-containing compound constituting the acrylic resin may be one, or two or more.

As a compound which has the said isocyanate group and a polymeric group, isocyanate group containing (meth)acrylic acid ester, such as 2-methacryloyloxyethyl isocyanate, etc. are mentioned, for example.

The number of the compound which comprises the said acrylic resin and which has the said isocyanate group and a polymeric group may be one, and 2 or more types may be sufficient as it.

One type may be sufficient as the acrylic resin which adhesive composition (ii) contains, and 2 or more types may be sufficient as it.

It is preferable that it is 80-99 mass % with respect to the total mass of all components other than the solvent in an adhesive composition (ii), and, as for content of the acrylic resin of an adhesive composition (ii), it is more preferable that it is 90-97 mass % .

(isocyanate-based crosslinking agent)

As said isocyanate type crosslinking agent, the thing similar to the said organic polyhydric isocyanate compound which is a crosslinking agent in an adhesive composition (i) is mentioned, for example. One type may be sufficient as the isocyanate type crosslinking agent which adhesive composition (ii) contains, and 2 or more types may be sufficient as it.

It is preferable that the mole number of the isocyanate groups which the isocyanate type crosslinking agent in an adhesive composition (ii) has is 0.2 to 3 times with respect to the mole number of the hydroxyl groups which the acrylic resin in an adhesive composition (ii) has. When the said number of moles of an isocyanate group is more than the said lower limit, the peelability from the to-be-adhered body by the adhesive fall of the adhesive layer after hardening improves, and the pick-up property of the semiconductor chip with a protective film improves. Moreover, when the said number of moles of an isocyanate group is below the said upper limit, generation|occurrence|production of the by-product by reaction of isocyanate type crosslinking agents can be suppressed more.

The content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition (ii) may be appropriately adjusted so that the number of moles of the isocyanate group falls within the range as described above. After satisfying these conditions, the content of the acrylic resin is 0.01 to 100 parts by mass, It is preferable that it is -20 mass parts, It is more preferable that it is 0.1-15 mass parts, It is especially preferable that it is 0.3-12 mass parts.

(Photoinitiator)

The adhesive composition (ii) may contain the photoinitiator other than the said acrylic resin and an isocyanate type crosslinking agent.

As said photoinitiator, the thing similar to the case of adhesive composition (i) is mentioned, for example. One type may be sufficient as the photoinitiator which adhesive composition (ii) contains, and 2 or more types may be sufficient as it.

When using a photoinitiator, it is preferable that content of the photoinitiator of an adhesive composition (ii) is 0.05-20 mass parts with respect to content 100 mass parts of acrylic resin.

When the said content of a photoinitiator is more than the said lower limit, the effect by using a photoinitiator is fully acquired. Moreover, when the said content of a photoinitiator is below the said upper limit, generation|occurrence|production of the by-product component from an excess photoinitiator is suppressed, and hardening of an adhesive layer advances more favorably.

(menstruum)

It is preferable that adhesive composition (ii) contains a solvent other than the said acrylic resin and an isocyanate type crosslinking agent further.

As said solvent, the thing similar to the case of adhesive composition (i) is mentioned, for example. One type may be sufficient as the solvent which adhesive composition (ii) contains, and 2 or more types may be sufficient as it.

It is preferable that it is 40-90 mass % with respect to the gross mass of an adhesive composition (ii), and, as for content of the solvent in case an adhesive composition (ii) contains a solvent, it is more preferable that it is 50-80 mass %.

(Other ingredients)

The adhesive composition (ii) may contain the other component which does not correspond to the said photoinitiator and a solvent other than the said acrylic resin and an isocyanate type crosslinking agent within the range which does not impair the effect of this invention.

As said other component, the thing similar to the case of adhesive composition (i) is mentioned, for example. One type may be sufficient as the said other component which adhesive composition (ii) contains, and 2 or more types may be sufficient as it.

Heretofore, although the adhesive composition containing the component superposed|polymerized by irradiation of an energy ray was demonstrated, you may use the adhesive composition which does not contain the component superposed|polymerized by irradiation of an energy ray for formation of an adhesive layer. That is, a non-energy-ray-curable thing which does not have energy-beam sclerosis|hardenability may be sufficient as an adhesive layer.

As a preferable thing in such a non-energy-ray-curable adhesive composition, for example, the thing containing an acrylic resin and a crosslinking agent (Hereinafter, it may abbreviate as "adhesive composition (iii)".) etc. are mentioned, and a solvent , may contain optional components such as other components that do not correspond to solvents.

[Adhesive composition (iii)]

All of the said acrylic resin, a crosslinking agent, a solvent, and other components which adhesive composition (iii) contains are the same thing as the thing in adhesive composition (i).

It is preferable that it is 40-99 mass % with respect to the gross mass of all components other than the solvent in an adhesive composition (iii), and, as for content of the acrylic resin of an adhesive composition (iii), it is more preferable that it is 50-97 mass %.

It is preferable that it is 2-30 mass parts with respect to content of 100 mass parts of acrylic resin, and, as for content of the crosslinking agent of adhesive composition (iii), it is more preferable that it is 4-25 mass parts.

The adhesive composition (iii) is the same as the adhesive composition (i) except for the point mentioned above.

<<The manufacturing method of an adhesive composition>>

The said adhesive compositions, such as adhesive composition (i) - (iii), are obtained by mix|blending each component for constituting the adhesive composition, such as components other than the said adhesive, as needed with the said adhesive.

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

The method of mixing each component at the time of mixing|blending is not specifically limited, The method of rotating a stirrer, a stirring blade, etc. and mixing; How to mix using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not specifically limited as long as each compounding component does not deteriorate, What is necessary is just to adjust suitably, It is preferable that the temperature is 15-30 degreeC.

○ release film

As a peeling film, the well-known peeling film etc. which are used in this field and which have a peeling process surface are mentioned, for example. As a peeling process in the said peeling process surface, the process by various peeling agents, such as an alkyd type, a silicone type, a fluorine type, an unsaturated polyester type, a polyolefin type, or a wax type, is mentioned. From the viewpoint of having heat resistance, the release agent is preferably an alkyd-based, silicone-based or fluorine-based release agent.

Although the thickness of a peeling film is not specifically limited, It is preferable that it is 20-85 micrometers, and it is more preferable that it is 25-75 micrometers. When the thickness of a peeling film is more than the said lower limit, peeling of the peeling film in the step made into the objective becomes easier, and after winding up the sheet for protective film formation and setting it as a roll, a winding trace becomes difficult to appear on a peeling film. On the other hand, when the thickness of a peeling film is below the said upper limit, the effect which suppresses peeling of the peeling film in a step other than the objective becomes higher.

<The manufacturing method of the sheet|seat for protective film formation>

The sheet for forming a protective film according to the present embodiment includes a step of forming a laminated structure of the support sheet and the film for forming a protective film (hereinafter, sometimes referred to as a “lamination step (P1)”), and the film for forming a protective film. And it can manufacture by the manufacturing method containing the process (Hereinafter, it may call "lamination process (P2)") of forming the laminated structure of the said peeling film.

When a support sheet consists of multiple layers, what is necessary is just to laminate|stack these some layer and just to manufacture a support sheet.

In the case of manufacturing a support sheet in which another layer (for example, a pressure-sensitive adhesive layer, an intermediate layer, a coating layer, etc.) is laminated on a substrate, for example, a composition containing a component for constituting the other layer (for example, , a pressure-sensitive adhesive composition, a composition for forming an intermediate layer, a coating composition, etc.) is coated on the surface of the substrate and dried as necessary to laminate the other layer on the substrate. Moreover, when manufacturing the support sheet in which another layer is laminated|stacked on the base material, for example, the composition containing the component for comprised said other layer is coated on the peeling process surface of a peeling material, and drying is needed as needed. You may laminate the said other layer on a base material by bonding together the surface (exposed surface) of the formed said other layer in advance on a release material by making it and the surface of the said base material, after forming in advance. In this case, what is necessary is just to remove the said peeling material until it performs a certain operation on the said other layer, such as the time of lamination|stacking of the film for protective film formation with respect to the said other layer as needed.

As said release material, a well-known thing may be used in this field|area, for example, you may use the thing similar to the above-mentioned peeling film which comprises the sheet|seat for protective film formation which concerns on this embodiment.

For example, it is possible to form another layer by directly coating the target composition with respect to the base material in which the said other layer has already been laminated|stacked on one or both surfaces. However, in such a case, as mentioned above, it is preferable to employ|adopt the method of bonding together the said other layer previously formed on the release material with the other layer already laminated|stacked on the base material or base material.

In the lamination step (P1), in the laminated structure of the support sheet and the film for forming a protective film, for example, a composition for a film for forming a protective film is coated on the surface of the support sheet and dried as necessary, the film for forming a protective film (Hereinafter, this process may be specifically referred to as "lamination process (P1)-11").

In the lamination process (P1), the laminated structure of the support sheet and the film for forming a protective film can be formed, for example, by the same method as in the case of the production of the support sheet comprising a plurality of layers described above. That is, after coating the composition for a film for forming a protective film on the release treatment surface of the release material and drying as necessary, the film for forming a protective film on the release material is previously formed, and then the release material of the formed film for forming a protective film is The laminated structure of the support sheet and the film for protective film formation can be formed also by bonding the surface on the side which is not formed with the surface of a support sheet (hereafter, this process is specifically referred to as "lamination process (P1)-12"). sometimes called).

As said release material in this method, a thing well-known in this field|area may just be used, for example, the thing similar to the above-mentioned release film which comprises the sheet|seat for protective film formation which concerns on this embodiment is preferable.

For example, even when the support sheet is formed by laminating the other layer on one or both surfaces of the base material, the composition for a protective film forming film is directly coated on such a support sheet to obtain a protective film forming film. It is possible to form However, it is preferable to employ|adopt the method of bonding together the film for protective film formation previously formed on the peeling material with a support sheet as above-mentioned in the lamination|stacking process (P1) also in such a case.

When the lamination process (P1)-11 mentioned above is employ|adopted as lamination|stacking process (P1), in the said lamination|stacking process (P2), on the surface of the side on which the support sheet of the film for protective film formation is not formed, the said What is necessary is just to stick a peeling film together.

On the other hand, when the lamination process (P1)-12 mentioned above is employ|adopted as lamination process (P1), in the said lamination process (P2), the side opposite to the side on which the support sheet of the film for protective film formation is formed. After removing the peeling material formed in the surface and exposing one surface of the film for protective film formation, what is necessary is just to bond the said peeling film together on the exposed surface of this film for protective film formation.

Moreover, when the above-mentioned lamination|stacking process (P1)-12 is employ|adopted as lamination|stacking process (P1), as said release material which forms the film for protective film formation in advance, the said release film (for protective film formation which concerns on this embodiment) By employing the release film constituting the sheet), this lamination step (P1)-12 also serves as the lamination step (P2). This manufacturing method can be said to be preferable at the point which can simplify a manufacturing process. The process of forming the laminated structure of the support sheet and the film for protective film formation in this manufacturing method may be specifically called "lamination process (P1')" below.

For example, as shown in FIG. 7 etc., when looking down at the sheet for protective film formation from the peeling film side and planar view, when the film for protective film formation manufactures the sheet|seat for protective film formation with a smaller surface area than an adhesive layer, the above-mentioned In one manufacturing method, what is necessary is just to form the film for protective film formation previously cut into predetermined size and shape on an adhesive layer.

In the production of the sheet for forming a protective film according to the present embodiment, the film for forming a protective film can be formed by coating the composition for the film for forming a protective film on the formation target surface of the film for forming a protective film as described above. .

At the time of manufacture of the sheet|seat for protective film formation which concerns on this embodiment, for example, an adhesive layer can be formed by coating the said adhesive composition on the formation target surface of an adhesive layer, Preferably it is made to dry. The adhesive composition can be coated by the method similar to the case of the composition for films for protective film formation.

The coated adhesive composition may be bridged by heating, and bridge|crosslinking by this heating may serve also as drying and may perform. Although heating conditions can be made into 1 to 5 minutes at 100-130 degreeC, for example, it is not limited to this.

Hereinafter, among the sheets for forming a protective film according to the present embodiment, as an example, a manufacturing method having the lamination step (P1') as a manufacturing method of the one having the configuration shown in FIG. 2 will be described with reference to FIG. 9 . In addition, the manufacturing method described here is an example, The manufacturing method of the other manufacturing method of the sheet|seat for protective film formation shown in FIG. 2, and another manufacturing method of the sheet|seat for protective film formation are the same as or similar to the process demonstrated below. When it has, such a process can also be implemented similarly to the process demonstrated below.

In this method, a composition for a film for forming a thermosetting protective film or a composition for a film for forming an energy ray-curable protective film is applied to the release-treated surface 15b of the release film 15, and as shown in Fig. 9(a), a protective film is formed. The film 13 for use is formed. In addition, although the example arrange|positioned here so that comparison with the sheet|seat 1B for protective film formation may become easy, the film 13 for protective film formation may become a lower layer than the peeling film 15, this is coating of a protective film formation composition It does not mean that the direction of the peeling surface 15b in the peeling film 15 at the time is limited to the downward direction as shown to Fig.9 (a), the opposite upward direction may be sufficient as this, It is preferable to be upward.

Moreover, you may bond a peeling material separately on the surface (exposed surface) on the opposite side to the side in contact with the peeling film 15 in the formed film 13 for protective film formation (not shown). The same thing as the peeling material which is the coating object of the adhesive composition mentioned later with a peeling material here is mentioned.

In this method, the adhesive composition is then coated on the peeling process surface 90b of the peeling material 90, and as shown to FIG.9(b), the adhesive layer 12 is formed. Also here, although the example arrange|positioned so that comparison with the sheet|seat 1B for protective film formation may become easy so that the adhesive layer 12 may become lower than the peeling material 90 may be shown, this is peeling at the time of coating of an adhesive composition It does not mean that the direction of the peeling process surface 90b of the ash 90 is limited to the downward direction as shown to Fig.9(b), the upward direction opposite to this may be sufficient, and it is preferable that it is upward.

In this method, then, as shown in FIG.9(c), on the surface (exposed surface) on the opposite side to the side which is contacting the peeling material 90 in the adhesive layer 12, the base material 11 concatenate At this time, the bonding surface of the adhesive layer 12 in the base material 11 so that the surface roughness of the surface 11b on the side which does not bond the adhesive layer 12 in the base material 11 may be set to 0.5 micrometer or less at this time. choose

By the above, the support sheet 10 is obtained.

In this method, as shown to Fig.9(d) then, the adhesive layer 12 exposed by removing the peeling material 90 currently formed in the adhesive layer 12 in the support sheet 10 is exposed By bonding a surface and the exposed surface of the film 13 for protective film formation, as shown to FIG.9(e), the sheet|seat 1B for protective film formation is obtained. When the peeling material mentioned above is bonded separately by the surface (exposed surface) on the opposite side to the side which is in contact with the peeling film 15 of the film 13 for protective film formation, after removing this peeling material, a protective film What is necessary is just to bond the exposed surface of the film 13 for formation, and the exposed surface of the adhesive layer 12 together.

Next, among the sheet|seats for protective film formation which concerns on this embodiment, the manufacturing method of the thing of the structure shown in FIG. 1 is demonstrated (not shown).

In this method, the manufacturing method of the said sheet|seat 1B for protective film formation can be used.

First, using the lamination sheet in which the release film 15 was laminated|stacked on one side of the adhesive tape for forming the adhesive bond layer 16 for a jig, a cut is formed so that it may become a target shape at the target point of an adhesive tape. . Here, the target shape is, for example, a shape used as a circular shape in planar view so that the surface of this lamination sheet may be looked down.

Next, the adhesive tape having the desired shape (for example, circular in plan view) is removed from the lamination sheet, and in the region from which the adhesive tape has been removed, the processing in the state where the release material is exposed is completed. Let it be a laminated sheet. That is, when the circular adhesive tape is removed in the said planar view, in the lamination sheet with this process completed, the adhesive tape will be taken out roundly in the target point.

Next, from the sheet 1B for protective film formation obtained above, the peeling film 15 is removed, the exposed surface of the film 13 for protective film formation, and the adhesive tape of the laminated sheet on which this process was completed are bonded together, FIG. 1 The sheet|seat 1A for protective film formation shown to is obtained. In this method, when a sheet 1B for forming a protective film is not wound in roll shape, a known release material other than the release film 15 is used instead of the release film 15 as a bonding object of the lamination sheet for which the above processing has been completed. You may use the sheet|seat for protective film formation of the same structure as the sheet|seat 1B for protective film formation except the point provided with it.

However, the manufacturing method mentioned above is an example, and the manufacturing method of 1 A of sheet|seats for protective film formation is not limited to this.

<How to use the sheet for forming a protective film>

The usage method of the sheet|seat for protective film formation which concerns on this embodiment is as showing below, for example.

First, the usage method of the sheet|seat for protective film formation in case the film for protective film formation is thermosetting is demonstrated.

When the film for protective film formation is thermosetting, while affixing the back surface of a semiconductor wafer to the film for protective film formation of the sheet|seat for protective film formation first, the sheet for protective film formation is fixed to a dicing apparatus.

Next, the film for protective film formation is hardened by heating, and it is set as a protective film. When the back grind tape is affixed on the surface (electrode formation surface) of a semiconductor wafer, after removing this back grind tape from a semiconductor wafer normally, a protective film is formed.

Next, a semiconductor wafer is diced together with a protective film, and it is set as a semiconductor chip. During the period from forming the protective film until dicing, the protective film can be irradiated with a laser beam from the supporting sheet side of the protective film forming sheet to perform printing (laser printing) on the surface of the protective film.

Next, the semiconductor chip with a protective film is obtained by peeling and picking up a semiconductor chip together with the protective film after the cut|disconnection affixed on the back surface from a support sheet. For example, when the support sheet is a sheet in which a base material and an adhesive layer are laminated, and the adhesive layer is an energy ray-curable layer, the adhesive layer is cured by irradiation with energy rays, and a semiconductor chip is formed from the cured adhesive layer. By picking up together with the protective film affixed on the back surface, the semiconductor chip in which the protective film was formed more easily is obtained.

The obtained semiconductor chips with a protective film are picked up one by one, and are conveyed to the next process.

After that, the semiconductor chip on which the protective film is formed is mounted in the reflow process. For example, the obtained semiconductor chip with a protective film can be flip-chip-connected to the circuit surface of a board|substrate, and can be mounted. Then, it is set as a semiconductor package by sealing the whole with resin. And what is necessary is just to manufacture the target semiconductor device using this semiconductor package.

In addition, although the case where dicing was demonstrated until here, after hardening the film for protective film formation and forming a protective film, dicing is performed without hardening|curing the film for protective film formation, After this dicing, the film for protective film formation may be cured to form a protective film. Moreover, you may perform laser printing in the non-hardened state of the film for protective film formation. Laser printing is performed on the film for protective film formation, and the semiconductor wafer which has the protective film by which laser printing was carried out is obtained by hardening the film for protective film formation after that.

Next, the usage method of the sheet|seat for protective film formation in case the film for protective film formation is energy-beam sclerosis|hardenability is demonstrated.

When the film for protective film formation is energy ray-curable, first, similarly to the case where the film for protective film formation mentioned above is thermosetting, while affixing the back surface of a semiconductor wafer to the film for protective film formation of the sheet for protective film formation, a protective film The forming sheet is fixed to the dicing apparatus.

Next, the film for protective film formation is hardened by irradiation of an energy ray, and it is set as a protective film. When the back grind tape is affixed on the surface (electrode formation surface) of a semiconductor wafer, after removing this back grind tape from a semiconductor wafer normally, a protective film is formed.

Next, a semiconductor wafer is diced together with a protective film, and it is set as a semiconductor chip. During the period from forming the protective film until dicing, the protective film can be irradiated with a laser beam from the supporting sheet side of the protective film forming sheet, and the surface of the protective film can be printed.

Next, the semiconductor chip with a protective film is obtained by peeling and picking up a semiconductor chip together with the protective film after cutting|disconnection affixed on the back surface from a support sheet.

This method is particularly preferable when, for example, a sheet for forming a protective film in which a support sheet is formed by laminating a base material and a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is other than energy ray-curable.

For example, when a support sheet uses the sheet|seat for protective film formation which consists of a base material and an adhesive layer laminated|stacked, and the said adhesive layer is an energy-ray-curable thing, the method demonstrated below is preferable.

That is, first, while affixing the back surface of a semiconductor wafer to the film for protective film formation of the sheet|seat for protective film formation similarly to the said case, the sheet for protective film formation is fixed to a dicing apparatus.

Next, after irradiating a laser beam to the film for protective film formation from the support sheet side of the sheet|seat for protective film formation as needed, and printing on the surface of the film for protective film formation, a semiconductor wafer is diced and it is set as a semiconductor chip.

Next, by irradiation with an energy ray, the film for forming a protective film is cured to form a protective film, the pressure-sensitive adhesive layer is cured, and the semiconductor chip is picked up from the cured pressure-sensitive adhesive layer together with the protective film affixed on the back surface. The formed semiconductor chip is obtained. The printing applied to the surface of the film for protective film formation is maintained in the same state also in a protective film.

A subsequent process is the same as the case where the film for protective film formation mentioned above is thermosetting.

Moreover, the method demonstrated here can add a change similarly to the case where the film for protective film formation mentioned above is thermosetting. That is, until here, although the case where dicing was demonstrated after hardening the film for protective film formation and forming a protective film, dicing is performed without hardening the film for protective film formation, After this dicing, the film for protective film formation may be cured to form a protective film.

Example

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

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

[Polymer component (A)]

(A)-1: Acrylic polymer: An acrylic polymer obtained by copolymerizing 15 parts by mass of n-butyl acrylate, 10 parts by mass of methyl methacrylate, 60 parts by mass of methyl acrylate, and 15 parts by mass of 2-hydroxyethyl acrylate ( Weight average molecular weight: 600,000, glass transition temperature: 1°C)

[thermosetting component (B)]

・Epoxy resin (B1)

(B1)-1: bisphenol A liquid epoxy resin (manufactured by Nippon Catalyst, BPA328, epoxy equivalent 230)

(B1)-2: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800 to 900)

(B1)-3: bisphenol F-type liquid epoxy resin ("jERYL983U" manufactured by Mitsubishi Chemical, epoxy equivalent 165 to 175)

· Thermosetting agent (B2)

(B2)-1: dicyandiamide (thermally active latent epoxy resin curing agent, "ADEKA HARDNER EH-3636AS" manufactured by ADEKA)

[curing accelerator (C)]

(C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.)

[Filling material (D)]

(D)-1: Silica filler (Admatex, SC105G-MMQ: spherical silica, average particle diameter 0.3 µm)

[Coupling agent (E)]

(E)-1: 3-glycidoxypropyltrimethoxysilane (3-glycidyloxypropyltrimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)

[Colorant (I)]

(I)-1: carbon black (“MA600B” manufactured by Mitsubishi Chemical, average particle size 28 nm)

The used support sheet and peeling film are as follows. A support sheet is an adhesive tape marketed as a dicing sheet.

Base: Adwill G-535H manufactured by Lintec, (thickness 90 µm)

Release film: SP-PET381130 manufactured by Lintec (38 µm thick)

[Example 1]

<Production of sheet for forming a protective film>

(Preparation of a composition for a film for forming a thermosetting protective film)

As shown in Table 1, polymer component (A)-1 (20 parts by mass), epoxy resin (B1)-1 (15 parts by mass), epoxy resin (B1)-2 (1.8 parts by mass), thermosetting agent (B2) )-1 (0.45 parts by mass), curing accelerator (C)-1 (0.45 parts by mass), filler (D)-1 (60 parts by mass), coupling agent (E)-1 (0.4 parts by mass), and a colorant ( I)-1 (1.9 mass parts) is mixed, methyl ethyl ketone is further mixed, and by stirring at 23 degreeC for 60 minutes, content of solid content is 52 mass % Composition (1-1) for films for protective film formation got it In addition, all the compounding quantities of components other than methyl ethyl ketone shown here and Table 1 are solid content.

(Formation of film for protective film formation)

On the peeling treatment surface of the peeling film, the composition (1-1) for protective film formation obtained above is coated with a knife coater and dried at 110 degreeC for 2 minutes, The film for protective film formation with a thickness of 25 micrometers formed. Moreover, the peeling process surface of the peeling film was pasted together on the exposed surface on the opposite side to the side in which the peeling film of this film for protective film formation is formed.

(Manufacture of sheet for forming a protective film)

The peeling film is removed from one surface of the film for protective film formation obtained above, and the peeling film currently formed in the adhesive layer of the support sheet is removed, and the exposed surface of the film for protective film formation and the exposed surface of an adhesive layer are laminated. The sheet for protective film formation in which a base material, the said adhesive layer, the said film for protective film formation, and a peeling film are laminated|stacked in this order by doing was obtained.

(Manufacture of silicon chip with protective film formed)

On the #2000 polished surface of a 6-inch silicon wafer (thickness 100 µm), the obtained sheet for forming a protective film was affixed through the film for forming a protective film, and this sheet was further fixed to a ring frame, and left still for 30 minutes. did.

Next, the film for protective film formation was hardened|cured and it was set as the protective film by heat-processing the silicon wafer which has the film for protective film formation at 130 degreeC for 2 hours.

Next, laser printing was performed on the film for protective film formation on the following conditions using the green laser marker (CSM300M by EO tech company).

Wavelength: 532 nm

Output: 0.38 W

Frequency: 20 kHz

Scan speed: 100 mm/s

Argument Character: ABCD

Character size: 300 ㎛ (height) × 200 ㎛ (width)

Character line width: 35 ㎛

Then, using a dicing blade, the protective film was diced to separate the silicon wafer into pieces to obtain a silicon chip having a size of 3 mm long and 3 mm wide, a protective layer thickness of 25 µm, and a Si layer thickness of 350 µm. Next, the silicon chip with the protective film was picked up using a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.). A silicon chip on which a printed protective film was formed was obtained.

The silicon chip with a protective film was heat-processed at 260 degreeC for 10.8 minutes, and it returned to room temperature. This operation was repeated 3 times. This operation imitates the reflow process performed in the mounting process. Chips before heat treatment are indicated as "before reflow process", and chips after heat treatment are indicated as "after reflow process".

(Measurement of color)

Before and after the reflow process, for the printing part and the non-printing part, using SE6000 manufactured by Nippon Denshoku Industries Co., Ltd., the reflection furnace of a C/2 light source, CIE1976L ^* a ^* b ^* Brightness L ^* in the color space system, chromaticity a ^* , chromaticity b ^* was measured.

The color difference ΔE ^* _ab and the lightness difference ΔL ^* of the printing part and the non-printing part were calculated. A result is shown in Table 1.

(Evaluation of visibility)

The following criteria evaluated whether printing could be visually recognized before and behind a reflow process. In addition, a result is shown in Table 1.

· Good: The number of people who were able to recognize the printing was 4 out of 5 people or more

· Possible: 2 to 3 people out of 5 who were able to recognize the printing

Defect: The number of people who were able to recognize the print was less than 1 out of 5 people.

[Examples 2, 3, Comparative Example 1]

Production of the composition for films for thermosetting protective film formation WHEREIN: Except having changed each component as shown in Table 1, it carried out similarly to Example 1, the protective film formation sheet was manufactured, and the silicone chip with a protective film was obtained. Evaluation was carried out in the same manner as in Example 1. A result is shown in Table 1.

From the above result, according to the film for protective film formation which concerns on this embodiment, at the time of hardening of the film for protective film formation, or a reflow process. WHEREIN: Even when the line|wire width of printing is narrow, it was confirmed that sufficient printing visibility is acquired.

1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H: sheet for forming a protective film
10: support sheet
10a: surface of support sheet
10b: the back side of the support sheet (exposed side)
11: description
11a: the surface of the substrate
11b: the back side of the substrate
12: adhesive layer
12a: the surface of the pressure-sensitive adhesive layer
13, 23: protective film forming layer
13a, 23a: the surface of the protective film forming layer
14: coating layer;
14a: surface of the coating layer
14b: the back side of the coating layer
15: release film
15a: surface of release film

Claims (7)

A film for forming a protective film that is laser-printed on the surface,
In the coordinates specified by the CIE1976L ^* a ^* b ^* color space system, the color of the printing part is set to lightness L ^* _p , chromaticity a ^* _p , and chromaticity b ^* _p , and at the coordinates specified by the CIE1976L ^* a ^* b ^* color space system , when the color of the non-printing part is lightness L ^* _N , chromaticity a ^* _N , and chromaticity b ^* _N ,
The film for protective film formation whose color difference (DELTA)E ^* _ab of the printing part and the non-printing part defined by following formula (A) is 8 or more.
ΔE ^* _ab = [(L ^* _p - L ^* _N ) ² + (a ^* _p - a ^* _N ) ² + (b ^* _p - b ^* _N ) ² ] ^1/2 … (A) The method of claim 1,
The film for protective film formation whose brightness difference (DELTA)L ^* of the printing part and the non-printing part defined by following formula (B) is 8 or more.
ΔL ^* = [(L ^* _p - L ^* _N ) ² ] ^1/2 … (B) 3. The method according to claim 1 or 2,
The brightness L ^* _p of the printing part and the brightness L ^* _N of the non-printing part satisfy L ^* _p > L ^* _N , the film for forming a protective film. 4. The method according to any one of claims 1 to 3,
The color of the printing part and the color of the non-printing part are the colors measured after laser printing and curing the protective film forming film by heating at 130° C., the protective film forming film. 4. The method according to any one of claims 1 to 3,
The color of the printing part and the color of the non-printing part are the colors measured after laser printing, curing the protective film forming film by heating at 180 ° C., and then heating at 260 ° C. for 10.8 minutes three times. film. 6. The method according to any one of claims 1 to 5,
A film for forming a protective film, wherein the printing portion includes a portion having a line width of 50 μm or less. The film for forming a protective film according to any one of claims 1 to 6;
A sheet for forming a protective film comprising a supporting sheet.

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