KR20220020768A - Protective film formation sheet roll and manufacturing method for protective film formation sheet roll - Google Patents

Abstract

An object of the present invention is to provide a protective film forming sheet roll and a manufacturing method thereof, in which marks caused by winding of a protective film forming film resulting in marks on a protective film are less likely to occur. The present invention relates to a protective film forming sheet roll and a manufacturing method thereof. The protective film forming sheet roll is a sheet roll formed by winding a long sheet having a protective film forming film, a first release film on one side of the same, and a second release film on the other side. When the peeling force of the first release film from the protective film forming film is F1, and the peeling force of the second release film is F2, F1 > F2 is satisfied. A loss tangent tanδ_10 of the protective film forming film at 10℃ is 1.2 or less. In a direction where the winding axis of the sheet roll is vertical, when gravity is applied to the wound long sheet and when a maximum displacement amount of the long sheet in the vertical direction is A [mm], A / tanδ_10 is greater than or equal to 2.0.

Description

The manufacturing method of the sheet roll for protective film formation, and the sheet roll for protective film formation TECHNICAL FIELD

This invention relates to the manufacturing method of the sheet roll for protective film formation, and the sheet roll for protective film formation. In particular, it relates to a sheet roll for forming a protective film in which traces resulting from winding of a film for forming a protective film that cause traces of the protective film are less likely to occur, and a method for manufacturing the sheet roll for forming the protective film.

In recent years, manufacturing a semiconductor device by the mounting method called flip-chip bonding is implemented. In this mounting method, when a semiconductor chip having a circuit surface on which convex electrodes such as bumps are formed is mounted, the circuit surface side of the semiconductor chip is inverted (face down) to the chip mounting portion and joined. Accordingly, the semiconductor device has a structure in which the back side of the semiconductor chip on which no circuit is formed is exposed.

For this reason, in many cases, a hard protective film made of an organic material is formed on the back side of the semiconductor chip in order to protect the semiconductor chip from impacts such as during transport. Such a protective film is made to harden, for example, after sticking a protective film formation film on the back surface of a semiconductor wafer, or it is formed in the non-hardened state.

A protective film formation film comprises the sheet|seat for protective film formation of a long picture with the support film which supports a protective film formation film. Before using this elongate sheet|seat normally using a protective film formation film, it is wound up and it is set as a sheet roll. And when using a protective film formation film, the elongate protective film formation sheet unwound from a sheet roll is affixed on a semiconductor wafer, after cut out in the shape substantially the same as the semiconductor wafer to be affixed.

Patent Document 1 discloses a long adhesive sheet in which a first sheet and a second sheet are formed on both surfaces of an adhesive layer. An adhesive bond layer is isolate|separated into a punching part and a continuous dregs part, and the adhesive bond layer of a punching part is affixed as an adhesive bond film on the back surface of a semiconductor wafer, for example.

International Publication No. 2017/145735

The sheet roll for protective film formation is formed by fixing the manufactured long sheet for protective film formation to a core part using a seam fixing tape, and winding it up, applying predetermined tension to the elongate protective film formation sheet with a winding device. As a result, stress remains in the wound-up sheet|seat for protective film formation (sheet roll for protective film formation) of the elongate shape, and the winding pressure is generate|occur|produced in the direction toward a core part. This winding pressure is large in the sheet|seat for protective film formation close to a core part, ie, the sheet|seat for protective film formation which has begun to wind up, and it exists in the tendency small in the sheet|seat for protective film formation on the outer peripheral side of a sheet roll.

In addition, even in the same sheet roll for forming a protective film due to variations in tension at the time of winding, a point under strong pressure and a point under pressure are generated. In some cases, traces (winding traces) resulting from In particular, the winding pressure is large at the point at which the sheet for forming a protective film is started to be wound, and at the same time, the deviation in the winding pressure between the winding points in the width direction is likely to occur. Moreover, since the level|step difference resulting from the thickness of the seam fixing tape and the sheet|seat for protective film formation arises, it originates in this level|step difference, and a winding pressure becomes large, or it becomes easy to generate|occur|produce the dispersion|variation of a winding pressure in the width direction. Therefore, it is easy to generate|occur|produce after winding up the winding trace by strongly pressurizing the sheet|seat for protective film formation close to a deep part rather than the sheet|seat for protective film formation of the outer peripheral side of a sheet roll partially. When such a winding trace generate|occur|produces, a winding trace will generate|occur|produce also in the protective film formation film which comprises the sheet|seat for protective film formation. As a result, even when the protective film forming film is affixed to a work and a protective film is formed, the wound trace remains and will raise the appearance defect of a protective film.

However, even if it adjusted the setting conditions of a winding device when forming a sheet roll, there existed a problem that it was difficult to suppress completely the winding trace accompanying the dispersion|variation in the said winding pressure, etc.

The present invention has been made in view of such an actual situation, and a sheet roll for forming a protective film in which traces resulting from winding of a film for forming a protective film causing traces of the protective film are less likely to occur, and a method for manufacturing the sheet roll for forming a protective film is intended to provide

Aspects of the present invention are as follows.

[1] a protective film forming film;

A first peeling film formed on one surface of the protective film forming film;

A sheet roll formed by winding a long sheet having a second release film formed on the other surface of the protective film forming film,

When the peeling force of the first release film from the protective film-forming film is F1 and the peeling force of the second release film from the protective film-forming film is F2, the relationship of F1 > F2 is satisfied,

When the loss tangent at 10° C. of the protective film forming film is tan δ ₁₀ , tan δ ₁₀ is 1.2 or less,

In the direction in which the winding axis of the sheet roll becomes the vertical direction, when gravity is applied to the wound long sheet, when the maximum displacement of the long sheet in the vertical direction is A [mm], A/tanδ ₁₀ is 2.0 It is a sheet roll for protective film formation which satisfy|fills the above relationship.

[2] The sheet roll for forming a protective film according to [1], wherein in the first release film and/or the second release film, the surface not in contact with the protective film forming film is subjected to a release treatment.

[3] The sheet roll for forming a protective film according to [1] or [2], wherein the maximum displacement A is 2 mm or more.

[4] The sheet roll for forming a protective film according to any one of [1] to [3], wherein tanδ ₁₀ is 0.04 or more.

[5] A method for producing the sheet roll for forming a protective film according to any one of [1] to [4], the method comprising:

It is a manufacturing method of the sheet roll for protective film formation which has the process of storing the sheet roll for protective film formation at the storage temperature of 10 degrees C or less for 25 days or more among 60 days after formation of the sheet roll for protective film formation.

ADVANTAGE OF THE INVENTION According to this invention, the sheet roll for protective film formation in which the trace resulting from winding-up of the protective film formation film which causes traces of a protective film does not generate|occur|produce easily, and the method of manufacturing the sheet roll for protective film formation can be provided.

It is a perspective schematic diagram of an example of the sheet roll for protective film formation which concerns on this embodiment.
FIG. 1B is an enlarged cross-sectional schematic view of a portion IB of FIG. 1A .
It is a schematic diagram for demonstrating the maximum displacement amount A of an elongate sheet|seat.
3 : is a cross-sectional schematic diagram of an example of the sheet|seat for protective film formation which concerns on this embodiment.
It is a cross-sectional schematic diagram which shows that a 1st peeling film and a 2nd peeling film have a 1st release agent layer and a 2nd release agent layer.
5 : is a perspective schematic diagram of the elongate sheet|seat in which the cut-out was formed by drawing out from the sheet roll for protective film formation which concerns on this embodiment.
It is a cross-sectional schematic diagram which shows that the laminated body of a protective film formation film and a 1st peeling film is affixed to a work.
It is a cross-sectional schematic diagram which shows that the protective film formation film affixed to the work was turned into a protective film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail using drawings based on specific embodiment.

First, the main terms used in this specification will be described.

The work is a plate-shaped body to which a protective film forming film is affixed and processed. As a work, a wafer and a panel are mentioned, for example. Specifically, a semiconductor wafer and a semiconductor panel are mentioned. As a workpiece of a workpiece, a chip obtained by dividing a wafer into pieces is mentioned, for example. Specifically, a semiconductor chip obtained by separating a semiconductor wafer into pieces is exemplified. In this case, the protective film is formed on the back surface side of the wafer.

The "front" of the work indicates a surface on which convex electrodes such as circuits and bumps are formed, and the "back" indicates a surface on which no circuits are formed.

In this specification, for example, "(meth)acrylate" is used as a word indicating both of "acrylate" and "methacrylate", and the same applies to other similar terms.

In this specification, the weight ratio of the component which comprises each composition is represented by solid content ratio.

(1. Sheet roll for forming a protective film)

The sheet roll 100 for protective film formation which concerns on this embodiment is a roll by which the elongate sheet 1 for forming a protective film was wound, as shown to FIG. 1A.

In the present embodiment, the long sheet 1 has a protective film forming film, a first peeling film formed on one main surface of the protective film forming film, and a second peeling formed on the other main surface of the protective film forming film. It is a sheet for forming a protective film having a film. Hereinafter, the elongate sheet|seat 1 may be called the sheet|seat 1 for protective film formation. The detail of the elongate sheet|seat 1 is mentioned later.

As shown in FIG. 1B, after such a sheet roll 100 fixes the elongate sheet|seat 1 to the core part 70 through fixing means 80, such as a seam fixing tape, by a winding device. It is formed by winding the elongate sheet 1 around the core 70 while applying a predetermined tension to the sheet 1 . As described above, in the sheet roll in which winding has been completed, variations in winding pressure are generated, and particularly, in the long sheet close to the core, the protective film forming film is wound at the point being strongly pressurized, resulting in traces of the protective film. traces are easy to form.

It is estimated that the winding pressure at the point where the winding pressure is high gradually decreases with the lapse of time after the formation of the back side and the sheet roll, that is, after the winding is finished, and approaches the winding pressure at the point where the winding pressure is low. In other words, it is estimated that the dispersion|variation in a winding pressure is eliminated with time, and the winding pressure in a sheet roll is stabilized (averaged). Therefore, although the dispersion|variation in the winding pressure in a sheet roll is finally eliminated considerably, the winding trace formed until the dispersion|variation in a winding pressure is eliminated remains in a protective film formation film even if the dispersion|variation in a winding pressure is eliminated.

Then, in this embodiment, suppressing generation|occurrence|production of a winding trace by controlling the characteristic of a sheet roll and a protective film formation film as follows until the winding pressure in a sheet roll is stabilized based on the said guess, It promotes pressure stabilization.

(1.1 Slippery properties of long sheets)

In order to promote the stabilization of the winding pressure, it is necessary to disperse the winding pressure concentrated at a point where the winding pressure is high. As shown in FIG. 1B, in the sheet roll 100, the long sheets 1 are laminated|stacked in the radial direction, and the long sheets 1 comrades are in direct contact. Therefore, even at a point where the winding pressure is high, if the contacting long sheets 1 comrades can move to each other, the long sheet 1 slides in the direction in which the winding pressure decreases, and the winding pressure is dispersed.

However, when the long sheets are in strong contact with each other (when the winding pressure is high), the long sheets are less slippery, so that they are difficult to move to each other. On the other hand, when the long sheets are in weak contact (when the winding pressure is low), the long sheets are easily slippery, so they are easy to move to each other. Therefore, it is necessary to consider the winding pressure of a sheet roll, and to make the sliding property of an elongate sheet|seat into a predetermined|prescribed relationship.

In this embodiment, as a parameter indicating the slipperiness of the long sheet taking the winding pressure of the sheet roll into account, in the direction in which the winding axis of the sheet roll becomes the vertical direction, when gravity is applied to the long sheet wound in the core, the vertical The maximum amount of displacement of the long sheet in the direction is adopted. Specifically, as shown in FIG. 2 , in a state in which only the core portion 70 of the sheet roll is supported, the sheet roll 100 is lifted 150 mm in the direction in which the winding axis O of the sheet roll 100 is in the vertical direction. up and hold for a certain amount of time. After a predetermined time elapses, the maximum value of the slip amount of the long sheet from the upper end of the core is defined as the maximum displacement amount of the long sheet. This maximum displacement amount is shown as A [mm] in FIG. 2 .

This maximum amount of displacement A is the maximum amount of displacement A when the winding conditions (tension, etc.) at the time of winding the long sheet are different even if the materials and dimensions of the films (protective film-forming film, release film, etc.) constituting the long sheet are the same. is changing That is, the maximum displacement amount A is a parameter in which the slipperiness|slidability of the elongate sheet|seat in a sheet roll was reflected as a result of considering predetermined|prescribed winding condition.

This inventor found that stabilization of a winding pressure could be accelerated|stimulated, suppressing generation|occurrence|production of a winding trace by the maximum displacement amount A and the loss tangent of the protective film formation film in 10 degreeC mentioned later satisfy|filling a predetermined|prescribed relationship . As a result, a sheet roll WHEREIN: It becomes difficult to generate|occur|produce a wound trace especially in the protective film formation film of the elongate sheet|seat close|similar to a deep part. Therefore, the appearance defect of the protective film does not occur, and the long sheet wound on the sheet roll can be used up without waste. In addition, the loss tangent of the protective film formation film in 10 degreeC is a parameter concerning generation|occurrence|production of a winding trace.

Specifically, when the loss tangent of the protective film formation film at 10°C is tanδ ₁₀ , A/tanδ ₁₀ is 2.0 or more. A/tanδ ₁₀ is preferably 10 or more, 40 or more, 90 or more, and 200 or more. Moreover, although the upper limit of A/tan δ ₁₀ is not particularly limited, in the present embodiment, it is preferably 3750 or less, 1500 or less, and 750 or less.

Moreover, in this embodiment, the maximum displacement A becomes like this. Preferably they are 2 mm or more, 4 mm or more, 10 mm or more, 20 mm or more, 35 mm or more, and 50 mm or more. When the lower limit of the maximum displacement A is the above value, stabilization of the winding pressure can be further promoted. Moreover, the maximum displacement amount A becomes like this. Preferably they are 150 mm or less, less than 150 mm, less than 125 mm, and less than 100 mm. When the upper limit of the maximum displacement amount A is the above value, the long sheet wound up unintentionally slips away from the core during handling of the sheet roll, and the long sheet falls off from the core, and the handling property of the sheet roll decreases. it can be prevented

(2. Sheet for forming a protective film)

Next, the sheet|seat for protective film formation which is a long sheet|seat of the sheet roll which concerns on this embodiment is demonstrated. As for the sheet|seat 1 for protective film formation as an elongate sheet, as shown in FIG. 3, the 1st peeling film 20 is arrange|positioned on one main surface 10a of the protective film formation film 10, The other main surface 10b ) has a configuration in which the second release film 30 is disposed. The sheet|seat 1 for protective film formation is used in order to stick a protective film formation film to a workpiece|work. The protective film forming film is formed into a protective film after being affixed to the work to form a protective film for protecting the work or the workpiece of the work.

In this embodiment, in order to affix a protective film formation film to a work, the sheet|seat for protective film formation is drawn out from the sheet roll for protective film formation, and it cut|disconnects into a predetermined shape. Thereafter, the protective film forming film is affixed to the back surface of the work to form a protective film.

(3. Protective film forming film)

As described above, the protective film forming film is formed into a protective film after being affixed to the work to form a protective film for protecting the work or the workpiece of the work.

"To form a protective film" means to make the protective film-forming film into a state having sufficient characteristics to protect a work or a workpiece of the work. Specifically, when a protective film formation film is curable, "it turns into a protective film" means using an uncured protective film formation film as hardened|cured material. In other words, the protective film formation film formed into a protective film is hardened|cured material of the protective film formation film, and is different from a protective film formation film.

After the work is superposed on the curable protective film-forming film, by curing the protective film-forming film, the protective film can be firmly adhered to the work and a durable protective film can be formed.

On the other hand, when the protective film forming film does not contain a curable component and is used in a non-hardened state, when the protective film forming film is affixed to the work, the protective film forming film is turned into a protective film. In other words, the protective film formation film formed into a protective film is the same as that of the protective film formation film.

When high protective performance is not required, since it is not necessary to harden the protective film-forming film, use of the protective film-forming film is easy.

In this embodiment, it is preferable that the protective film formation film is curable. Therefore, it is preferable that a protective film is hardened|cured material. As a hardened|cured material, a thermosetting material and an energy-beam hardened|cured material are illustrated, for example. In this embodiment, it is more preferable that a protective film is a thermosetting material.

Moreover, it is preferable that a protective film formation film has adhesiveness at normal temperature (23 degreeC), or exhibits adhesiveness by heating. Thereby, when superimposing a workpiece|work on a protective film formation film, both can be bonded together. Therefore, before hardening a protective film formation film, positioning can be performed reliably.

The protective film formation film may be comprised by one layer (single layer), and may be comprised by multiple layers of two or more layers. When a protective film formation film has multiple layers, these multiple layers may mutually be same or different, and the combination in particular of the layer which comprises these multiple layers is not restrict|limited.

In this embodiment, it is preferable that the protective film formation film is one layer (single layer). The one-layer protective film forming film is easy to produce because high precision with respect to the thickness is obtained. Moreover, when a protective film formation film is comprised by multiple layers, it is necessary to consider the adhesiveness between layers and elasticity of each layer, and it originates in these and there exists a risk that peeling from a to-be-adhered body arises. When the protective film formation film is one layer, the said risk can be reduced and the freedom degree of design also increases.

Although the thickness in particular of a protective film formation film is not restrict|limited, Preferably they are less than 100 micrometers, 70 micrometers or less, 45 micrometers or less, and 30 micrometers or less. By making the upper limit of the thickness of a protective film formation film into the said value, the level|step difference resulting from the thickness of the sheet|seat for protective film formation at the point which started to wind up can be made small.

Moreover, the thickness of a protective film formation film becomes like this. Preferably they are 5 micrometers or more, 10 micrometers or more, and 15 micrometers or more. By setting the lower limit of the thickness of the protective film forming film to the above value, the performance of protecting the work as a protective film is easily obtained, and in the sheet roll for forming a protective film, the protective film forming film functions to relieve stress, The length from the deep part that begins to occur can be made shorter.

In addition, the thickness of a protective film formation film means the thickness of the whole protective film formation film. For example, the thickness of the protective film formation film comprised from multiple layers means the thickness of the sum total of all the layers which comprise a protective film formation film.

(3.1 Loss tangent of protective film forming film at 10°C)

In this embodiment, the loss tangent (tanδ ₁₀ ) of the protective film formation film at 10°C is 1.2 or less. The loss tangent is defined as "loss modulus/storage modulus", and is a value measured in response to a stress applied to an object by a dynamic viscoelasticity measuring device. By making the loss tangent of the protective film forming film within the above range at 10 ° C., the components constituting the protective film forming film become slightly elastic and the protective film forming film is not easily deformed. It tends to not turn out well. In addition, by storing the sheet roll at a temperature lower than normal temperature (23° C.) until the winding pressure of the sheet roll is stabilized, it becomes easy to suppress the formation of winding traces on the protective film forming film in the sheet roll, so in this embodiment, The loss tangent of the protective film formation film in 10 degreeC is controlled.

It is preferable that it is 1.0 or less, as for the loss tangent (tanδ ₁₀ ) of the protective film formation film in 10 degreeC, it is more preferable that it is 0.9 or less, It is still more preferable that it is 0.8 or less. Moreover, it is preferable that it is 0.04 or more, and, as for the loss tangent (tanδ ₁₀ ) of the protective film formation film at 10 degreeC, it is more preferable that it is 0.1 or more, It is still more preferable that it is 0.2 or more, It is especially preferable that it is 0.3 or more. When the lower limit of the loss tangent of the protective film formation film in 10 degreeC is the said value, the phenomenon in which the protective film formation film curved in the sheet roll cracks in 10 degreeC can be prevented.

The loss tangent (tanδ ₁₀ ) of the protective film formation film at 10°C may be measured by a known method. For example, using the protective film forming film as a sample of a predetermined size, applying a deformation to the sample at a predetermined frequency in a predetermined temperature range by a dynamic viscoelasticity measuring device, measuring the elastic modulus, from the measured elastic modulus, The loss tangent (tanδ ₁₀ ) at 10°C can be calculated. A specific measurement method will be described in detail in Examples to be described later.

(3.2 Composition for protective film forming film)

As long as the protective film forming film has the above physical properties, the composition of the protective film forming film is not particularly limited. In this embodiment, it is preferable that the composition (composition for protective film formation films) which comprises a protective film formation film is a resin composition containing a polymer component (A), a curable component (B), and a filler (E) at least. The polymer component is a component that can be regarded as formed by a polymerization reaction of the polymerizable compound. Moreover, a sclerosing|hardenable component is a component which can harden (polymerize) react. In addition, in this invention, a polycondensation reaction is also contained in a polymerization reaction.

Moreover, the component contained in a polymer component may correspond also to a sclerosing|hardenable component. In this embodiment, when the composition for protective film formation films contains the component corresponding to both such a polymer component and a sclerosing|hardenable component, it is considered that the composition for protective film formation films contains both a polymer component and a sclerosing|hardenable component.

(3.2.1 Polymer Component)

A polymer component (A) provides an appropriate tack|tack and ensures uniform sticking of the protective film formation film with respect to a work|work, giving film formation (film-forming property) to a protective film formation film. The weight average molecular weight of a polymer component is 50,000-2 million normally, Preferably it is 100,000-1,500,000, Especially preferably, it exists in the range of 200,000-1 million. As such a polymer component, an acrylic resin, a urethane resin, a phenoxy resin, a silicone resin, saturated polyester resin etc. are used, for example, Especially an acrylic resin is used preferably.

In addition, in this specification, unless otherwise indicated, a "weight average molecular weight" is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method. The measurement by such a method is, for example, in a high-speed GPC apparatus "HLC-8120GPC" manufactured by Tosoh Corporation, a high-speed column "TSK guard column H _XL -H", "TSK Gel GMH _XL ", "TSK Gel G2000 H" _XL " (above, all manufactured by Tosoh Corporation) is used in this order, column temperature: 40 degreeC, liquid feeding rate: 1.0 ml/min, the detector is carried out as a differential refractometer.

As an acrylic resin, the (meth)acrylic acid ester copolymer which consists of structural units derived from a (meth)acrylic acid ester monomer and a (meth)acrylic acid derivative is mentioned, for example. Here, as a (meth)acrylic acid ester monomer, Preferably (meth)acrylic acid alkylester of C1-C18 alkyl group is mentioned, Specifically, (meth)acrylate methyl, (meth)ethyl acrylate, (meth) Propyl acrylate, (meth)butyl acrylate, etc. are mentioned. Moreover, as a (meth)acrylic acid derivative, (meth)acrylic acid, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. are mentioned, for example.

In this embodiment, it is preferable to introduce|transduce a glycidyl group into an acrylic resin using glycidyl methacrylate etc. The compatibility of the acrylic resin into which the glycidyl group is introduce|transduced and the epoxy resin as a thermosetting component mentioned later improves, and there exists a tendency for the protective film formation film of stable performance to be easy to be obtained. Moreover, in this embodiment, in order to control the adhesiveness with respect to a workpiece|work, and adhesive physical property, it is preferable to introduce|transduce a hydroxyl group into an acrylic resin using hydroxyethyl acrylate etc.

Preferably the glass transition temperature of an acrylic resin is -70-40 degreeC, -35-35 degreeC, -20-30 degreeC, -10-25 degreeC, and -5-20 degreeC. By making the lower limit of the glass transition temperature of an acrylic resin into the said value, it becomes easy to make tan-delta ₁₀ of a protective film formation film small. Moreover, by making the upper limit of the glass transition temperature of an acrylic resin into the said value, while raising the tack of a protective film formation film moderately, the adhesive force of the protective film formation film with the workpiece|work is improved, and the adhesive force of a protective film with the workpiece|work improves moderately.

When an acrylic resin has the structural unit of m types (m is an integer of 2 or more), the glass transition temperature of the said acrylic resin is computable as follows. That is, when a non-overlapping number from 1 to m is sequentially assigned to each of the m types of monomers that induce structural units in the acrylic resin, and named "monomer m", the glass transition temperature of the acrylic resin ( Tg) is computable using the formula of Fox shown below.

(wherein Tg is the glass transition temperature of the acrylic resin; m is an integer of 2 or more; Tg _k is the glass transition temperature of the homopolymer of the monomer m; W _k is a structural unit derived from the monomer m in the acrylic resin It is the mass fraction of m, provided that W _k satisfies the following formula)

(wherein m and W _k are the same as above)

As Tg _k , the value described in a polymer data handbook, an adhesive handbook, a Polymer Handbook, etc. can be used. For example, the Tg _k of the homopolymer of methyl acrylate is 10 ° C., the Tg _k of the homopolymer of n-butyl acrylate is -54 ° C., the Tg _k of the homopolymer of methyl methacrylate is 105 ° C., 2-hydride The Tg k of the homopolymer of oxyethyl acrylate is -15°C, the Tg _k of the homopolymer of glycidyl methacrylate is 41°C, and the Tg _k of 2-ethylhexyl acrylate _is -70°C.

Content of the polymer component when the total weight of the composition for protective film formation films makes 100 mass parts becomes like this. Preferably 5-80 mass parts, 8-70 mass parts, 10-60 mass parts, 12-55 mass parts, 14- It is 50 mass parts and 15-45 mass parts. By carrying out content of a polymer component in the said range, while raising the tack of a protective film formation film moderately, the adhesive force with the workpiece|work of a protective film formation film improves moderately. Moreover, there exists a tendency which is easy to suppress generation|occurrence|production of a winding trace.

(3.2.2 thermosetting components)

A sclerosing|hardenable component (B) hardens a protective film formation film, and forms a hard protective film. As the curable component, a thermosetting component, an energy ray-curable component, or a mixture thereof can be used. When hardening by irradiation of an energy ray, since a protective film formation film contains the filler, coloring agent, etc. which are mentioned later, the light transmittance falls. Therefore, for example, when the thickness of a protective film formation film becomes thick, energy-beam hardening tends to become inadequate.

On the other hand, even if the thickness of a thermosetting protective film formation film becomes thick, since it fully hardens|cures by heating, a protective film with high protective performance can be formed. Moreover, by using normal heating means, such as a heating oven, many protective film formation films can be heated collectively, and can be thermosetted.

Therefore, in this embodiment, it is preferable that a sclerosing|hardenable component is thermosetting. That is, it is preferable that a protective film formation film is thermosetting.

Whether or not the protective film forming film is thermosetting can be judged as follows. First, the protective film formation film of normal temperature (23 degreeC) is heated until it becomes the temperature exceeding normal temperature, Then, it is made into the protective film formation film after a heating and cooling by cooling until it becomes normal temperature. Next, when the hardness of the protective film forming film after heating and cooling is compared with the hardness of the protective film forming film before heating at the same temperature, when the protective film forming film after heating and cooling is harder, this protective film forming film is thermosetting judged to be

As a thermosetting component, an epoxy resin, a thermosetting polyimide resin, an unsaturated polyester resin, and these mixtures are used preferably, for example. Thermosetting polyimide resin is a generic term for the polyimide precursor and thermosetting polyimide which form a polyimide resin by thermosetting.

An epoxy resin as a thermosetting component has a property of forming a three-dimensional network structure when heated and forming a strong film. As such an epoxy resin, a well-known various epoxy resin is used. In this embodiment, the molecular weight (food) of an epoxy resin becomes like this. Preferably they are 300 or more and less than 50000, 300 or more and less than 10000, 300 or more and less than 5000, 300 or more and less than 3000. Moreover, it is preferable that it is 50-5000 g/eq, as for the epoxy equivalent of an epoxy resin, it is more preferable that it is 100-2000 g/eq, It is more preferable that it is 150-1000 g/eq.

Specific examples of such an epoxy resin include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl-type or alkylglycidyl-type epoxy resins in which active hydrogen bonded to a nitrogen atom, such as aniline isocyanurate, is substituted with a glycidyl group; Vinylcyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) ) such as cyclohexane-m-dioxane and the like, so-called alicyclic epoxides into which an epoxy is introduced by, for example, oxidation of a carbon-carbon double bond in the molecule. In addition, the epoxy resin which has a biphenyl skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, etc. can also be used.

When using a thermosetting component as a sclerosing|hardenable component (B), it is preferable to use a hardening|curing agent (C) together as an adjuvant. As the curing agent for the epoxy resin, a heat-activated latent epoxy resin curing agent is preferable. A "thermal active latent epoxy resin curing agent" is a curing agent of a type that does not react well with an epoxy resin at room temperature (23°C), but is activated by heating at a certain temperature or higher and reacts with the epoxy resin. Examples of the activation method of the thermally active latent epoxy resin curing agent include a method of generating active species (anions, cations) by a chemical reaction by heating; a method in which it is stably dispersed in the epoxy resin in the vicinity of room temperature, and is compatible and dissolved with the epoxy resin at a high temperature to initiate a curing reaction; A method of initiating a curing reaction by eluting at a high temperature with a molecular sieve encapsulation type curing agent; A method using microcapsules and the like exist.

Among the exemplified methods, a method is preferable in which it is stably dispersed in the epoxy resin near room temperature and is compatible and dissolved with the epoxy resin at a high temperature to initiate a curing reaction.

Specific examples of the thermally active latent epoxy resin curing agent include various onium salts, dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, and high melting point active hydrogen compounds such as imidazole compounds. there is. These thermally active latent epoxy resin curing agents can be used individually by 1 type or in combination of 2 or more type. In this embodiment, dicyandiamide is especially preferable.

Moreover, as a hardening|curing agent with respect to an epoxy resin, a phenol resin is also preferable. As a phenol resin, the condensate in particular of phenols, such as alkylphenol, polyhydric phenol, and naphthol, and aldehydes, etc. are not restrict|limited and used. Specifically, phenol novolac resin, o-cresol novolac resin, p-cresol novolak resin, t-butylphenol novolac resin, dicyclopentadiencresol resin, polyparavinylphenol resin, bisphenol A type novolac resin , or modified products thereof, etc. are used.

The phenolic hydroxyl group contained in these phenol resins can easily add-react with the epoxy group of the said epoxy resin by heating, and can form the hardened|cured material with high impact resistance.

To [ content of a hardening|curing agent (C) / 100 mass parts of epoxy resins], Preferably they are 0.01-30 mass parts, 0.1-20 mass parts, 0.2-15 mass parts, 0.3-10 mass parts. By making the range of content of a hardening|curing agent (C) into the said range, the performance which protects a workpiece|work as a protective film is easy to be acquired.

When using dicyandiamide as a hardening|curing agent (C), it is preferable to use together a hardening accelerator (D) further. Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, Preferred are imidazoles such as 2-phenyl-4-methyl-5-hydroxymethylimidazole (imidazole in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms). Among these, 2-phenyl-4,5-dihydroxymethylimidazole is especially preferable.

To [ content of a hardening accelerator / 100 mass parts of epoxy resins ], Preferably they are 0.01-30 mass parts, 0.1-20 mass parts, 0.2-15 mass parts, 0.3-10 mass parts. By making the range of content of a hardening accelerator (D) into the said range, the performance which protects a workpiece|work as a protective film is easy to be acquired.

The total content of the thermosetting component and the curing agent when the total weight of the composition for protective film forming films is 100 parts by mass is preferably 3 to 80 parts by mass, 5 to 60 parts by mass, 7 to 50 parts by mass, and 9 to 40 parts by mass. part, 10-30 mass parts. When a thermosetting component and a hardening|curing agent are mix|blended in such a ratio, the performance which protects a workpiece|work as a protective film is easy to be acquired.

(3.2.3 Energy-ray-curable component)

When a sclerosing|hardenable component (B) is an energy ray-curable component, it is preferable that it is non-hardened, and, as for an energy-beam sclerosing|hardenable component, it is preferable to have adhesiveness, and it is more preferable to have non-hardening and adhesiveness.

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

As an energy-beam curable component, the compound which has an energy-beam curable group is preferable, for example. As such a compound, a well-known thing is mentioned.

(3.2.4 Filling)

When a protective film formation film contains a filler (E), adjustment of a thermal expansion coefficient becomes easy for the protective film obtained by making a protective film formation film into a protective film. By bringing this coefficient of thermal expansion closer to the coefficient of thermal expansion of the work, the reliability of adhesion to the work is further improved. Moreover, when a protective film formation film contains a filler (E), a hard protective film is obtained and the performance which protects a workpiece|work is easy to be acquired, and the moisture absorption rate of a protective film can be reduced.

Although any of an organic filler and an inorganic filler may be sufficient as a filler (E), it is preferable that it is an inorganic filler from a viewpoint of the shape stability in high temperature like 260 degreeC.

As a preferable inorganic filler, For example, powders, such as a silica, an alumina, a talc, a calcium carbonate, bengala, a silicon carbide, and boron nitride; Beads obtained by spheroidizing these inorganic fillers; The surface-modified product of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned. Among these, silica and surface-modified silica are preferable. The surface-modified silica is preferably surface-modified with a coupling agent, and more preferably surface-modified with a silane coupling agent.

The average particle diameter of the filler is preferably 0.02 to 10 µm, 0.05 to 5 µm, and 0.10 to 3 µm.

By making the range of the average particle diameter of a filler into the said range, the handleability of the composition for protective film formation films becomes favorable. As a result, the composition for protective film formation films and the quality of a protective film formation film are easy to stabilize.

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

Content of the filler when the total weight of the composition for protective film formation films is 100 mass parts becomes like this. Preferably they are 15-80 mass parts, 30-75 mass parts, 40-70 mass parts, 45-65 mass parts.

By making the lower limit of content of a filler into the said value, it exists in the tendency for it to become easy to make small tan-delta ₁₀ of a protective film formation film. Moreover, by making the upper limit of content of a filler into the said value, the adhesive force of a protective film formation film with the workpiece|work improves, and there exists a tendency for the adhesive force of a protective film with the workpiece|work to improve moderately.

(3.2.5 Coupling agent)

It is preferable that a protective film formation film contains a coupling agent (F). By containing a coupling agent, after hardening of a protective film formation film WHEREIN: While not impairing the heat resistance of a protective film, while being able to improve the adhesiveness of a protective film and a workpiece|work, water resistance (moisture and heat resistance) can be improved. As a coupling agent, a silane coupling agent is preferable from a viewpoint of the versatility and cost advantage.

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. -(methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ- Aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types.

(3.2.6 Colorant)

It is preferable that a protective film formation film contains a coloring agent (G). Thereby, since the back surface of the workpiece|work of a workpiece|work, such as a chip|tip, is concealed, various electromagnetic waves generated in an electronic device can be interrupted|blocked, and malfunction of the workpiece|work of a workpiece|work, such as a chip|tip, can be reduced.

As a coloring agent (G), well-known things, such as an inorganic type pigment, an organic type pigment, and organic type dye, can be used, for example. In this embodiment, an inorganic pigment is preferable.

Examples of inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium pigments). Tin oxide) type pigment|dye, ATO (antimony tin oxide) type pigment|dye, etc. are mentioned. Among these, it is especially preferable to use carbon black. According to carbon black, electromagnetic waves in a wide wavelength range can be blocked.

The compounding amount of the colorant (especially carbon black) in the protective film-forming film also varies depending on the thickness of the protective film-forming film. For example, when the thickness of the protective film-forming film is 20 µm, with respect to the total mass of the protective film-forming film. , Preferably it is 0.01-10 mass %, 0.04-7 mass %, and 0.07-4 mass %. By making the compounding quantity of a coloring agent into the said range, there exists a tendency which can make the trace of the protective film which the winding trace of the sheet|seat roll for protective film formation produces inconspicuous on an external appearance.

It is preferable that the average particle diameter of a coloring agent (especially carbon black) is 1-500 nm, It is especially preferable that it is 3-100 nm, Furthermore, it is preferable that it is 5-50 nm. When the average particle diameter of the colorant is within the above range, it is easy to control the light transmittance to a desired range.

(3.2.7 Other additives)

The composition for protective film formation films is within the range which does not impair the effect of this invention, As another additive, For example, a photoinitiator, a crosslinking agent, a plasticizer, an antistatic agent, antioxidant, a gettering agent, a tackifier, You may contain a release agent etc.

(4. First release film)

A 1st peeling film is a film which can support a protective film formation film so that peeling is possible. In this embodiment, it is preferable that a 1st peeling film peels from a protective film formation film, after affixing a protective film formation film to a workpiece|work.

The 1st peeling film may be comprised from the base material of one layer (single layer) or two or more layers, and from a viewpoint of controlling peelability, the peeling process of the surface of a base material may be carried out. That is, the surface of the base material may be modified, and a material not derived from the base material may be formed on the surface of the base material.

In this embodiment, it is preferable that a 1st peeling film has a base material and a 1st release agent layer. By having a 1st releasing agent layer, it is easy to control the physical property of the surface in which the 1st releasing agent layer is formed in a 1st peeling film.

Moreover, in this embodiment, in addition to the surface by the side of the protective film formation film of a 1st peeling film, it is preferable that a 1st release agent layer is formed also in the surface on the opposite side. That is, as shown in FIG. 4, in the sheet|seat 1 for protective film formation, the 1st peeling film 20 is the 1st release agent layer 22 formed in the main surface of both the base material 21 and the base material 21. , 23) has The main surface 20b of the 1st release film (the main surface 20b of the 1st release agent layer 22) contact|connects the main surface 10a of the protective film formation film. The 1st releasing agent layer 22 and the 1st releasing agent layer 23 may be comprised from the same composition, and may be comprised from the different composition.

In the sheet roll, since the long sheets 1 are laminated in the radial direction, the surface 20a of the first release film not in contact with the protective film forming film is the surface 30b of the second release film not in contact with the protective film forming film. ) is in contact with Therefore, in a 1st peeling film, when the surface 20a which is not in contact with a protective film formation film is peeled (by forming the 1st release agent layer 23), the contacting elongate sheets slide. Since it becomes easy, stabilization of a winding pressure can be accelerated|stimulated.

1st release film WHEREIN: It is preferable that the 1st release agent layer is formed directly in the surface of a base material. By forming the 1st release agent layer directly on the surface of a base material, since production of a 1st release film becomes easy, cost reduction is implement|achieved.

Moreover, when a 1st release agent layer is formed on both main surfaces of a base material, you may apply|coat and form the coating agent containing the composition for 1st release agent layers mentioned later to both main surfaces of a base material, and you may form 1st on one main surface of a base material. After applying the coating agent containing the release agent layer composition, the base material is wound into a roll, and the component of the first release agent layer composition is transferred from the main surface on which the coating agent is applied to the main surface on which the coating agent is not applied (transition phenomenon). Then, you may form a 1st release agent layer in the main surface to which the coating agent is not apply|coated.

Although the thickness in particular of a 1st peeling film is not restrict|limited, It is preferable that they are 30 micrometers or more and 100 micrometers or less. Moreover, as for the thickness of a 1st peeling film, it is more preferable that it is 40 micrometers or more, and it is still more preferable that it is 45 micrometers or more. Moreover, it is more preferable that it is 80 micrometers or less, and, as for the thickness of a 1st peeling film, it is still more preferable that it is 70 micrometers or less.

When the lower limit of the thickness of a 1st peeling film is the said value and forms the cut which reaches to a part of 1st peeling film using the cutting blade mentioned later, a cutting blade penetrates a 1st peeling film, and a 1st peeling film can be prevented from being cut. Moreover, the sheet|seat roll for protective film formation WHEREIN: A 1st peeling film functions to relieve|moderate a stress, and length from the core part which a winding trace begins to produce can be made shorter more.

Further, since the upper limit of the thickness of the first release film is the above value, the protective film forming sheet is fed out, the protective film forming film is cut out, and the protective film forming sheet is passed through rollers such as guide rollers in the apparatus until it is conveyed to the next step. However, it can prevent that a protective film formation film peels from a 1st peeling film at that time. Moreover, the level|step difference resulting from the thickness of the sheet|seat for protective film formation at the point where winding-up started can be made small.

In addition, the thickness of a 1st peeling film means the thickness of the whole 1st peeling film. For example, the thickness of the 1st peeling film comprised from multiple layers means the thickness of the sum total of all the layers which comprise a 1st peeling film.

1st peeling film WHEREIN: WHEREIN: Whether the peeling process is carried out by the base material can be judged as follows, for example. When the first release agent layer contains a silicone-based release agent described later, surface analysis is performed on both main surfaces of the first release film by X-ray photoelectron spectroscopy (XPS), and the ratio of silicon atoms is calculated from the obtained spectrum, , it is judged that the peeling process is carried out as it is more than a predetermined value. A specific measurement method will be described in detail in Examples to be described later.

Moreover, when a base material is comprised from the polyethylene terephthalate film mentioned later, in both main surfaces of the 1st peeling film, the contact angle of water is measured, and if the contact angle is a predetermined value or more, it is judged that the peeling process has been carried out. A specific measurement method will be described in detail in Examples to be described later.

In the present embodiment, in the sheet for forming a protective film, when the peeling force of the first release film from the protective film forming film is F1, and the peeling force of the second release film described later from the protective film forming film is F2 , F1 and F2 satisfy the relationship F1 > F2. By satisfying such a relationship, when removing a 2nd peeling film from the sheet|seat for protective film formation, the protective film formation film 10 which should remain is not removed together with a 2nd peeling film, but the protective film formation film 10 is first It becomes easy to leave on a peeling film.

Accordingly, the first release film is a medium release film, and the second release film is a light release film.

In the present embodiment, F1 and F2 are load values measured using a tensile tester. A specific measurement method will be described in detail in Examples to be described later.

Hereinafter, the case where a 1st peeling film has a base material and a 1st release agent layer is demonstrated.

(4.1 Description)

The base material of the first release film is not particularly limited as long as it is a material capable of supporting the protective film-forming film until the protective film-forming film is affixed to the work, and usually a film mainly composed of a resin-based material (hereinafter referred to as "resin film").

Specific examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutyl Renterephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyvinyl chloride film A mid film, a fluororesin film, etc. are used. Moreover, these crosslinked films are also used. Moreover, these laminated|multilayer films may be sufficient. In this embodiment, a polyethylene terephthalate film is preferable from a viewpoint of suppressing the winding accompanying extending|stretching of a base material in addition to viewpoints, such as environmental safety and cost.

A base material may contain various additives, such as a coloring agent, a flame retardant, a plasticizer, an antistatic agent, a lubricating agent, and a filler, in the said resin film.

The thickness of a base material can function suitably in each process in which the sheet|seat for protective film formation is used, In the range of the thickness of the said 1st peeling film, it is not specifically limited. It is preferable that the thickness of a base material is 30 micrometers or more and 100 micrometers or less. Moreover, as for the thickness of a base material, it is more preferable that it is 40 micrometers or more, and it is still more preferable that it is 45 micrometers or more. Moreover, it is more preferable that it is 80 micrometers or less, and, as for the thickness of a base material, it is still more preferable that it is 70 micrometers or less.

(4.2 First Release Agent Layer)

A 1st release agent layer provides peelability from a protective film formation film to a 1st peeling film. Moreover, in a 1st peeling film, when the 1st release agent layer is formed in the surface which is not in contact with the protective film formation film, slipperiness is provided to the contacting elongate sheet|seat. The first release agent layer will not be particularly limited as long as it is composed of a material capable of imparting peelability. In this embodiment, a 1st releasing agent layer hardens|cures the composition for 1st releasing agent layers containing a mold release agent, and is obtained.

In addition, when the first release agent layer is formed on the surface that is not in contact with the protective film-forming film, the first release agent layer is formed on the surface that is in contact with the protective film-forming film and is formed on the surface that is not in contact with the protective film-forming film The 1st release agent layer may be comprised from the same composition, and may be comprised from the different composition.

Although the thickness in particular of a 1st releasing agent layer is not restrict|limited, It is preferable that they are 30 nm or more and 200 nm or less. Moreover, it is more preferable that it is 50 nm or more, and, as for the thickness of a 1st releasing agent layer, it is still more preferable that it is 80 nm or more. Moreover, as for the thickness of a 1st releasing agent layer, it is more preferable that it is 180 nm or less.

When the thickness of a 1st release agent layer is in the said range and affixes a protective film formation film on a work, stable peeling performance can be exhibited.

(4.3 Composition for first release agent layer)

In the present embodiment, the composition for the first release agent layer may contain, for example, an alkyd-based release agent, a silicone-based release agent, a fluorine-based release agent, an unsaturated polyester-based release agent, a polyolefin-based release agent, and a wax-based release agent. It is preferable to contain When the composition for a 1st release agent layer contains a silicone type release agent, it is preferable to contain a silicone type release agent and a heavy release additive.

(4.3.1 Silicone-based mold release agent)

As a silicone type mold release agent, the silicone mold release agent which mix|blended the silicone which has dimethylpolysiloxane as a basic skeleton can be used.

When the total weight of the first release agent layer composition (excluding the catalyst described later) is 100 parts by mass, the content of silicone composed of dimethylpolysiloxane is preferably less than 100 parts by mass, less than 90 parts by mass, less than 80 parts by mass, less than 70 parts by mass.

The silicone may be any of an addition reaction type, a condensation reaction type, and an energy ray curing type such as an ultraviolet curing type and an electron beam curing type, but it is preferably an addition reaction type silicone. The addition reaction type silicone has advantages such as high reactivity and excellent productivity, small change in peel force after manufacture, and no cure shrinkage compared to condensation reaction type silicones.

Specific examples of the addition-reaction silicone include an organo having two or more alkenyl groups having 2 to 10 carbon atoms, such as a vinyl group, an allyl group, a propenyl group, and a hexenyl group, in the terminal and/or side chain of the molecule. and polysiloxane.

When using such an addition reaction type silicone, it is preferable to use a crosslinking agent and a catalyst together.

As a crosslinking agent, the organopolysiloxane which has the hydrogen atom couple|bonded with at least 2 silicon atoms in 1 molecule is mentioned, for example.

Specific examples of the crosslinking agent include terminal-blocking dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxane-methylhydrogensiloxane copolymer, terminal-blocking trimethylsiloxy group methylhydrogenpolysiloxane, poly (hydrogen silsesquioxane) etc. are mentioned.

Examples of the catalyst include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, an olefin complex of chloroplatinic acid, and platinum group metal compounds such as palladium and rhodium.

By using such a catalyst, hardening reaction of the composition for 1st releasing agent layers can be advanced more efficiently.

The content of the silicone-based mold releasing agent when the total weight of the first releasing agent layer composition (excluding the catalyst) is 100 parts by mass is preferably 30 to 100 parts by mass, 50 from the viewpoint of bringing the peeling force F1 into the above-mentioned range. - 100 parts by mass.

(4.3.2 Jungbak Additive)

A heavy peeling additive is used in order to enlarge the peeling force F1 of the 1st peeling film from a protective film formation film. As a heavy release additive, although organosilanes, such as a silicone resin and a silane coupling agent, are mentioned, for example, Among these, it is preferable to use a silicone resin.

As the silicone resin, it is preferable to use, for example, MQ resin including M units that are monofunctional siloxane units [R ₃ SiO _1/2 ] and Q units that are tetrafunctional siloxane units [SiO _4/2 ]. . In addition, three R in M unit respectively independently represent a hydrogen atom, a hydroxyl group, or an organic group. From the viewpoint of easily suppressing silicone migration, at least one of the three Rs in the M unit is preferably a hydroxyl group or a vinyl group, and more preferably a vinyl group.

Content of the heavy release additive when the total weight of the 1st composition for release agent layers (catalyst is excluded) is 100 mass parts becomes like this. Preferably they are 0-50 mass parts, 5-45 mass parts, and 10-40 mass parts.

The 1st composition for release agent layers may contain the additive generally used in a release agent layer in the range which does not impair the effect of this invention. As such an additive, a dye, a dispersing agent, etc. are mentioned.

Moreover, you may add silicone oil to the 1st composition for release agent layers from a viewpoint of adjusting peeling force low, and a viewpoint more easily forming the release agent layer using the above-mentioned transition phenomenon.

(5. Second release film)

A 2nd peeling film is a film which can support a protective film formation film so that peeling is possible. In this embodiment, it is preferable that a 2nd peeling film peels from a protective film formation film, before affixing a protective film formation film on a workpiece|work.

Similar to the first release film, the second release film may be composed of one layer (single layer) or two or more layers of the substrate, and from the viewpoint of controlling the peelability, the surface of the substrate may be subjected to a peeling treatment. That is, the surface of the base material may be modified, and a material not derived from the base material may be formed on the surface of the base material.

In this embodiment, it is preferable that a 2nd peeling film has a base material and a 2nd release agent layer. By having a 2nd releasing agent layer, it is easy to control the physical property of the surface in which the 2nd releasing agent layer is formed in a 2nd peeling film.

Moreover, in this embodiment, a 2nd release agent layer is formed in the surface by the side of the protective film formation film of a 2nd peeling film. That is, as shown in FIG. 4, in the sheet|seat 1 for protective film formation, the 2nd peeling film 30 is the base material 31 and the 2nd release agent formed in the surface of the protective film formation film side of the base material 31. layer 32 . The main surface 30a of the 2nd release film (the main surface 30a of the 2nd release agent layer 32) contact|connects the main surface 10b of the protective film formation film. Moreover, in addition to the surface by the side of the protective film formation film of a 2nd peeling film, a 2nd release agent layer may be formed also in the surface 30b on the opposite side.

Moreover, when a 2nd release agent layer is formed on the main surface of both sides of a base material, you may apply|coat and form the coating agent containing the composition for 2nd release agent layers mentioned later to both main surfaces of a base material, and you may form a 2nd on one main surface of a base material. After coating the coating agent containing the release agent layer composition, the base material is wound into a roll, and a phenomenon in which the component of the second release agent layer composition is transferred from the main surface to which the coating agent is applied to the main surface not to which the coating agent is not applied (transition phenomenon) is used Then, you may form a 2nd release agent layer in the main surface to which the coating agent is not apply|coated.

Like the 1st peeling film, it is a 2nd peeling film WHEREIN: It is preferable that the 2nd release agent layer is directly formed in the surface of a base material. By forming the 2nd release agent layer directly on the surface of a base material, since production of a 2nd release film becomes easy, cost reduction is implement|achieved.

Although the thickness in particular of a 2nd peeling film is not restrict|limited, It is preferable that they are 10 micrometers or more and 75 micrometers or less. Moreover, it is more preferable that it is 18 micrometers or more, and, as for the thickness of a 2nd peeling film, it is still more preferable that it is 24 micrometers or more. Moreover, it is more preferable that it is 60 micrometers or less, and, as for the thickness of a 2nd peeling film, it is still more preferable that it is 45 micrometers or less. It is preferable that it is less than the thickness of a 1st peeling film from a viewpoint of making peeling force F2 and peeling force F1 above-mentioned F1>F2, and, as for the thickness of a 2nd peeling film, it is more preferable that it is less than the thickness of a 1st peeling film.

In addition, the thickness of a 2nd peeling film means the thickness of the whole 2nd peeling film. For example, the thickness of the 2nd peeling film comprised from multiple layers means the thickness of the sum total of all the layers which comprise a 2nd peeling film.

(listed in 5.1)

The base material of a 2nd peeling film can be suitably selected from the material illustrated as a base material of a 1st peeling film.

(5.2 Second release agent layer)

When a 2nd release film has a 2nd release agent layer, if the 2nd release agent layer is comprised from the material which can provide peelability, it will not restrict|limit in particular. For example, a 2nd releasing agent layer hardens the composition for 2nd releasing agent layers containing a silicone type mold release agent similarly to a 1st releasing agent layer, and is obtained.

The composition for 2nd release agent layers can be selected from the material illustrated by the composition for 1st release agent layers, as long as the relationship of said F1 and F2 is satisfy|filled. However, it is preferable that there is less content than content in the composition for 1st release agent layers, or it is not contained in the material illustrated as a heavy release additive.

Moreover, you may add silicone oil to the composition for 2nd release agent layers from a viewpoint of adjusting peeling force low, and a viewpoint more easily forming the release agent layer using the above-mentioned transition phenomenon.

(6. Manufacturing method of sheet roll for protective film formation)

The manufacturing method in particular of the sheet roll for protective film formation which concerns on this embodiment is not restrict|limited, A well-known method is employable. For example, first, the composition for release agent layers (the composition for 1st release agent layers and the composition for 2nd release agent layers) for forming a 1st release film and a 2nd release film is prepared. In this embodiment, it is preferable to apply|coat to a base material the coating agent which diluted the composition for release agent layers containing each component mentioned above with a dilution solvent from a viewpoint of improving the applicability|paintability to a base material by adjusting a viscosity.

Examples of the dilution solvent include organic solvents such as aromatic hydrocarbons such as toluene, fatty acid esters such as ethyl acetate, ketones such as methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and heptane. These dilution solvents may be used individually by 1 type, and may use 2 or more types together.

As solid content concentration of the coating agent containing the composition for 1st release agent layers, Preferably it is 0.3-10 mass %, More preferably, it is 0.5-5 mass %, More preferably, it is 0.5-3 mass %. Solid content concentration of the coating agent containing the composition for 2nd release agent layers is also the same as solid content concentration of the coating agent containing the composition for 1st release agent layers.

In this embodiment, after apply|coating the coating agent containing the composition for 1st release agent layers to one surface of a base material by a well-known method, a 1st release agent layer is formed by drying and hardening the coating film. Thereby, a 1st peeling film is obtained. A 2nd peeling film can also be carried out similarly and can be manufactured.

Then, when a release agent layer is formed in the both main surfaces of a base material, you may apply|coat and form the coating agent of the composition for release agent layers to the other surface of a base material. Alternatively, in order to utilize the above-described transition phenomenon, the first release film formed by applying the coating agent of the composition for release agent layer is wound up into a roll, for example, 30 ° C., stored for a period of 7 days, etc., the other side You may form by transferring the component of the composition for release agent layers to .

The composition for protective film formation films for forming a protective film formation film is prepared. Like the composition for release agent layers, in this embodiment, it is preferable to apply|coat the coating agent which diluted the composition for protective film formation films with the dilution solvent to a release film. What is necessary is just to make the kind of a dilution solvent similar to the composition for release agent layers.

On the other hand, as solid content concentration of the coating agent containing the composition for protective film formation films, Preferably it is 20-80 mass %, More preferably, it is 30-70 mass %.

In this embodiment, after apply|coating the coating agent containing the composition for protective film formation films by a well-known method on the 1st release agent layer of a 1st release film, or on the 2nd release agent layer of a 2nd release film, heating; Dry to form a coating film. Next, on the said coating film, the 2nd release agent layer of a 2nd peeling film or the 1st release agent layer of a 1st peeling film is pasted together, and the sheet|seat for protective film formation (long sheet) is manufactured. In this embodiment, the composition for a protective film formation film is not on the 2nd release agent layer, but on the 1st release agent layer of a 1st release film from a viewpoint of making peeling force F1 into the above-mentioned range, and a viewpoint of making F1 > F2. It is preferable to apply the coating agent containing.

As a coating method of the coating agent containing each composition, for example, a spin coat method, a spray coat method, a bar coat method, a knife coat method, a roll coat method, a roll knife coat method, a blade coat method, a die coat method, a gravure method The coat method is exemplified.

The produced sheet for forming a protective film is wound with a predetermined tension applied by a winding device while both sides in the width direction are cut according to the size of the work to which the protective film forming film is to be adhered and the size in the width direction is adjusted, thereby forming a protective film It becomes a sheet roll for When the width of the workpiece is 150 mm, the length in the width direction after cutting is preferably in the range of 155 to 194 mm, and when the width of the workpiece is 200 mm, the length in the width direction after cutting is 205 to 250 mm It is preferable to be in the range, and when the width of the work is 300 mm, the length in the width direction after cutting is preferably in the range of 305 to 350 mm, and when the width of the work is 450 mm, the length in the width direction after cutting It is preferable to exist in the range of 455-500 mm.

As above-mentioned, the sheet roll immediately after winding-up has the location where the dispersion|variation in winding-up pressure generate|occur|produces and is being pressurized strongly. However, even when the winding pressure varies, when the loss tangent of the protective film forming film is low and the protective film forming film is not easily deformed, winding traces are hardly formed in the protective film forming film. Moreover, when temperature becomes low, it will be easy to keep the loss tangent of a protective film formation film low. Moreover, as mentioned above, there exists a tendency for the winding-up pressure in a sheet roll to stabilize with time.

Then, in this embodiment, in order to suppress formation of the winding trace with respect to the protective film formation film in a sheet roll, the sheet roll immediately after winding up is stored for a predetermined period until the winding pressure is stabilized, and the loss of a protective film formation film Keep the tangent low. Specifically, it is preferable to store the sheet roll for 60 days from after the sheet roll formation, and to store the sheet roll at a storage temperature of 10°C or less in a period of 25 days or more out of 60 days. In this embodiment, Preferably, the sheet roll is stored at the storage temperature of 10 degrees C or less for 30 days or more, 35 days or more, 40 days or more, out of 60 days.

The storage period at a storage temperature of 10° C. or less is preferably started within 10 days after the sheet roll is formed, more preferably within 7 days, and still more preferably within 4 days. The sheet roll immediately after winding up WHEREIN: Since there exists a tendency for the dispersion|variation in winding pressure to be large, formation of the winding trace with respect to the protective film formation film in a sheet roll can be suppressed more by keeping the loss tangent of a protective film formation film reliably low.

The storage temperature is preferably -10°C or higher, more preferably -5°C or higher, and still more preferably 0°C or higher. When the lower limit of the storage temperature is the above value, it is suppressed that the elastic modulus of the protective film forming film becomes too high, and peeling occurs between the protective film forming film and the release film, in particular, between the protective film forming film and the second release film It can be suppressed .

Through such a storage process, the sheet roll for protective film formation which concerns on this embodiment is obtained. The sheet roll for forming a protective film according to the present embodiment has a loss tangent tan δ ₁₀ of 1.2 or less at 10°C of the protective film forming film, and the winding axis of the sheet roll is a vertical direction. When A/tanδ ₁₀ satisfies the relationship of 2.0 or more when the maximum displacement amount of the long sheet in the vertical direction is A [mm], in order to form a protective film, Even if it feeds out the sheet|seat for protective film formation from a sheet roll, formation of the winding trace in a protective film formation film is suppressed to the sheet|seat for protective film formation by the side of a core part. Therefore, the appearance defect of a protective film is suppressed, and the sheet roll for protective film formation which concerns on this embodiment can be used up without waste.

(7. Method of manufacturing the device)

As an example of the manufacturing method of the apparatus using the sheet roll for protective film formation which concerns on this embodiment, the method of manufacturing the chip with a protective film obtained by processing the wafer to which the protective film formation film was affixed is demonstrated.

First, as shown in FIG. 5, the elongate sheet 1 is fed out from the sheet roll 100 for protective film formation, and the 2nd peeling film 30 and protective film formation film are used for the long sheet using the cutting blade 50. The cutout 40 which penetrates (10) and reaches to a part of the 1st peeling film 20 is formed. A circular protective film formation film is obtained by removing a 2nd peeling film and an unnecessary protective film formation film from the elongate sheet which provided the cutout 40.

Next, as shown in FIG. 6A, the circular protective film forming film 11 is affixed to the back surface 60b of the wafer 60 as a work, and, as shown in FIG. 6B, the 1st peeling film ( 20) is peeled, the protective film formation film 11 is turned into a protective film, and the protective film 15 is formed. Then, the wafer having a protective film is separated into pieces, and a chip with a protective film is obtained. In addition, you may perform protective film formation, after dividing a wafer into pieces.

In the protective film formation film, since formation of a winding trace is suppressed, also in the surface of a protective film, a trace is suppressed. Accordingly, it is possible to obtain a chip with a protective film in which the appearance defect of the protective film is suppressed.

(8. Modifications)

4, in the 1st peeling film 20, the 1st release agent layer 23 is formed in the surface 20a which is not in contact with the protective film formation film 10, In the 2nd peeling film 30 Although the structure in which the 2nd release agent layer is not formed in the surface 30b which is not in contact with the , protective film formation film 10 is shown, in this embodiment, it is not limited to this structure.

For example, in a 1st peeling film, the 1st release agent layer is formed in the surface which is not in contact with the protective film formation film, In a 2nd peeling film, the 2nd release agent layer is formed in the surface which is not in contact with the protective film formation film. The formed structure may be sufficient. Moreover, in a 1st peeling film, the 1st release agent layer is not formed in the surface which is not in contact with the protective film formation film, In a 2nd peeling film, the 2nd release agent layer is formed in the surface which is not in contact with the protective film formation film. It may be a configured configuration.

In addition, in FIG. 5, although the cutout which forms the protective film formation film to be affixed to a work is circular, if it is a closed shape, another shape may be sufficient. As another shape, polygons, such as a triangle, an ellipse, etc. are illustrated, for example. Moreover, it is preferable that the closed shape respond|corresponds to the shape of a workpiece|work.

As mentioned above, although embodiment of this invention was described, this invention is not limited at all to the said embodiment, You may change in various aspects within the scope of this invention.

Example

Hereinafter, the present invention will be described in more detail using Examples, but the present invention is not limited to these Examples.

(Preparation of 1st peeling film)

First, in order to prepare the composition for 1st release agent layers, the following component was prepared.

(α) silicone-based mold release agent

(α-1) a silicone-based release agent containing an organopolysiloxane having a vinyl group and an organopolysiloxane having a hydrosilyl group (manufactured by Toray Dow Corning Co., Ltd., BY24-561, solid content 30% by mass)

(α-2) dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-62-1387, weight average molecular weight: 2000)

(β) silicone resin

MQ resin with vinyl group (manufactured by Toray Dow Corning, SD-7292, solid content 71% by mass)

(γ) catalyst

Platinum (Pt) catalyst (manufactured by Toray Dow Corning Co., Ltd., SRX-212, solid content 100% by mass)

Next, (α-1) is 67.5 parts by mass (solid content), (α-2) is 2.5 parts by mass (solid content), (β) is 30 parts by mass (solid content), and (γ) is 6.7 parts by mass (Solid content ratio) The mixture is blended and diluted with a mixed solvent of toluene and methyl ethyl ketone (toluene/methyl ethyl ketone = 1/1 (mass ratio)) so that the solid content concentration is 2 mass%, and the first release agent layer composition is contained. A coating agent was prepared.

In Experimental Examples 1 to 6, the composition for forming the first release agent layer prepared on both main surfaces of the PET film (manufactured by Mitsubishi Chemical, trade name: Diafoil (registered trademark) T-100, thickness: 50 µm) as a base material was contained. The coating agent was apply|coated so that the film thickness after heating and drying might be set to 0.15 micrometer, the 1st release agent layer was formed on both main surfaces of PET film, and the 1st release film was manufactured.

In Experimental Examples 7 and 8, the composition for forming a first release agent layer prepared on one main surface of a PET film (manufactured by Mitsubishi Chemical, trade name: Diafoil (registered trademark) T-100, thickness: 50 µm) as a substrate was contained in Experimental Examples 7 and 8. The coating agent was apply|coated so that the film thickness after heating and drying might be set to 0.15 micrometer, the 1st release agent layer was formed on one main surface of PET film, the 1st release film was manufactured, This was wound up and it was set as the roll.

In Experimental Example 9, the coating agent containing the composition for forming the first release agent layer was not applied to both main surfaces of the PET film (manufactured by Mitsubishi Chemical, trade name: Diafoil (registered trademark) T-100, thickness: 50 µm), No peeling treatment was performed.

(Preparation of the 2nd release film)

In Experimental Examples 1 to 6, a film (“SP-PET381031” manufactured by Lintech, 38 µm in thickness) in which one side of the PET film was subjected to a peeling treatment was used as the second release film.

In Experimental Examples 7 and 8, 35 parts by mass (solid content) of an addition-reaction silicone-based release agent (trade name "KS-3656A", solid content: 30 mass%, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) containing polyorganohydrogensiloxane as a crosslinking agent , platinum catalyst (trade name "PL50T", manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by mass (solid content) is blended and mixed, and a mixed solvent of toluene and methyl ethyl ketone (toluene/methyl ethyl ketone =) so that the solid content concentration is 2 mass % 1/1 (mass ratio)), and the coating agent containing the composition for 2nd release agent layers was prepared. Next, the coating agent containing the composition for forming a second release agent layer prepared on one main surface of a PET film as a base material (manufactured by Mitsubishi Chemical, trade name: Diafoil (registered trademark) T-100, thickness: 38 µm) is heated. It apply|coated so that the film thickness after drying might be set to 0.15 micrometers, the 2nd release agent layer was formed on one main surface of PET film, and the 2nd release film was manufactured. The roll of the wound second release film is stored at 30 ° C. for 7 days, and the film is peeled off on both main surfaces of the PET film by using the transition phenomenon from the surface to which the coating agent is applied to the surface to which the coating agent is not applied. treatment was carried out.

In Experimental Example 9, the coating agent containing the composition for forming the second release agent layer was not applied to both main surfaces of the PET film (manufactured by Mitsubishi Chemical, trade name: Diafoil (registered trademark) T-100, thickness: 38 µm). That is, the PET film in which both main surfaces of the PET film were not peeled was made into the 2nd peeling film.

(Production of protective film forming film)

Each of the following components was mixed at the compounding ratio (solid content conversion) shown in Table 1, diluted with methyl ethyl ketone so that solid content concentration might be 50 mass %, and the coating agent containing the composition for protective film formation films was prepared.

(A) polymer component

(A-1) (meth)acrylic acid ester air obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate Coalescing (weight average molecular weight: 400,000, glass transition temperature: -1 ° C)

(A-2) (meth)acrylic acid ester copolymer formed by copolymerizing 10 parts by mass of n-butyl acrylate, 65 parts by mass of methyl acrylate, 12 parts by mass of glycidyl methacrylate and 13 parts by mass of 2-hydroxyethyl acrylate Coalescing (weight average molecular weight: 450,000, glass transition temperature: 2°C)

(A-3) (meth)acrylic acid ester air obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate Coalescing (weight average molecular weight: 800,000, glass transition temperature: -28 ° C)

(A-4) (meth)acrylic acid ester air obtained by copolymerizing 27 parts by mass of n-butyl acrylate, 38 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate Coalescing (weight average molecular weight: 500,000, glass transition temperature: -9 °C)

(A-5) (meth)acrylic acid ester air obtained by copolymerizing 17 parts by mass of n-butyl acrylate, 48 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate Coalescing (weight average molecular weight: 500,000, glass transition temperature: -2 °C)

(B) curable component (thermosetting component)

(B-1) bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent of 184 to 194 g/eq)

(B-2) acrylic rubber fine particles dispersed bisphenol A liquid epoxy resin (manufactured by Nippon Catalyst, BPA328, epoxy equivalent 230 g/eq, acrylic rubber content 20 phr)

(B-3) Dicyclopentadiene type epoxy resin (Dainippon Ink Chemicals Co., Ltd., Epiclone HP-7200HH, softening point 88 to 98°C, epoxy equivalent 255 to 260 g/eq)

(C) Curing agent: dicyandiamide (manufactured by Mitsubishi Chemical, DICY7)

(D) curing accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemical Industry Co., Ltd., Curesol 2PHZ)

(E) filling material

(E-1) Epoxy group-modified spherical silica filler (manufactured by Admatex, SC2050MA, average particle diameter of 0.5 µm)

(E-2) Silica filler (manufactured by Admatex, YC100C-MLA, average particle diameter 0.1 μm)

(F) Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403, methoxy equivalent 12.7 mmol/g, molecular weight 236.3)

(G) Colorant: carbon black (manufactured by Mitsubishi Chemical, MA600B, average particle diameter of 28 nm)

The coating agent containing the prepared composition for protective film formation films was applied to the surface on which the 1st release agent layer was formed of the prepared 1st release film, and it dried at 100 degreeC for 2 minutes, and the protective film formation film with a thickness of 20 micrometers was formed. Then, by affixing the side on which the 2nd release agent layer of the prepared 2nd release film was formed (in Experimental Examples 7 and 8, the surface opposite to the surface on which the release agent layer was formed by using transition phenomenon) on the protective film formation film, a protective film A sheet for forming a protective film in which the first release film was formed on one main surface of the forming film and the second release film was formed on the other main surface (constituent body of the first release film/protective film forming film/second release film) was obtained. As for sticking conditions, the temperature was 60 degreeC, the pressure was 0.4 MPa, and the speed|rate was 1 m/min.

(Manufacture of sheet roll)

Using a seam fixing tape having a width of 5 mm and a thickness of 40 µm, while cutting the sheets for forming a protective film of the obtained Experimental Examples 1 to 9 to a width of 320 mm using a twin-screw slitter machine (manufactured by Toyizaki Corporation), The sheet for forming a protective film having the same width (320 mm) as the width at which the protective film forming sheet was cut and being cut into a hollow plastic core (core part) having a diameter of 3 inches was wound in a roll shape under the following winding conditions a to d. did That is, in each experimental example, four types of sheet rolls wound on four winding conditions were formed. The length of the wound sheet for forming a protective film was 50 m. The cutting speed was 5 m/min.

In the winding condition a, the current meter of the powder brake for controlling the tension during winding indicates 0.25 A, in the winding condition b, the current meter of the powder brake indicates 0.30 A, and in the winding condition c, the current meter of the powder brake shows 0.35 A, and under the winding condition d, the current meter of the powder break shows 0.40 A. Tension becomes large, so that the electric current value shown by the electric current meter of a powder break is large, and the sheet|seat for protective film formation is wound up firmly.

The sheet roll for protective film formation was obtained by leaving the wound sheet for protective film formation still at 23 degreeC for 3 days after winding-up, then leaving still at 5±4 degreeC for 40 days, and leaving still at 23 degreeC for 17 days again. .

Then, the following measurement and evaluation were performed.

(loss tangent tanδ ₁₀ of the protective film formation film at 10°C)

From the prepared sheet for forming a protective film, the first release film and the second release film were peeled off, and a plurality of protective film forming films were laminated to form a laminate of a protective film forming film having a thickness of 200 µm±20 µm. This laminated body was cut|disconnected so that width might be set to 4 mm, and the sample for a measurement was obtained.

Using a viscoelasticity measuring device (“RHEOVIBRON DDV-01FP” manufactured by Orientec Co., Ltd.), the sample for measurement was subjected to the measurement conditions of a frequency of 11 Hz, a distance between chucks of 15 mm, and a temperature increase rate of 3° C./min, in a tensile mode, The tan-delta of the sample for a measurement from -20 degreeC to 50 degreeC was measured, and the loss tangent tan-delta ₁₀ in 10 degreeC was computed from those values. Table 1 shows the measurement results of the samples of Experimental Examples 1 to 9.

(Evaluation of the presence or absence of peeling treatment of the peeling film)

The sheet for forming a protective film was fed out from the obtained sheet roll, and the sheet for forming a protective film of 50 mm × 50 mm was moved in the width direction at a point 1 m from the part where the sheet for forming a protective film was started to be fixed to the plastic core with the seam fixing tape. was cut at three points.

The 1st peeling film and the 2nd peeling film were peeled from the cut-out sheet for protective film formation, and XPS measurement was performed on the surface which was not pasted together with the protective film formation film in the 1st peeling film under the following conditions. Similarly, XPS measurement was performed on the surface which was not pasted together with the protective film formation film in the 2nd peeling film on condition of the following. The XPS measurement was performed once each about the 1st peeling film of 3 sheets and the 2nd peeling film of 3 sheets obtained by cutting out the sheet|seat for protective film formation.

XPS device: QuanteraSXM manufactured by Alvacpai

X-ray: AlKα (1486.6 eV)

Take-out angle: 45°

Measured elements: silicon (Si), carbon (C), oxygen atom (O)

From the obtained measurement result, the silicon atom ratio shown below was computed about each of the 1st peeling film and the 2nd peeling film from each measurement element amount (XPS count number), and the average value was computed.

Silicon atomic ratio (atomic %) = [(Si element amount)/[(C element amount) + (O element amount) + (Si element amount)]] x 100

Based on the obtained average value, the following criteria evaluated. In the case of judgment A and B, it was judged that the peeling process was carried out. Table 1 shows the measurement results of the samples of Experimental Examples 1 to 9.

Judgment A: The average value of at least one of a 1st peeling film and a 2nd peeling film is 1.0 atomic% or more

Judgment B: Judgment A is not satisfied, and the average value of at least one of a 1st peeling film and a 2nd peeling film is 0.1 atomic% or more and less than 1.0 atomic%.

Judgment C: The average value of both of a 1st peeling film and a 2nd peeling film is less than 0.1 atomic%

The 1st peeling film before apply|coating the coating agent containing the composition for protective film formation films was prepared, and it cut out three points|pieces in the width direction at the size of 50 mm x 50 mm from the 1st peeling film. About the surface to which the coating agent containing the composition for protective film formation films is apply|coated among both main surfaces of the 1st peeling film, the presence or absence of a peeling process was evaluated by the conditions similar to the above using the said XPS apparatus.

About the sample of the 1st peeling film of Experimental Examples 1-9, it was confirmed that the average value of three points|pieces of a silicon atom ratio was 1.0 atomic% or more.

The 2nd peeling film before affixing on the protective film formation film was prepared, and it cut out three points|pieces in the width direction at the size of 50 mm x 50 mm from the 2nd peeling film. The presence or absence of a peeling process was evaluated on the conditions similar to the above using the said XPS apparatus about the surface to be affixed to the protective film formation film among both main surfaces of a 2nd peeling film.

About the sample of the 2nd peeling film of Experimental Examples 1-9, it was confirmed that the average value of three points|pieces of the silicon atom ratio was 1.0 atomic% or more.

(Evaluation of the water contact angle of the peeling film)

The sheet for forming a protective film was fed out from the obtained sheet roll, and the sheet for forming a protective film of 50 mm × 50 mm was moved in the width direction at a point 1 m from the part where the sheet for forming a protective film was started to be fixed to the plastic core with the seam fixing tape. was cut at three points.

The 1st peeling film and the 2nd peeling film were peeled from the cut-out sheet|seat for protective film formation, and the contact angle of water was measured under the following conditions with respect to the surface which was not bonded together with the protective film formation film in the 1st peeling film. Similarly, in the 2nd peeling film, the contact angle of water was measured by the following conditions with respect to the surface which was not pasted together with the protective film formation film. The measurement of the contact angle of water was performed 5 times each about the 1st peeling film of 3 sheets and the 2nd peeling film of 3 sheets obtained by cutting out the sheet|seat for protective film formation.

Contact angle measuring device: Kyowa Interface Science Co., Ltd., fully automatic contact angle meter DM-701

Drop amount: 2 μl

Environment: temperature 23 ℃, humidity 50%

About each of the 1st peeling film and the 2nd peeling film, the average value of the obtained measurement result was computed. Based on the obtained average value, the following criteria evaluated. In the case of judgment A, it was judged that the peeling process had been carried out. Table 1 shows the measurement results of the samples of Experimental Examples 1 to 9.

Judgment A: The average value of at least one of a 1st peeling film and a 2nd peeling film is 78 or more

Judgment C: The average value of both a 1st peeling film and a 2nd peeling film is 77 or less

(The peeling force F1 from the protective film formation film of a 1st peeling film)

The 2nd peeling film was peeled from the obtained sheet|seat for protective film formation. On the surface of the protective film forming film exposed by peeling, both adhesive surfaces of 25 µm thick positive adhesive PET (PET25A-4100, manufactured by Toyobo Corporation) were laminated (70°C, 1 m/min) by thermal lamination (70°C, 1 m/min). It affixed and the laminated body sample was manufactured. A sample of the laminate was cut out to a width of 100 mm to prepare a sample for measurement. The back surface of the 1st peeling film of the sample for a measurement was fixed to the hard support plate with a double-sided tape.

Using a universal tensile tester (manufactured by Shimadzu Corporation, product name "Autograph (registered trademark) AG-IS"), a composite (integral) sieve of protective film-forming film/double-adhesive PET was measured at a distance of 100 mm and a peeling angle of 180 °, it peeled from the 1st peeling film at the peeling rate of 1 m/min, and the load at that time was measured. Among the measured loads, the average value of the load between 80 mm excluding the load in the first 10 mm and the load in the last 10 mm of the measurement distance was made into peeling force F1.

(Peeling force F2 from the protective film formation film of a 2nd peeling film)

The obtained sheet for forming a protective film was cut out to a width of 100 mm to prepare a sample for measurement. The back surface of the 1st peeling film of the sample for a measurement was fixed to the hard support plate with a double-sided tape.

Using a universal tensile testing machine (manufactured by Shimadzu Corporation, product name “Autograph (registered trademark) AG-IS”), the second peeling film was measured from the sample for measurement at a measurement distance of 100 mm, a peeling angle of 180°, and a peeling rate of 1 It peeled at m/min, and the load at that time was measured. The average value of the load between 80 mm excluding the load in the first 10 mm and the load in the last 10 mm of the measurement distance among the measured loads was made into peeling force F2.

By comparing the obtained peeling forces F1 and F2, it was confirmed for all samples that F1 was greater than F2.

(Evaluation of sliding properties of long sheets)

In each experimental example, the sheet roll for forming a protective film obtained by winding under the winding conditions a to d was placed on a horizontal stand so that the winding axis was in the vertical direction, and the speed was 150 mm/min while supporting only the core. The sheet roll for protective film formation was lifted up to the height of 150 mm, gravity was made to act on the long sheet|seat wound up, and it hold|maintained for 1 minute.

After holding for 1 minute, as shown in FIG. 2 , when the height of the upper end of the core is set to 0, the maximum amount of displacement of the upper end of the long sheet that was flush with the upper end of the core in the vertical direction is defined as the maximum displacement A. did. In addition, when the lower end part of the elongate sheet contacted the base|base, the maximum displacement amount A was made into 150 mm. In each experimental example, Table 1 shows the evaluation result with respect to 4 types of sheet rolls wound up under the winding conditions a-d.

Moreover, as a result of performing the same evaluation also about the sheet roll manufactured on the same conditions except having made the length of the width direction into 305 mm and 335 mm, it has confirmed that the maximum displacement amount A hardly changes.

(Evaluation of winding traces)

From the sheet roll for forming a protective film after slipping evaluation, a long sheet was drawn out from the outermost layer at a speed of 3 m/min, and the "length from the core" at which winding traces outside the allowable range began to occur, was measured. Whether or not the winding traces were outside the allowable range was visually checked by 5 judges at the same time, and 3 judges judged that it was outside the allowable range. In each experimental example, Table 1 shows the evaluation result with respect to 4 types of sheet rolls wound up under the winding conditions a-d.

Judgment A: 0 meters or more, less than 4 meters

Judgment B: 4 meters or more, less than 6 meters

Judgment C: 6 meters or more, less than 8 meters

Judgment D: 8 meters or more, less than 10 meters

Judgment E: 10 meters or more

From Table 1, when the loss tangent (tanδ ₁₀ ) of the protective film forming film at 10°C and A/tanδ ₁₀ indicating the relationship between the maximum displacement A [mm] of the elongated sheet and tanδ ₁₀ are within the above-mentioned ranges, It has confirmed that the formation of the wound trace with respect to the protective film formation film in the sheet roll for protective film formation was suppressed.

100: sheet roll for forming a protective film
1: Sheet for forming a protective film
10: protective film forming film
20: first release film
21: description
22, 23: first release agent layer
30: second release film
31: description
32: second release agent layer
70: deep
80: fixing means

Claims (5)

a protective film forming film;
a first peeling film formed on one surface of the protective film forming film;
A sheet roll formed by winding a long sheet having a second release film formed on the other surface of the protective film forming film,
When the peeling force of the first release film from the protective film-forming film is F1 and the peeling force of the second release film from the protective film-forming film is F2, the relationship F1 > F2 is satisfied,
When the loss tangent at 10° C. of the protective film-forming film is tan δ ₁₀ , tan δ ₁₀ is 1.2 or less,
In the direction in which the winding axis of the sheet roll becomes the vertical direction, when gravity is applied to the wound long sheet, when the maximum displacement of the long sheet in the vertical direction is A [mm], A/tanδ ₁₀ is A sheet roll for forming a protective film that satisfies the relationship of 2.0 or more. The method of claim 1,
A said 1st peeling film and/or a said 2nd peeling film WHEREIN: The sheet roll for protective film formation by which the peeling process is carried out on the surface which is not in contact with the said protective film formation film. 3. The method of claim 1 or 2,
The sheet roll for protective film formation in which the said maximum displacement amount A is 2 mm or more. 4. The method according to any one of claims 1 to 3,
A sheet roll for forming a protective film having a tanδ ₁₀ of 0.04 or more. A method of manufacturing the sheet roll for forming a protective film according to any one of claims 1 to 4, comprising:
The manufacturing method of the sheet roll for protective film formation which has the process of storing the said sheet roll for protective film formation at the storage temperature of 10 degrees C or less for 25 days or more out of 60 days after formation of the said protective film formation sheet roll.

Images