TWI745314B - Sheet for forming protective film - Google Patents

Abstract

A sheet for forming a protective film 1 of the present application is formed by laminating a heat-curable resin layer 12 on a first supporting sheet 101, the heat-curable resin layer 12 is adhered to a surface having bumps of a semiconductor wafer and is cured by heat, whereby the first protective film is formed on the semiconductor wafer surface, wherein the difference between the surface free energy of a surface of the first supporting sheet 101 side of the pre-heated heat-curable resin layer 12 and that of a surface of the heat-curable resin layer 12 side of the first supporting sheet 101 is 10mJ/m² or more.

Description

Sheet for forming protective film

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

This application is based on Japanese Patent Application No. 2015-217115 filed in Japan on November 4, 2015 and claims its priority, and its content is incorporated herein.

Previously, the multi-pin LSI (Large Scale Integration; large scale integrated circuit) package used in MPU (Microprocessing Unit) or gate array (gate array) was installed on the printed circuit board. In the case of wiring boards, the flip-chip mounting method has been used. The flip-chip mounting method uses a semiconductor chip with convex electrodes (bumps) made of eutectic solder, high-temperature solder, gold, etc. formed on the connection pad. In a so-called face down method, the bumps face the corresponding terminals on the chip mounting substrate and are brought into contact with each other to perform fusion/diffusion bonding.

The semiconductor wafer used in this mounting method is obtained, for example, by polishing the surface of the semiconductor wafer with bumps formed on the circuit surface on the opposite side to the circuit surface, or dicing to form a single piece change. In the process of obtaining such a semiconductor wafer, in order to protect the circuit surface and bumps of the semiconductor wafer, the curable resin film laminated on the support sheet is usually attached to the bump forming surface, and the film is cured and applied to the bumps. The formation surface forms a protective film.

As such a curable resin film, one containing a thermosetting component that is cured by heating is widely used. As a sheet for forming a protective film having such a thermosetting resin layer, it has been disclosed that the above-mentioned film laminate has specific characteristics. A thermoplastic resin layer having a thermoelastic modulus, and a thermoplastic resin layer that is non-plastic at 25°C is laminated on the uppermost layer of the thermoplastic resin layer (see Patent Document 1). Furthermore, according to Patent Document 1, the protective film forming sheet can be said to be excellent in bump filling properties of the protective film, wafer processability, electrical connection reliability after resin sealing, and the like.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-028734.

However, if an attempt was made to form a protective film on the bump formation surface using a protective film forming sheet formed by laminating a thermosetting resin layer on a support sheet, a large amount of the support sheet and The interface of the thermosetting resin layer cannot be peeled off well, or if it is to be peeled off forcefully, it must be on the substrate / The interface in the support sheet such as the adhesive layer peels off, and the adhesive adheres to the protective film side.

The present invention was developed in view of the above circumstances, and its object is to provide a protective film forming sheet having excellent peelability at the interface between a support sheet and a thermosetting resin layer.

The present invention is a sheet for forming a protective film, which is formed by laminating a thermosetting resin layer on a first support sheet; and the sheet for forming a protective film is characterized in that the thermosetting resin layer is used to The surface of the semiconductor wafer with bumps is thermally cured to form a protective film layer on the surface; the surface free energy of the first support sheet side surface of the thermally curable resin layer before thermal curing and the first support The difference in surface free energy of the surface on the side of the thermosetting resin layer of the sheet is 10 mJ/m ² or more.

The sheet for forming a protective film is preferably a contact angle of the thermosetting resin layer on the side surface of the first support sheet before heat curing with water, and the contact angle of the surface on the side of the thermosetting resin layer of the first support sheet with water The difference in contact angle is more than 30°.

The interface between the first support sheet and the thermosetting resin layer of the protective film forming sheet of the present invention is excellent in easy peelability.

1, 2, 3‧‧‧Sheet for forming protective film

11‧‧‧First substrate

11a‧‧‧The side surface of the thermosetting resin layer of the first substrate

12‧‧‧curable resin layer

12'‧‧‧First protective film

13‧‧‧First adhesive layer

13a‧‧‧The surface of the first adhesive layer

14‧‧‧The first middle layer

101, 102, 103‧‧‧First support film

101a, 102a, 103a‧‧‧The surface of the first support sheet

90‧‧‧Semiconductor Wafer

90a‧‧‧Circuit surface of semiconductor wafer

91‧‧‧ bump

91a‧‧‧The surface of the bump

911‧‧‧The top of the bump

Fig. 1 is a cross-sectional view schematically showing one embodiment of the protective film forming sheet of the present invention.

Fig. 2 is a cross-sectional view schematically showing another embodiment of the protective film forming sheet of the present invention.

Fig. 3 is a cross-sectional view schematically showing still another embodiment of the protective film forming sheet of the present invention.

FIG. 4 is a cross-sectional view schematically showing an example of a semiconductor wafer having bumps.

5 is a cross-sectional view schematically showing a state in which the protective film forming sheet of the present invention is attached to the bumped surface of the semiconductor wafer.

6 is a cross-sectional view schematically showing an example of a semiconductor wafer provided with a protective film formed using the protective film forming sheet of the present invention.

The present invention is a sheet for forming a protective film, which is formed by laminating a thermosetting resin layer on a first support sheet; and the aforementioned sheet for forming a protective film is characterized in that the thermosetting resin layer is used to The surface of the semiconductor wafer with bumps is thermally cured to form a protective film layer on the surface; the surface free energy of the first support sheet side surface of the thermally curable resin layer before thermal curing and the first support The difference in surface free energy of the surface on the side of the thermosetting resin layer of the sheet is 10 mJ/m ² or more.

Regarding the surface free energy γ _s ^total of each solid, the surface free energy γ _L ^{d of the} dispersion force component, the surface free energy γ _L ^{p of the} polar component, and the surface free energy γ _L ^h of the hydrogen bonding component can be used For known liquids, such as pure water, diiodomethane, 1-bromine, the contact angles of the solid surface are measured, and the surface free energy γ _s ^d and polarity of the dispersing force component are solved for the following formula (2) The simultaneous equations related to the surface free energy γ _s ^{p of the} component and the surface free energy γ _s ^h of the hydrogen bonding component are substituted into the following formula (1) to obtain.

γ _s ^total =γ _s ^d +γ _s ^p +γ _s ^h (1)

γ _L (1+cosθ)=2. (γ _s ^d. _{γ L} ^d ) ^1/2 +2. (γ _s ^p ．γ _L ^p ) ^1/2 +2. (γ _s ^h ．γ _L ^h ) ^1/2 (2)

The sheet for forming a protective film of the present invention is used by attaching it to the bumpy surface of a semiconductor wafer via its thermosetting resin layer. In addition, the heat-curable resin layer after attachment is heated to increase fluidity, spreads between the bumps to cover the bumps and is in close contact with the circuit surface, and covers the surface of the bumps, especially the circuit surface. The surface of the nearby part is filled with bumps. The thermosetting resin layer in this state is further thermally cured by heating, and finally a first protective film is formed to protect the bump in the state of being in close contact with the surface of the bump on the circuit surface.

For example, regarding the semiconductor wafer after the protective film forming sheet is attached, the surface opposite to the aforementioned circuit surface is polished, the first support sheet is removed, and then the thermosetting resin layer is heated to perform bumping The filling and the formation of the first protective film are finally incorporated into the semiconductor device with the first protective film.

For the protective film forming sheet of the present invention, the surface free energy of the first support sheet side surface of the thermosetting resin layer before heat curing and the thermosetting resin layer side of the first support sheet The difference between the surface free energy of the surface is 10 mJ/m ² or more, and there is no component movement at the interface between the two. When the first support sheet is removed, the interface between the first support sheet and the thermosetting resin layer has excellent peelability. The difference between the surface free energy of the first support sheet side surface of the thermosetting resin layer before heat curing and the surface free energy of the first support sheet side surface of the thermosetting resin layer is preferably 12 mJ/m ² To 100mJ/m ² , more preferably ^{15mJ/m 2} to 90mJ/m ² , preferably 18mJ/m ² to 85mJ/m ² , particularly preferably 20mJ/m ² to 80mJ/m ² .

In addition, the contact angle of the first support sheet side surface of the thermosetting resin layer with respect to water before heat curing and the contact angle of the thermosetting resin layer side surface of the first support sheet with respect to water When the difference is 30° or more, when the first support sheet is removed, the easy peelability of the interface between the first support sheet and the thermosetting resin layer becomes more excellent.

Furthermore, in the sheet for forming a protective film of the present invention, the surface on the side of the thermosetting resin layer of the first support sheet may be composed of an energy ray curable adhesive or a non-energy ray curable adhesive. In the case of an energy ray curable adhesive, the difference between the surface free energy before the energy ray curing becomes the above range, and there is no component movement at the interface between the two before the energy ray curing. Even when the first support sheet is removed after the energy ray is cured, the interface between the first support sheet and the thermosetting resin layer is easy to peel off The sex is also excellent. Even if the value of the aforementioned surface free energy difference after energy ray curing deviates from the above range, it will have less influence on the component movement of the interface between the two before energy ray curing, and it will affect the first support sheet and heat when the first support sheet is removed. The effect of the easy peelability of the interface of the curable resin layer is small.

Hereinafter, the sheet for forming a protective film of the present invention will be described in detail with reference to the drawings.

In addition, the drawings used in the following description are sometimes shown as different from the actual protective film formation sheet for the sake of easy understanding of features. In addition, the materials, conditions, etc. exemplified in the following description are just examples, and the present invention is not necessarily limited to these, and can be implemented with appropriate changes within the scope not changing the gist.

◎The first supporting film

The aforementioned first support sheet may be composed of one layer (single layer), or may be composed of multiple layers of more than two layers. When the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.

Furthermore, in this specification, it is not limited to the case of the first support sheet. The so-called "plural layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only a part may be used. "The layers are the same", and "a plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

As a preferable first support sheet, for example, a first adhesive layer is laminated on a first substrate, a first intermediate layer is laminated on the first substrate, and a first intermediate layer is laminated on the first intermediate layer. Those made of an adhesive layer, those made of only the first substrate, etc.

Hereinafter, an example of the protective film forming sheet of the present invention will be described with reference to the drawings according to the type of the first support sheet.

Fig. 1 is a cross-sectional view schematically showing one embodiment of the protective film forming sheet of the present invention. The sheet 1 for forming a protective film shown here is used as the first support sheet 101 in which the first adhesive layer 13 is laminated on the first base material. That is, the sheet 1 for forming a protective film is configured to include a first adhesive layer 13 on the first base material 11 and a thermosetting resin layer 12 on the first adhesive layer 13. The first support sheet 101 is a laminate of the first substrate 11 and the first adhesive layer 13, and heat is provided on one surface 101a of the first support sheet 101, that is, on one surface 13a of the first adhesive layer 13. Curable resin layer 12. For the sheet 1 for forming a protective film, the surface free energy of the surface of the thermosetting resin layer 12 on the side of the first support sheet 101 before thermal curing is compared with the surface free energy of the surface of the first adhesive layer 13 on the side of the thermosetting resin layer 12 The difference in surface free energy is 10 mJ/m ² or more, whereby there is no component movement at the interface between the two, and the adhesive force is stable, and the interface between the first support sheet 101 and the thermosetting resin layer 12 is excellent in peelability. The difference between the surface free energy of the first support sheet 101 side surface of the thermosetting resin layer 12 before heat curing and the surface free energy of the first adhesive layer 13 side surface of the thermosetting resin layer 12 is preferably 12 mJ/ m ² to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

Fig. 2 is a cross-sectional view schematically showing another embodiment of the protective film forming sheet of the present invention. In addition, in FIG. 2, the same components as those shown in FIG. 1 are denoted by the same reference numerals as in the case of FIG. 1, and detailed descriptions thereof are omitted. This situation is the same in Figure 3 and subsequent figures.

The protective film forming sheet 2 shown here is used as a first support sheet formed by laminating a first intermediate layer 14 on a first substrate 11 and laminating a first adhesive layer 13 on the aforementioned first intermediate layer 14 102. That is, the protective film forming sheet 2 is configured to include a first intermediate layer 14 on the first substrate 11, a first adhesive layer 13 on the first intermediate layer 14, and a first adhesive layer 13 on the first adhesive layer 13. Thermosetting resin layer 12. The first support sheet 102 is a laminate formed by sequentially stacking the first substrate 11, the first intermediate layer 14 and the first adhesive layer 13 on one surface 102a of the first support sheet 102, that is, the first A thermosetting resin layer 12 is provided on one surface 13a of the adhesive layer 13.

In other words, the protective film forming sheet 2 is in the protective film forming sheet 1 shown in FIG. 1, and the first intermediate layer 14 is further provided at the interface between the first base material 11 and the first adhesive layer 13.

For the sheet 2 for forming a protective film, the surface free energy of the surface of the thermosetting resin layer 12 on the side of the first support sheet 102 before thermal curing is compared with the surface free energy of the surface of the first adhesive layer 13 on the side of the thermosetting resin layer 13 The difference in surface free energy is 10 mJ/m ² or more, whereby there is no component movement at the interface between the two, and the adhesive force is stable, and the interface between the first support sheet 102 and the thermosetting resin layer 12 is excellent in peelability. The difference between the surface free energy of the surface of the first support sheet 102 side of the thermosetting resin layer 12 before heat curing and the surface free energy of the surface of the first adhesive layer 13 on the side of the thermosetting resin layer 12 is preferably 12 mJ/ m ² to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

Fig. 3 is a cross-sectional view schematically showing still another embodiment of the protective film forming sheet of the present invention.

The sheet 3 for forming a protective film shown here uses only the first base material 11 as the first support sheet 103. That is, the sheet 3 for forming a protective film is configured to include a thermosetting resin layer 12 on the first base material 11. The first support sheet 103 is composed of only the first base material 11, and a thermosetting resin layer 12 is provided in direct contact with one surface 103a of the first support sheet 103, that is, one surface 11a of the first base material 11 .

In other words, the protective film forming sheet 3 is obtained by removing the first adhesive layer 13 from the protective film forming sheet 1 shown in FIG. 1. For the sheet 3 for forming a protective film, the surface free energy of the surface of the thermosetting resin layer 12 on the side of the first support sheet 103 before heat curing and the surface of the surface of the first support sheet 103 on the side of the thermosetting resin layer 12 The difference in free energy is 10 mJ/m ² or more, whereby there is no component movement at the interface between the two, the adhesive force is stable, and the interface between the first support sheet 103 and the thermosetting resin layer 12 is excellent in peelability. The difference between the surface free energy of the surface of the first support sheet 103 side of the thermosetting resin layer 12 before heat curing and the surface free energy of the surface of the first support sheet 103 on the side of the thermosetting resin layer 12 is preferably 12 mJ/m ² to 100mJ / m ^2, more preferably 15mJ / m ² to 90mJ / m ^2, more preferably 18mJ / m ² to 85mJ / m ^2, and particularly preferably 20mJ / m ² to 80mJ / m ^2.

FIG. 4 is a cross-sectional view schematically showing an example of a semiconductor wafer 90 having bumps 91. The circuit surface 90a of the semiconductor wafer 90 shown here is provided with a plurality of bumps 91.

The bump 91 has, for example, a shape in which a part of the ball is cut out by a plane, and the plane corresponding to the cut out portion is in contact with the circuit surface 90 a of the semiconductor wafer 90. The shape of the bump is not limited to the shape shown in the figure. The effect of the present invention (easy peelability of the interface between the first support sheet and the thermosetting resin layer) includes elliptical spherical bumps on the projection surface Especially effective.

5 is a cross-sectional view schematically showing a state in which the protective film forming sheet of the present invention is attached to the surface of the semiconductor wafer 90 having bumps 91. The attached thermosetting resin layer 12 has increased fluidity by heating, spreads between the bumps to cover the bumps and is in close contact with the circuit surface, and covers the surface of the bumps, especially the vicinity of the circuit surface The surface of the site is filled with bumps.

By setting the thickness of the thermosetting resin layer 12 to be thinner than the height of the bump 91, and combining the thermosetting resin layer 12 and the first adhesive layer 13 The gauge thickness is set to be thicker than the height of the bump 91, and the entire bump 91 is covered by the thermosetting resin layer 12 and the first adhesive layer 13.

Regarding the semiconductor wafer after the protective film forming sheet is attached, for example, after polishing the surface opposite to the aforementioned circuit surface, the first support sheet 101 is removed, and then the thermosetting resin layer 12 is heated to perform the second The formation of a protective film 12' is finally cut into a chip of a predetermined size with the first protective film 12' provided, and assembled into a semiconductor device.

6 is a cross-sectional view schematically showing an example of a semiconductor wafer 90 provided with a first protective film 12' formed using the protective film forming sheet 1 of the present invention. The first protective film 12' is formed by using the thermosetting resin film of the present invention to cover the circuit surface 90a of the semiconductor wafer 90, and further cover the top 911 of the bump 91 among the surface 91a of the bump 91 and its Areas outside the vicinity are covered.

In the protective film forming sheet 1 of the present invention, the easy peelability of the interface between the first support sheet 101 and the thermosetting resin layer 12, that is, the easy peeling of the interface between the first adhesive layer 13 and the thermosetting resin layer 12 It has excellent properties, so when the first support sheet 101 is peeled off, there will be no peeling failure. As shown in FIG. 6, after curing, the thermosetting resin layer 12 that becomes the first protective film 12' can remain to protect the circuit surface and convexity. Piece.

○First base material

The aforementioned first substrate may be composed of only one layer (single layer), or may be composed of multiple layers of two or more layers. When the aforementioned substrate is composed of multiple layers, the constituent materials and thicknesses of the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

Furthermore, in this specification, it is not limited to the case of the base material. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, all the layers may be different, or only a part of the layers may be the same. ", and "a plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

The aforementioned first base material is in a sheet shape or a film shape, and as its constituent material, various resins can be cited, for example.

Examples of the aforementioned resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, poly Polyolefins other than polyethylene such as methylpentene and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norbornane Vinyl copolymers such as olefin copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride as a monomer); polystyrene; poly Cyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene isophthalate, polyethylene 2,6-naphthalate, All structural units have aromatic cyclic groups such as fully aromatic polyesters Esters; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes; polyacrylate urethanes; polyimides; polyamides; polycarbonates; fluorine Resin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfide; polyether ketone, etc.

In addition, as the aforementioned resin, for example, polymer alloys such as a mixture of the aforementioned polyester and other resins can also be cited. The polymer alloy of the aforementioned polyester and other resins preferably has a relatively small amount of resins other than polyester.

In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or two or more of the aforementioned resins exemplified so far; and one or two or more of the aforementioned resins exemplified so far are used The ionic polymer and other modified resins.

Furthermore, in this specification, the term "(meth)acrylic acid" refers to the concept including both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the so-called "(meth)acrylate" includes the concepts of both "acrylate" and "methacrylate". The so-called "(meth)acrylic acid ester" "Is a concept that includes both "acrylic acid base" and "methacrylic acid base".

The resin constituting the first base material may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

The first substrate can be only one layer (single layer), or it can be a plurality of more than two layers In the case of multiple layers, the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited.

The thickness of the first substrate is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm, further preferably 15 μm to 300 μm, and particularly preferably 20 μm to 150 μm.

The "thickness of the first substrate" herein refers to the overall thickness of the first substrate. For example, the thickness of the first substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the first substrate.

The first base material is preferably one with high thickness accuracy, that is, one whose thickness deviation is suppressed regardless of the location. Among the above-mentioned constituent materials, as materials that can be used to construct the first base material with such a high accuracy of thickness, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-acetic acid can be cited. Vinyl ester copolymers, etc.

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

The first substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor-deposited with other layers.

In the case where the first adhesive layer or the curable resin layer described later has energy ray curability, the first base material preferably transmits energy rays.

The first substrate can be manufactured by a known method. For example, the first substrate containing resin can be manufactured by molding a resin composition containing the aforementioned resin.

○The first adhesive layer

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

As the aforementioned adhesives, for example, acrylic resins (adhesives composed of resins having (meth)acrylic groups), urethane resins (composed of resins having urethane bonds) Adhesive), rubber resin (adhesive composed of resin with rubber structure), silicone resin (adhesive composed of resin with silicone bond), epoxy resin (adhesive composed of resin with Adhesive resin composed of epoxy-based resin), polyvinyl ether, polycarbonate, and other adhesive resins are preferably acrylic resins.

Furthermore, in the present invention, the so-called "adhesive resin" includes the concept of both adhesive resin and adhesive resin. For example, not only the resin itself has adhesiveness, but also other materials such as adhesives and additives. A resin that exhibits adhesiveness when the ingredients are used in combination, or a resin that exhibits adhesiveness by the presence of a trigger such as heat or water.

The first adhesive layer can be only one layer (single layer), or multiple layers of more than two layers. In the case of multiple layers, the multiple layers may be the same or different from each other. The combination of the multiple layers There is no particular limitation.

The thickness of the first adhesive layer is preferably 1 μm to 1000 μm, more preferably 5 μm to 500 μm, and particularly preferably 10 μm to 100 μm.

The "thickness of the first adhesive layer" herein refers to the overall thickness of the first adhesive layer, for example, the thickness of the first adhesive layer composed of a plurality of layers refers to all the layers constituting the first adhesive layer The total thickness.

The first adhesive layer may be formed using an energy ray curable adhesive, or may be formed using a non-energy ray curable adhesive. The first adhesive layer formed by using an energy-ray curable adhesive can easily adjust the physical properties before and after curing.

In the present invention, the "energy rays" refer to electromagnetic waves or charged ion beams having energy quantum, and examples thereof include ultraviolet rays, electron beams, and the like.

The ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp (husion H lamp), a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as the ultraviolet source. Regarding the electron beam, the one generated by an electron beam accelerator or the like can be irradiated.

In the present invention, the "energy ray curability" refers to the property of curing by irradiation of energy rays, and the so-called "non-energy ray curability" refers to the property of not curing even if energy rays are irradiated.

<<The first adhesive composition>>

The first adhesive layer can be composed of a first adhesive containing an adhesive The thing is formed. For example, by coating the first adhesive composition on the surface to be formed of the first adhesive layer, and drying if necessary, the first adhesive layer can be formed on the target site. The method of forming other layers will be described in detail later. The ratio of the contents of the components that do not vaporize at room temperature in the first adhesive composition is usually the same as the ratio of the contents of the aforementioned components of the first adhesive layer. Furthermore, in this specification, the term "normal temperature" refers to a temperature that is not particularly cold or hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C.

The application of the first adhesive composition may be performed by a known method, for example, air knife coater, knife coater, bar coater, gravure coater, roll coater can be used. , Roll knife coater, curtain coater, pattern coater, blade coater, screen coater, wire bar coater, kiss coater and other coating machine methods.

The drying conditions of the first adhesive composition are not particularly limited. When the first adhesive composition contains the solvent described later, it is preferable to perform heating and drying. In this case, for example, it is preferably at 70°C to 130°C. And dry under the condition of 10 seconds to 5 minutes.

When the first adhesive layer is energy ray curable, as the first adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable first adhesive composition, for example, the following adhesives can be cited Agent composition Etc.: The first adhesive composition (I-1), which contains a non-energy-ray curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)"), and energy Linear curable compound; The first adhesive composition (I-2), which is contained in the side chain of a non-energy-ray-curable adhesive resin (I-1a). An energy-ray-curable adhesive with unsaturated groups introduced into the side chain Resin (I-2a) (hereinafter sometimes referred to as "adhesive resin (I-2a)"); and a first adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a), And energy ray curable low-molecular compound.

<First adhesive composition (I-1)>

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

[Adhesive resin (I-1a)]

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

As said acrylic resin, the acrylic polymer which has at least the structural unit derived from alkyl (meth)acrylate is mentioned, for example.

The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

As said (meth)acrylic acid alkyl ester, the carbon number of the alkyl group which comprises an alkyl ester is 1-20, for example, The said alkyl group is preferably linear or branched.

As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (also known as lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth) ) Cetyl acrylate (also known as palm ester (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as (meth)acrylic acid) Stearyl ester), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

In terms of improving the adhesion of the first adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group. Moreover, in terms of further improving the adhesive force of the first adhesive layer, the carbon number of the aforementioned alkyl group is preferably 4-12, and more preferably 4-8. In addition, the alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms is preferably an alkyl acrylate.

The aforementioned acrylic polymer is preferably in addition to (meth)acrylic acid In addition to the structural unit of the alkyl ester, it further has a structural unit derived from a monomer containing a functional group.

Examples of the aforementioned functional group-containing monomer include: the aforementioned functional group reacts with the crosslinking agent described later to become the starting point of crosslinking, or the aforementioned functional group reacts with the unsaturated group in the unsaturated group-containing compound, and This can introduce an unsaturated group into the side chain of the acrylic polymer.

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

That is, as a monomer containing a functional group, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing an epoxy group, and the like can be cited.

Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxymethyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylene unsaturated dicarboxylic acids such as maleic acid and citraconic acid (dicarboxylic acids with ethylenic unsaturated bonds); the aforementioned ethylene Anhydrides of unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate and other (meth)acrylate carboxyalkyl esters.

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

The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type or two or more types, and when there are two or more types, these combinations and ratios can be arbitrarily selected.

In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably from 1% by mass to 35% by mass, more preferably from 3% by mass to 32% by mass, relative to the total amount of structural units. More preferably, it is 5 mass% to 30 mass %.

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

The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylates and the like.

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

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

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

On the other hand, an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group (energy-ray polymerizable group) reacted with the functional group in the aforementioned acrylic polymer can be used as the aforementioned energy-ray curable Adhesive resin (I-2a).

Furthermore, the "energy ray polymerizability" in the present invention refers to the property of polymerization by irradiation of energy rays.

The adhesive resin (I-1a) contained in the first adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio may be arbitrary To choose.

In the first adhesive composition (I-1), relative to the total mass of the aforementioned first adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5% to 99% by mass %, more preferably 10% by mass to 95% by mass, particularly preferably 15% by mass to 90% by mass.

[Energy ray curable compound]

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

Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. (Meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylic urethane Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc.

Among the energy ray curable compounds, examples of the oligomer include oligomers formed by polymerizing the monomers exemplified above.

In terms of relatively large molecular weight and not easy to reduce the storage elastic modulus of the first adhesive layer, the energy ray curable compound is preferably (meth)acrylate urethane, (meth)acrylate amine group Formate oligomers.

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

In the first adhesive composition (I-1), relative to the total mass of the first adhesive composition (I-1), the content of the energy ray curable compound is preferably 1% by mass to 95% by mass , More preferably 5% by mass to 90% by mass, particularly preferably 10% by mass to 85% by mass.

[Crosslinking agent]

When using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from alkyl (meth)acrylate as the adhesive resin (I-1a), the first An adhesive composition (I-1) preferably further contains a crosslinking agent.

The aforementioned crosslinking agent reacts with the aforementioned functional group, for example, to crosslink the adhesive resins (I-1a) with each other.

Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of these diisocyanates; Epoxy crosslinking agent such as glycol glycidyl ether (crosslinking agent with glycidyl group); hexa[1-(2-methyl)-aziridinyl] triphosphatriazine and other aziridine crosslinking agents Linking agent (crosslinking agent with aziridin group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent (Crosslinking agent with isocyanuric acid skeleton) and so on.

The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of improving the cohesive force of the adhesive and improving the adhesive force of the first adhesive layer, and ease of availability.

The crosslinking agent contained in the first adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the aforementioned first adhesive composition (I-1), relative to 100 parts by mass of the adhesive resin (I-1a), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 Parts by mass to 20 parts by mass, particularly preferably 1 part by mass to 10 parts by mass.

[Photopolymerization initiator]

The first adhesive composition (I-1) may further contain a photopolymerization initiator. The first adhesive composition (I-1) containing a photopolymerization initiator fully undergoes a curing reaction even if it is irradiated with a relatively low-energy energy line such as ultraviolet rays.

Examples of the aforementioned photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds; benzyl Thioether compounds such as methyl phenyl sulfide and tetramethyl thiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; ferrocene and other two Ferrocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetin; benzil, benzil, benzophenone, 2,4-diethylthioxanthone , 1,2-Diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2-chloroanthraquinone, etc.

In addition, as the aforementioned photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

The photopolymerization initiator contained in the first adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the first adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass relative to 100 parts by mass of the content of the aforementioned energy ray curable compound Parts by mass to 10 parts by mass, particularly preferably from 0.05 parts by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-1) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention.

Examples of the aforementioned other additives include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, Known additives such as reaction delay agents and crosslinking accelerators (catalysts).

Furthermore, the so-called reaction delay agent is, for example, inhibited in the first adhesive composition (I-1) during storage by the action of the catalyst mixed into the first adhesive composition (I-1) It is not the target of the cross-linking reaction proceeder. As the reaction delay agent, for example, a chelate complex is formed by a chelate to a catalyst, and more specifically, a molecule having two or more carbonyl groups is mentioned. (-C(=O)-).

The other additives contained in the first adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combinations and ratios can be arbitrarily selected.

The content of other additives in the first adhesive composition (I-1) is not particularly limited, as long as it is appropriately selected according to the kind.

[Solvent]

The first adhesive composition (I-1) may also contain a solvent. When the first adhesive composition (I-1) contains a solvent, the coating suitability to the coating target surface is improved.

The aforementioned solvent is preferably an organic solvent. Examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane (dioxane); Aliphatic hydrocarbons such as hexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

As the aforementioned solvent, for example, the adhesive resin (I-1a) used in the manufacture of the adhesive resin (I-1a) may not be removed from the adhesive resin (I-1a), but may be used directly in the first adhesive composition (I-1), or may also be used. When manufacturing the first adhesive composition (I-1), a solvent of the same or different type as that used when manufacturing the adhesive resin (I-1a) can be added separately.

The solvent contained in the first adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the first adhesive composition (I-1), the content of the solvent is not particularly limited, as long as it is appropriately adjusted.

<First adhesive composition (I-2)>

As described above, the first adhesive composition (I-2) is contained in the side chain of the non-energy-ray-curable adhesive resin (I-1a). The side chain of the energy-ray-curable adhesive resin (I-1a) is I-2a).

[Adhesive resin (I-2a)]

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

The aforementioned unsaturated group-containing compound is that in addition to the aforementioned energy-ray polymerizable unsaturated group, it further has the ability to bond with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) The group of compounds.

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

Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include: isocyanate groups and glycidyl groups that can be bonded to hydroxyl or amino groups, and carboxyl or epoxy groups that can be bonded The hydroxyl and amino groups of the junction.

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

The adhesive resin (I-2a) contained in the first adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio may be arbitrary To choose.

In the first adhesive composition (I-2), relative to the total mass of the aforementioned first adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass %, more preferably 10% by mass to 95% by mass, particularly preferably 10% by mass to 90% by mass.

[Crosslinking agent]

For example, when the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the first adhesive The agent composition (I-2) may further contain a crosslinking agent.

Examples of the aforementioned crosslinking agent in the first adhesive composition (I-2) include The same as the crosslinking agent in the first adhesive composition (I-1).

The crosslinking agent contained in the first adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the aforementioned first adhesive composition (I-2), relative to 100 parts by mass of the adhesive resin (I-2a), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 Parts by mass to 20 parts by mass, particularly preferably 1 part by mass to 10 parts by mass.

[Photopolymerization initiator]

The first adhesive composition (I-2) may further contain a photopolymerization initiator. The first adhesive composition (I-2) containing a photopolymerization initiator fully undergoes a curing reaction even if it is irradiated with a relatively low-energy energy line such as ultraviolet rays.

As the photopolymerization initiator in the first adhesive composition (I-2), the same as the photopolymerization initiator in the first adhesive composition (I-1) can be cited.

The photopolymerization initiator contained in the first adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the first adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 mass parts relative to the content of the adhesive resin (I-2a) 100 parts by mass The amount is from 20 parts by mass, more preferably from 0.03 parts by mass to 10 parts by mass, and particularly preferably from 0.05 parts by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-2) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention.

Examples of the aforementioned other additives in the first adhesive composition (I-2) include the same ones as the other additives in the first adhesive composition (I-1).

The other additives contained in the first adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combinations and ratios can be arbitrarily selected.

The content of other additives in the first adhesive composition (I-2) is not particularly limited, as long as it is appropriately selected according to the kind.

[Solvent]

The first adhesive composition (I-2) can also contain a solvent for the same purpose as in the case of the first adhesive composition (I-1).

Examples of the aforementioned solvent in the first adhesive composition (I-2) include the same solvents as those in the first adhesive composition (I-1).

The solvent contained in the first adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the first adhesive composition (I-2), the content of the solvent is not particularly limited As long as it is adjusted appropriately.

<First adhesive composition (I-3)>

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

In the first adhesive composition (I-3), relative to the total mass of the aforementioned first adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5% to 99% by mass %, more preferably 10% by mass to 95% by mass, particularly preferably 15% by mass to 90% by mass.

[Energy ray curable low molecular compound]

Examples of the aforementioned energy ray curable low molecular compound contained in the first adhesive composition (I-3) include monomers and oligomers that have energy ray polymerizable unsaturated groups and can be cured by energy ray irradiation. Examples thereof include the same energy ray curable compounds contained in the first adhesive composition (I-1).

The aforementioned energy ray curable low-molecular compound contained in the first adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio may be arbitrary To choose.

In the aforementioned first adhesive composition (I-3), relative to 100 parts by mass of the adhesive resin (I-2a), the content of the energy ray curable low-molecular compound is preferably 0.01 to 300 parts by mass , More preferably 0.03 Parts by mass to 200 parts by mass, more preferably 0.05 parts by mass to 100 parts by mass.

[Photopolymerization initiator]

The first adhesive composition (I-3) may further contain a photopolymerization initiator. The first adhesive composition (I-3) containing a photopolymerization initiator fully undergoes a curing reaction even if it is irradiated with a relatively low-energy energy line such as ultraviolet rays.

Examples of the photopolymerization initiator in the first adhesive composition (I-3) include the same ones as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator contained in the first adhesive composition (I-3) may be only one type or two or more types, and when there are two or more types, the combination and ratio can be arbitrarily selected.

In the first adhesive composition (I-3), the content of the photopolymerization initiator is preferably 100 parts by mass relative to the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable low-molecular compound 0.01 parts by mass to 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives]

The first adhesive composition (I-3) may also contain other additives that are not equivalent to any of the above-mentioned components within a range that does not impair the efficacy of the present invention.

As the aforementioned other additives, the first adhesive composition can be listed The other additives in (I-1) are the same.

The other additives contained in the first adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combinations and ratios can be arbitrarily selected.

The content of other additives in the first adhesive composition (I-3) is not particularly limited, as long as it is appropriately selected according to the kind.

[Solvent]

The first adhesive composition (I-3) can also contain a solvent for the same purpose as in the case of the first adhesive composition (I-1).

Examples of the aforementioned solvent in the first adhesive composition (I-3) include the same solvents as those in the first adhesive composition (I-1).

The solvent contained in the first adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

In the first adhesive composition (I-3), the content of the solvent is not particularly limited, as long as it is appropriately adjusted.

<The first adhesive composition (I-1) to the first adhesive composition other than the first adhesive composition (I-3)>

So far, the first adhesive composition (I-1), the first adhesive composition (I-2), and the first adhesive composition (I-3) have been mainly described, but as these Contains the ingredients and the description is in the composition of the three first adhesives All first adhesive compositions other than the first adhesive composition (in this specification, referred to as "the first adhesive composition (I-1) to the first adhesive composition other than the first adhesive composition (I-3)" ) Can also be used in the same way.

As the first adhesive composition other than the first adhesive composition (I-1) to the first adhesive composition (I-3), in addition to the energy-ray curable adhesive composition, non-energy Linear curing adhesive composition.

Examples of non-energy-ray-curable adhesive compositions include acrylic resins (resins having (meth)acrylic groups) and urethane resins (resins having urethane bonds). ), rubber resin (resin with rubber structure), silicone resin (resin with silicone bond), epoxy resin (resin with epoxy group), polyvinyl ether or polycarbonate, etc. The resin is preferably one containing acrylic resin.

The first adhesive composition other than the first adhesive composition (I-1) to the first adhesive composition (I-3) preferably contains one or two or more crosslinking agents, and the content can be set to It is the same as the above-mentioned first adhesive composition (I-1) and the like.

<<Method for manufacturing the first adhesive composition>>

The first adhesive composition such as the first adhesive composition (I-1) to the first adhesive composition (I-3) can be obtained by combining the adhesive and, if necessary, components other than the adhesive, etc. It is obtained by blending the components used to form the first adhesive composition.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used in the following ways: mixing the solvent with any compounding component other than the solvent and pre-diluting the compounding component; or not pre-diluting any compounding component other than the solvent, but mixing the solvent with The blending ingredients are mixed.

The method of mixing the ingredients at the time of blending is not particularly limited, as long as it is appropriately selected from well-known methods such as the following methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; application The method of ultrasonic mixing.

Regarding the addition of each component and the temperature and time during mixing, there are no particular limitations as long as each compounding component does not deteriorate, as long as it is appropriately adjusted, and the temperature is preferably 15°C to 30°C.

○The first middle layer

The aforementioned first intermediate layer has a sheet shape or a film shape, and its constituent material may be appropriately selected according to the purpose, and is not particularly limited.

For example, in order to prevent the shape of the bumps existing on the semiconductor surface from being reflected on the protective film covering the semiconductor surface and causing deformation of the protective film, the preferred constituent material of the first intermediate layer is the In terms of further improvement in adhesiveness, (meth)acrylate urethane and the like can be mentioned.

The first intermediate layer can be only one layer (single layer), or it can be a complex with more than two layers In the case of multiple layers, the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited.

The thickness of the first intermediate layer can be appropriately adjusted according to the height of the bumps on the semiconductor surface to be protected, and in terms of easily absorbing the influence of bumps with relatively high height, it is preferably 50 μm to 600 μm, It is more preferably 70 μm to 500 μm, and particularly preferably 80 μm to 400 μm. .

The "thickness of the first intermediate layer" herein refers to the overall thickness of the first intermediate layer. For example, the thickness of the first intermediate layer composed of a plurality of layers refers to the total thickness of all the layers constituting the first intermediate layer.

<<The composition for forming the first intermediate layer>>

The first intermediate layer can be formed using a first intermediate layer forming composition containing its constituent material.

For example, the composition for forming the first intermediate layer is applied to the surface to be formed of the first intermediate layer, dried as necessary, or cured by irradiation of energy rays, thereby forming the first intermediate layer on the target site. A more specific method of forming the first intermediate layer will be described in detail later together with the method of forming other layers. The ratio of the contents of the components that do not vaporize at room temperature in the composition for forming the first intermediate layer is usually the same as the ratio of the contents of the aforementioned components of the first intermediate layer. The so-called "normal temperature" here is as explained above.

The coating of the composition for forming the first intermediate layer only needs to use a known method. The method can be carried out, for example, the use of an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, and a curtain coater , Pattern coater, blade coater, screen coater, wire bar coater, kiss coater and other coating machine methods.

The drying conditions of the composition for forming the first intermediate layer are not particularly limited. When the composition for forming the first intermediate layer contains a solvent described later, it is preferable to heat and dry. In this case, for example, it is preferably 70%. Dry under the conditions of ℃ to 130 ℃ and 10 seconds to 5 minutes.

In the case where the composition for forming the first intermediate layer has energy ray curability, it is preferable to further cure by energy ray irradiation after drying.

As the composition for forming the first intermediate layer, for example, the composition for forming the first intermediate layer (II-1) containing (meth)acrylate urethane, etc. may be cited.

<First Intermediate Layer Formation Composition (II-1)>

As described above, the first intermediate layer forming composition (II-1) contains (meth)acrylate urethane.

[(Meth) acrylate urethane]

The (meth)acrylate urethane is a compound having at least a (meth)acrylic group and a urethane bond in one molecule, and has energy-beam polymerizability.

The (meth)acrylate urethane can be monofunctional (one molecule has only one (meth)acrylic acid group), or it can be bifunctional or more (one molecule has more than two (form) (Base) acryloyl group), that is, polyfunctional, preferably at least monofunctional.

Examples of the aforementioned (meth)acrylate urethane contained in the composition for forming the first intermediate layer include: reacting a polyol compound and a polyisocyanate compound to obtain a terminal isocyanate urethane prepolymer, It is obtained by reacting a (meth)acrylic compound having a hydroxyl group and a (meth)acrylic acid group with the aforementioned terminal isocyanate urethane prepolymer. Here, the term "terminal isocyanate urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

The (meth)acrylate urethane contained in the composition for forming the first intermediate layer (II-1) may be only one type or two or more types. In the case of two or more types, the combination of these And the ratio can be arbitrarily selected.

(Polyol compound)

The aforementioned polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.

The aforementioned polyol compound may be used singly or in combination of two or more, and when two or more of them are used in combination, the combination and ratio can be arbitrarily selected.

As said polyol compound, alkylene glycol, polyether polyol, polyester polyol, polycarbonate polyol, etc. are mentioned, for example.

The aforementioned polyol compound may be any of difunctional diols, trifunctional triols, and tetrafunctional or higher polyols. In terms of easy availability and excellent versatility and reactivity, diols are preferred. .

. Polyether polyol

The polyether polyol is not particularly limited, but is preferably a polyether diol. Examples of the polyether diol include compounds represented by the following general formula (1).

(In the formula, n is an integer of 2 or more; R is a divalent hydrocarbon group, and a plurality of Rs may be the same or different from each other.)

In the formula, n represents the number of repeating units of the group represented by the general formula "-R-O-", and it is not particularly limited as long as it is an integer of 2 or more. Among them, n is preferably 10 to 250, more preferably 25 to 205, and particularly preferably 40 to 185.

In the formula, R is not particularly limited as long as it is a divalent hydrocarbon group. It is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an ethylene group, a propylene group or a tetramethylene group. , Particularly preferably propylene or tetramethylene.

The compound represented by the aforementioned formula (1) is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, more preferably polypropylene glycol or polytetramethylene glycol.

By reacting the polyether diol with the polyvalent isocyanate compound, one having an ether bond portion represented by the following general formula (1a) can be obtained as the terminal isocyanate urethane prepolymer. Moreover, by using such a terminal isocyanate urethane prepolymer, the (meth)acrylate urethane has the ether bond portion, that is, it has the polyether diol derived The structural unit.

(In the formula, R and n are the same as above.)

. Polyester polyol

The said polyester polyol is not specifically limited, For example, what is obtained by esterification reaction using a polybasic acid or its derivative(s) is mentioned. In addition, the term "derivative" in the present specification means that one or more groups of the original compound are substituted with other groups (substituents) unless otherwise specified. The so-called "group" here not only refers to a group of atoms formed by bonding multiple atoms, but also includes one atom.

Examples of the aforementioned polybasic acid and its derivatives include polybasic acids and their derivatives that are generally used as raw materials for polyester production.

As said polybasic acid, saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid, aromatic polybasic acid, etc. are mentioned, for example, and the dimer acid corresponding to any of these can also be used.

Examples of the saturated aliphatic polybasic acid include saturated aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. Sour etc.

As said unsaturated aliphatic polybasic acid, unsaturated aliphatic dibasic acids, such as maleic acid and fumaric acid, etc. are mentioned, for example.

Examples of the aforementioned aromatic polybasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid; and aromatic tribasic acids such as trimellitic acid. ; Aromatic tetrabasic acids such as pyromellitic acid.

Examples of derivatives of the aforementioned polybasic acid include acid anhydrides of the above-mentioned saturated aliphatic polybasic acid, unsaturated aliphatic polybasic acid, and aromatic polybasic acid, and hydrogenated dimer acid.

The aforementioned polybasic acid or its derivatives may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio of these can be arbitrarily selected.

In terms of being suitable for forming a coating film having moderate hardness, the aforementioned polybasic acid is preferably an aromatic polybasic acid.

In the esterification reaction used to obtain polyester polyols, well-known catalysts can also be used as needed.

Examples of the aforementioned catalyst include tin compounds such as dibutyltin oxide and stannous octoate; titanium alkoxides such as tetrabutyl titanate and tetrapropyl titanate.

. Polycarbonate polyol

The polycarbonate polyol is not particularly limited, and examples thereof include those obtained by reacting the same diol as the compound represented by the aforementioned formula (1) with alkylene carbonate.

Here, diol and alkylene carbonate may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, these combinations and ratios can be selected arbitrarily.

The number average molecular weight calculated from the hydroxyl value of the aforementioned polyol compound is preferably 1,000 to 10,000, more preferably 2,000 to 9,000, and particularly preferably 3,000 to 7,000. With the aforementioned number average molecular weight being 1000 or more, the excessive generation of urethane bonds is suppressed, and the control of the viscoelastic properties of the first intermediate layer becomes easier. In addition, since the aforementioned number average molecular weight is 10,000 or less, excessive softening of the first intermediate layer is suppressed.

The aforementioned number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated from the following formula.

[Number average molecular weight of polyol compound]=[Number of functional groups of polyol compound]×56.11×1000/[hydroxyl value of polyol compound (unit: mgKOH/g)]

The aforementioned polyol compound is preferably a polyether polyol, more preferably a polyether diol.

(Polyisocyanate compound)

The polyvalent isocyanate compound that reacts with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.

A polyvalent isocyanate compound may be used individually by 1 type, or may use 2 or more types together, and when using 2 or more types together, these combinations and ratios can be selected arbitrarily.

Examples of the aforementioned polyvalent isocyanate compound include: chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, norcampan Alkyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ω,ω'-diisocyanate dimethylcyclohexane and other cyclic aliphatic diisocyanates ; 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, toluidine diisocyanate, tetramethylene xylene diisocyanate, naphthalene-1,5-diisocyanate and other aromatic diisocyanates Wait.

Among them, in terms of handling properties, the polyvalent isocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate, or xylene diisocyanate.

((Meth)acrylic compound)

The (meth)acrylic compound to be reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth)acryloyl group in one molecule.

The aforementioned (meth)acrylic compound may be used singly or in combination of two or more, and when two or more are used in combination, the combination and ratio of these compounds can be arbitrarily selected.

As the aforementioned (meth)acrylic compound, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 5-hydroxy (meth)acrylate Cyclooctyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylic acid (Meth)acrylic acid esters containing hydroxyl groups such as esters; (meth)acrylic acid esters containing hydroxyl groups such as N-methylol(meth)acrylamide; combining (meth)acrylic acid with vinyl alcohol, vinyl phenol or The reactant obtained by the reaction of bisphenol A diglycidyl ether, etc.

Among them, the aforementioned (meth)acrylic compound is preferably a hydroxyl-containing (meth)acrylate, more preferably a hydroxyl-containing alkyl (meth)acrylate, and particularly preferably (meth)acrylic acid 2 -Hydroxyethyl ester.

The reaction of the aforementioned terminal isocyanate urethane prepolymer and the aforementioned (meth)acrylic compound can be carried out using a solvent, a catalyst, etc., as necessary.

The conditions for reacting the aforementioned terminal isocyanate urethane prepolymer with the aforementioned (meth)acrylic compound should be appropriately adjusted. For example, the reaction temperature is preferably 60°C to 100°C, and the reaction time is preferably 1 hour. To 4 hours.

The aforementioned (meth)acrylate urethane may be any of oligomers, polymers, and mixtures of oligomers and polymers, and is preferably an oligomer.

For example, the weight average molecular weight of the aforementioned (meth)acrylate urethane is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and particularly preferably 5,000 to 65,000. Since the aforementioned weight average molecular weight is 1000 or more, in the polymer of (meth)acrylate urethane and the polymerizable monomer described later, the molecules derived from the structure of (meth)acrylate urethane It is easy to realize the optimization of the hardness of the first intermediate layer.

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

[Polymerizable monomer]

In terms of further improving film formability, the first intermediate layer forming composition (II-1) may contain a polymerizable monomer in addition to the aforementioned (meth)acrylate urethane.

The aforementioned polymerizable monomer preferably excludes oligomers and polymers having energy ray polymerizability and a weight average molecular weight of 1000 or more, and is a compound having at least one (meth)acryloyl group in one molecule.

As the aforementioned polymerizable monomers, for example, alkyl (meth)acrylates having a chain-like alkyl group having 1 to 30 carbon atoms constituting the alkyl ester; having a hydroxyl group, an amino group, an amino group, or a ring (Meth)acrylic compounds containing functional groups such as oxy groups; (meth)acrylates with aliphatic cyclic groups; (meth)acrylates with aromatic hydrocarbon groups; those with heterocyclic groups (Meth)acrylates; compounds with vinyl groups; compounds with allyl groups, etc.

As the aforementioned alkyl (meth)acrylate having a chain alkyl group having a carbon number of 1 to 30, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-(meth)acrylate Propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, Amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, (A Base) n-nonyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) Lauryl acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylate Base) hexadecyl acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (also known as stearyl (meth)acrylate) Ester), isostearyl (meth)acrylate (isostearyl (meth)acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

Examples of the functional group-containing (meth)acrylic acid derivatives include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; (meth)acrylic acid Amine, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane (meth)acrylamide, (Meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, etc. (meth)acrylamide and its derivatives; with amine (Meth)acrylate (hereinafter sometimes referred to as "amino-containing (meth)acrylate"); a mono-substituted amino group in which one hydrogen atom with an amino group is substituted by a group other than a hydrogen atom (Meth)acrylate (hereinafter sometimes referred to as "monosubstituted amino group-containing (meth)acrylate"); two hydrogen atoms with amino groups are substituted by groups other than hydrogen atoms. Amino (meth)acrylate (hereinafter sometimes referred to as "containing two (Meth)acrylates with substituted amino groups"); (meth)acrylates with epoxy groups such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate (hereinafter sometimes referred to as "Epoxy-containing (meth)acrylate") and so on.

Here, the "amino group-containing (meth)acrylate" refers to a compound in which one or two or more hydrogen atoms of the (meth)acrylate are substituted with an _{amino group (-NH 2 ).} Similarly, the so-called "monosubstituted amino group-containing (meth)acrylate" refers to a compound in which one or more hydrogen atoms of (meth)acrylate are replaced by a monosubstituted amino group. The term "(meth)acrylate with substituted amino group" refers to a compound in which one or more hydrogen atoms of (meth)acrylate are substituted with disubstituted amino groups.

Examples of groups other than the hydrogen atom that replaces the hydrogen atom in the "monosubstituted amino group" and the "disubstituted amino group" (that is, substituent groups) include, for example, alkyl groups.

Examples of the (meth)acrylate having an aliphatic cyclic group include: isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, Dicyclopentenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, and the like.

Examples of the (meth)acrylate having an aromatic hydrocarbon group include: phenylhydroxypropyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Propyl propyl ester and so on.

The heterocyclic group in the (meth)acrylate having a heterocyclic group may be any of an aromatic heterocyclic group and an aliphatic heterocyclic group.

Examples of the (meth)acrylate having a heterocyclic group include tetrahydrofurfuryl (meth)acrylate, (meth)acrylomorpholine, and the like.

Examples of the compound having a vinyl group include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, and N-vinylcaprolactone. Amine etc.

Examples of the compound having an allyl group include allyl glycidyl ether and the like.

In terms of good compatibility with the aforementioned (meth)acrylate urethane, the aforementioned polymerizable monomer preferably has a relatively large group, and examples of such polymerizable monomer include ：(Meth)acrylate with aliphatic cyclic group, (meth)acrylate with aromatic hydrocarbon group, (meth)acrylate with heterocyclic group, etc., more preferably with aliphatic cyclic group The (meth)acrylate.

The polymerizable monomer contained in the composition for forming the first intermediate layer (II-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected .

In the first intermediate layer forming composition (II-1), the content of the polymerizable monomer relative to the total mass of the first intermediate layer forming composition (II-1) is preferably 10% by mass to 99% by mass % Is more preferably 15% by mass to 95% by mass, still more preferably 20% by mass to 90% by mass, and particularly preferably 25% by mass to 80% by mass.

[Photopolymerization initiator]

The composition (II-1) for forming the first intermediate layer may contain a photopolymerization initiator in addition to the aforementioned (meth)acrylate urethane and polymerizable monomers. The composition (II-1) for forming a first intermediate layer containing a photopolymerization initiator sufficiently undergoes a curing reaction even if it is irradiated with a relatively low-energy energy line such as ultraviolet rays.

Examples of the photopolymerization initiator in the first intermediate layer forming composition (II-1) include the same photopolymerization initiator as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator contained in the composition for forming the first intermediate layer (II-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio may be arbitrarily selected. choose.

In the composition (II-1) for forming the first intermediate layer, the content of the photopolymerization initiator relative to 100 parts by mass of the total content of the aforementioned (meth)acrylate urethane and polymerizable monomer is preferably 0.01 parts by mass to 20 parts by mass, better It is 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Resin components other than (meth)acrylate urethane]

The composition (II-1) for forming the first intermediate layer may contain resin components other than the aforementioned (meth)acrylate urethane within a range that does not impair the effects of the present invention.

The kind of the aforementioned resin component and the content in the composition (II-1) for forming the first intermediate layer may be appropriately selected according to the purpose, and are not particularly limited.

[Other additives]

The composition (II-1) for forming the first intermediate layer may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the efficacy of the present invention.

Examples of the aforementioned other additives include: crosslinking agents, antistatic agents, antioxidants, chain transfer agents, softeners (plasticizers), fillers, rust inhibitors, colorants (pigments, dyes), and other known additives .

For example, as the aforementioned chain transfer agent, a thiol compound having at least one thiol group (mercapto group) in one molecule can be cited.

As the aforementioned thiol compound, for example, nonyl mercaptan, 1-dodecyl mercaptan, 1,2-ethanedithiol, 1,3-propanedithiol, triazine mercaptan, triazine disulfide Alcohol, triazine trithiol, 1,2,3-propane trithiol, tetraethylene glycol- Bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetramercaptoacetate, dipentaerythritol hexa(3-mercapto) Propionate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,4-bis(3-mercaptobutyroxy)butane, pentaerythritol tetra(3- Mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc. .

The other additives contained in the composition for forming the first intermediate layer (II-1) may be only one type or two or more types, and in the case of two or more types, the combinations and ratios thereof can be arbitrarily selected.

The content of other additives in the composition (II-1) for forming the first intermediate layer is not particularly limited, as long as it is appropriately selected according to the kind.

[Solvent]

The composition (II-1) for forming the first intermediate layer may contain a solvent. The composition for forming the first intermediate layer (II-1) contains a solvent to improve the coating suitability of the coating target surface.

<<Method for manufacturing first intermediate layer forming composition>>

The composition for forming the first intermediate layer, such as the composition for forming the first intermediate layer (II-1), is obtained by blending the components that constitute the composition.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

When a solvent is used in the composition for forming the first intermediate layer, it can be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; or not diluting any component other than the solvent The compounding ingredients are pre-diluted, and the solvent is mixed with the compounding ingredients.

The method of mixing the ingredients at the time of blending is not particularly limited, as long as it is appropriately selected from well-known methods such as the following methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; application The method of ultrasonic mixing.

Regarding the addition of each component and the temperature and time during mixing, there are no particular limitations as long as each compounding component does not deteriorate, as long as it is appropriately adjusted, and the temperature is preferably 15°C to 30°C.

◎Thermosetting resin layer

The aforementioned thermosetting resin layer is a layer used to protect the circuit surface of the semiconductor wafer and the bumps provided on the circuit surface, and the first protective film is formed by curing.

As a preferable thermosetting resin layer, what contains a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is regarded as a component formed by the polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) can be cured (polymerized) by using heat as a trigger for the reaction. Should be the ingredients. Furthermore, in the present invention, a polycondensation reaction is also included in the polymerization reaction.

The aforementioned thermosetting resin layer may be only one layer (single layer), or plural layers of two or more layers. In the case of plural layers, the plural layers may be the same or different from each other. The combination of the plural layers It is not particularly limited.

The thickness of the aforementioned thermosetting resin layer is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the thermosetting resin layer is greater than the aforementioned lower limit, a first protective film with higher protection ability can be formed. In addition, when the thickness of the thermosetting resin layer is not more than the aforementioned upper limit, the effect of suppressing bubbles in the first protective film is further improved.

Here, the "thickness of the thermosetting resin layer" refers to the thickness of the entire thermosetting resin layer. For example, the thickness of the thermosetting resin layer composed of a plurality of layers refers to the thickness of all layers constituting the thermosetting resin layer. Total thickness.

<<Composition for forming thermosetting resin layer>>

The thermosetting resin layer can be formed using a composition for forming a thermosetting resin layer containing its constituent materials. For example, the composition for forming a thermosetting resin layer is applied to the surface to be formed of the thermosetting resin layer, and dried as necessary, whereby the thermosetting resin layer can be formed on the target site. Regarding the components that do not vaporize at room temperature in the composition for forming a thermosetting resin layer The ratio of this content is usually the same as the ratio of the content of the aforementioned components of the thermosetting resin layer. The so-called "normal temperature" here is as explained above.

The coating of the composition for forming a thermosetting resin layer may be performed by a known method, for example, the use of an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll coater can be used. Coating machine, roller knife coater, curtain coater, pattern coater, blade coater, screen coater, wire bar coater, kiss coater, etc. method.

The drying conditions of the composition for forming a thermosetting resin layer are not particularly limited. When the composition for forming a thermosetting resin layer contains a solvent described later, it is preferable to heat and dry. In this case, for example, Drying is performed under the conditions of 70°C to 130°C and 10 seconds to 5 minutes.

<Composition for forming resin layer (III-1)>

Examples of the composition for forming a thermosetting resin layer include a composition (III-1) for forming a thermosetting resin layer containing a polymer component (A) and a thermosetting component (B) (in this specification, there is In this case, it is simply referred to as "composition for resin layer formation (III-1)") and the like.

[Polymer component (A)]

The polymer component (A) is a polymer compound for imparting film-forming properties or flexibility to the thermosetting resin layer.

The composition for forming a resin layer (III-1) and the polymer component (A) contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, the combination of these And the ratio can be arbitrarily selected.

As the polymer component (A), for example, acrylic resin (resin having a (meth)acrylic acid group), polyester, urethane resin (resin having a urethane bond), Acrylic urethane resin, silicone resin (resin with silicone bond), rubber resin (resin with rubber structure), phenoxy resin, thermosetting polyimide, etc., preferably Acrylic resin.

As the aforementioned acrylic resin of the polymer component (A), known acrylic polymers can be cited.

The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or greater than the aforementioned lower limit, the shape stability (stability with time during storage) of the thermosetting resin layer improves. In addition, since the weight average molecular weight of the acrylic resin is equal to or less than the aforementioned upper limit, the thermosetting resin layer easily follows the uneven surface of the adherend.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is equal to or higher than the aforementioned lower limit, the adhesion between the first protective film and the first support sheet is suppressed, and the releasability of the first support sheet is improved. In addition, with acrylic resin The Tg of is below the above-mentioned upper limit, and the adhesive force between the thermosetting resin layer and the first protective film and the adherend is improved.

Examples of acrylic resins include: one or two or more (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxy Copolymers of two or more monomers in methacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Alkyl esters such as hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl is a (meth)acrylic acid alkyl ester with a chain structure of 1 to 18 carbon atoms; (meth)acrylic acid cycloalkanes such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. Base ester; benzyl (meth)acrylate (Meth) aralkyl acrylate; (meth) acrylate, etc. cycloalkenyl (meth) acrylate; (meth) acrylate, etc. (meth) cyclopentenyl acrylate; (meth) acrylate, etc. (meth) Cycloalkenyloxyalkyl acrylate; (meth)acrylimines; (meth)acrylates containing glycidyl groups such as glycidyl (meth)acrylate; hydroxymethyl (meth)acrylate, (meth) Base) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxy (meth)acrylate Hydroxyl-containing (meth)acrylates such as butyl ester and 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid containing substituted amino groups such as N-methylaminoethyl (meth)acrylate Ester etc. The "substituted amino group" here refers to a group in which one or two hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms.

The acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the aforementioned (meth)acrylate. It is formed by copolymerization of one or more than two monomers.

The monomers constituting the acrylic resin may be only one type or two or more types, and in the case of two or more types, the combinations and ratios can be arbitrarily selected.

The acrylic resin may also have functional groups such as vinyl groups, (meth)acrylic groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional groups of the acrylic resin can pass through the crosslinking agent (F) described later The bonding with other compounds may also directly bond with other compounds without the crosslinking agent (F). Since the acrylic resin is bonded to other compounds via the aforementioned functional group, the reliability of the package obtained by using the protective film forming sheet tends to be improved.

In the present invention, as the polymer component (A), instead of using acrylic resin, a thermoplastic resin other than acrylic resin (hereinafter, sometimes simply referred to as "thermoplastic resin") may be used alone, or the thermoplastic resin may be combined with acrylic resin. System resins are used together. By using the aforementioned thermoplastic resin, the releasability of the first protective film from the first support sheet may be improved, or the thermosetting resin layer may easily follow the uneven surface of the adherend.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

As said thermoplastic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The composition (III-1) for forming a resin layer and the aforementioned thermoplastic resin contained in the thermosetting resin layer may be one type or two or more types. In the case of two or more types, the combination and ratio may be Choose arbitrarily.

In the resin layer forming composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the content of the polymer component (A) of the thermosetting resin layer) ) Does not depend on the type of the polymer component (A), but is preferably 5 to 85% by mass, more preferably 5 to 80% by mass.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the resin layer forming composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), it is regarded as the resin layer forming composition The substance (III-1) contains a polymer component (A) and a thermosetting component (B).

[Thermosetting component (B)]

The thermosetting component (B) is a component for curing the thermosetting resin layer to form a hard first protective film.

The composition for forming a resin layer (III-1) and the thermosetting component (B) contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., and cyclic resins are preferred. Oxygen-based thermosetting resin.

(Epoxy-based thermosetting resin)

The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).

The composition for forming a resin layer (III-1) and the epoxy-based thermosetting resin contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be arbitrarily selected.

. Epoxy resin (B1)

Examples of the epoxy resin (B1) include well-known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, and o-cresol novolac epoxy Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc., ring with more than two functions Oxygen compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the protective film forming sheet is improved.

Examples of epoxy resins having unsaturated hydrocarbon groups include: converting part of epoxy groups of polyfunctional epoxy resins into unsaturated hydrocarbons A compound made up of a group of radicals. Such a compound can be obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an epoxy group addition reaction.

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

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include: vinyl (ethenyl), 2-propenyl (allyl), (meth)acrylic acid, and (meth)acrylic acid The amino group and the like are preferably acryloyl group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but it is preferably 300 to 30,000 in terms of the curability of the thermosetting resin layer and the strength and heat resistance of the first protective film after curing. More preferably, it is 400 to 10,000, particularly preferably 500 to 3,000.

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

The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1000 g/eq, more preferably 300 g/eq to 800 g/eq.

In this specification, the so-called "epoxy equivalent" refers to the number of grams (g/eq) of epoxy compounds containing 1 gram equivalent of epoxy groups, which can be based on JIS (Japanese Jndustrial Standards, Japanese Industrial Standards) K 7236: 2001 Method determination.

The epoxy resin (B1) may be used individually by 1 type, or may use 2 or more types together, and when using 2 or more types together, these combinations and ratios can be selected arbitrarily.

. Thermal curing agent (B2)

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

As a thermosetting agent (B2), the compound which has two or more functional groups which can react with an epoxy group in one molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned. Preferably, a phenolic hydroxyl group, an amino group or an acid group is formed by an anhydride. The resulting group is more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), as phenolic curing agents having phenolic hydroxyl groups, for example, polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene phenol resins, and aralkylphenols can be cited Resin etc.

In the thermal curing agent (B2), as an amine curing agent having an amine group, for example, dicyanodiamide (hereinafter sometimes abbreviated as "DICY") and the like can be cited.

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

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

The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

In the case of using a phenolic curing agent as the thermosetting agent (B2), in terms of improving the peelability of the first protective film from the first support sheet, the softening point of the thermosetting agent (B2) or the glass The transfer temperature is high.

In the thermosetting agent (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene-based phenol resin, and aralkylphenol resin is preferably 300 to 30,000, more preferably It is 400 to 10,000, particularly preferably 500 to 3,000.

In the thermosetting agent (B2), for example, the molecular weight of non-resin components such as biphenol and dicyanodiamide is not particularly limited. For example, it is preferably 60 to 500.

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

In the resin layer forming composition (III-1) and the thermosetting resin layer, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass relative to 100 parts by mass of the epoxy resin (B1). Parts, more preferably 1 part by mass to 200 parts by mass. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of a thermosetting resin layer becomes easier. In addition, when the aforementioned content of the thermosetting agent (B2) is below the aforementioned upper limit, the thermosetting properties are reduced. The moisture absorption rate of the resin layer and the reliability of the package obtained by using the protective film forming sheet are further improved.

In the resin layer forming composition (III-1) and the thermosetting resin layer, the content of the thermosetting component (B) relative to 100 parts by mass of the polymer component (A) (for example, epoxy resin (B1) And the total content of the thermosetting agent (B2)) is preferably 50 parts by mass to 1000 parts by mass, more preferably 100 parts by mass to 900 parts by mass, and particularly preferably 150 parts by mass to 800 parts by mass. When the aforementioned content of the thermosetting component (B) is in this range, the adhesion between the first protective film and the first support sheet is suppressed, and the releasability of the first support sheet is improved.

[Curing accelerator (C)]

The composition (III-1) for forming a resin layer and the thermosetting resin layer may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the resin layer forming composition (III-1).

As a preferable curing accelerator (C), for example, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. can be cited Tertiary amine; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl Imidazoles such as 5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one The hydrogen atoms are substituted by organic groups); tetraphenyl phosphonium tetraphenyl borate, triphenyl phosphine tetraphenyl borate and other tetraphenyl borate salts.

The composition for forming a resin layer (III-1) and the curing accelerator (C) contained in the thermosetting resin layer may be one type or two or more types. In the case of two or more types, the combination of these And the ratio can be arbitrarily selected.

In the case of using a curing accelerator (C), in the resin layer forming composition (III-1) and the thermosetting resin layer, with respect to 100 parts by mass of the thermosetting component (B), the curing accelerator The content of (C) is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the curing accelerator (C) is more than the aforementioned lower limit, the effect of using the curing accelerator (C) can be more remarkably obtained. In addition, since the content of the curing accelerator (C) is below the aforementioned upper limit, for example, the high-polarity curing accelerator (C) is prevented from moving in the thermosetting resin layer to the adherend under the conditions of high temperature and high humidity. The effect of segregation on the adhering interface side is improved, and the reliability of the package obtained by using the protective film forming sheet is further improved.

[Filling material (D)]

The composition (III-1) for forming a resin layer and the thermosetting resin layer may contain a filler (D). Since the thermosetting resin layer contains the filler (D), the thermal expansion coefficient of the first protective film obtained by curing the thermosetting resin layer can be easily adjusted. The thermal expansion coefficient of the first protective film is measured Optimum, the package obtained by using the protective film forming sheet The reliability is further improved. In addition, since the thermosetting resin layer contains the filler (D), the moisture absorption rate of the first protective film can be reduced, or the heat dissipation can be improved.

The filling material (D) may be any one of an organic filling material and an inorganic filling material, and it is preferably an inorganic filling material.

As a preferable inorganic filler, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by forming a spherical shape. The beads; the surface modification products of the inorganic fillers; the single crystal fibers of the inorganic fillers; glass fibers, etc.

Among them, the inorganic filler material is preferably silica or alumina.

The composition for forming a resin layer (III-1) and the filler (D) contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, the combination and The ratio can be selected arbitrarily.

When the filler (D) is used, in the resin layer forming composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (ie, thermosetting The content of the filler (D) of the resin layer) is preferably 5 to 35% by mass, more preferably 7 to 25% by mass.

[Coupling agent (E)]

The composition (III-1) for forming a resin layer and the thermosetting resin layer may contain a coupling agent (E). By using a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the thermosetting resin layer to the adherend can be improved. In addition, by using the coupling agent (E), the water resistance of the first protective film obtained by curing the thermosetting resin layer is improved without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A) and the thermosetting component (B), and more preferably a silane coupling agent.

As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane Ethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl bis Ethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyl Trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc.

The composition for forming a resin layer (III-1) and the coupling agent (E) contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, the combination and The ratio can be selected arbitrarily.

When the coupling agent (E) is used, relative to the total content of the polymer component (A) and the thermosetting component (B) in the resin layer forming composition (III-1) and the thermosetting resin layer 100 parts by mass, the content of the coupling agent (E) is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (E) is more than the aforementioned lower limit, the dispersibility of the filler (D) in the resin is improved, or the adhesiveness of the thermosetting resin layer and the adherend is more significantly obtained. Improve the effects brought about by the use of coupling agent (E). In addition, when the aforementioned content of the coupling agent (E) is not more than the aforementioned upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (F)]

When using, as the polymer component (A), those having functional groups such as vinyl groups, (meth)acrylic groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds, such as the above-mentioned acrylic resins, The composition (III-1) for forming a resin layer and the thermosetting resin layer may contain a crosslinking agent (F) for bonding and crosslinking the aforementioned functional group with another compound. By cross-linking with the cross-linking agent (F), the initial adhesive force and cohesive force of the thermosetting resin layer can be adjusted.

Examples of the crosslinking agent (F) include: organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. . The aforementioned "adduct" refers to the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound with low content of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. The reactant of the molecular active hydrogen compound can be exemplified by the xylene diisocyanate adduct of trimethylolpropane and the like described later. In addition, the term "terminal isocyanate urethane prepolymer" is as described above.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-Diisocyanate; Diphenylmethane-2,4'-Diisocyanate; 3-Methyldiphenylmethane Diisocyanate; Hexamethylene Diisocyanate; Isophor Ketone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of toluene diisocyanate to all or part of the hydroxyl groups of polyols such as trimethylolpropane , Hexamethylene diisocyanate and xylene diisocyanate or two or more compounds; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxyamide), trimethylolpropane-tris-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinyl carboxyamide) trimethylene Based on melamine and so on.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction between the crosslinking agent (F) and the polymer component (A) can be used in the thermosetting resin layer Easy introduction of cross-linked structure.

The composition for forming a resin layer (III-1) and the crosslinking agent (F) contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, a combination of these And the ratio can be arbitrarily selected.

In the case of using a crosslinking agent (F), in the composition (III-1) for forming a resin layer, the content of the polymer component (A) is 100 parts by mass. The content of the agent (F) is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass. Since the aforementioned content of the cross-linking agent (F) is above the aforementioned lower limit, the effect brought about by the use of the cross-linking agent (F) can be obtained more remarkably. In addition, by making the aforementioned content of the crosslinking agent (F) below the aforementioned upper limit value, excessive use of the crosslinking agent (F) is suppressed.

[Energy ray curable resin (G)]

The composition (III-1) for forming a resin layer may contain an energy ray-curable resin (G). Since the thermosetting resin layer contains the energy ray-curable resin (G), the characteristics can be changed by the irradiation of the energy ray.

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound.

As the aforementioned energy ray-curable compound, for example, a compound having at least one polymerizable double bond in the molecule is mentioned, and an acrylate-based compound having a (meth)acryloyl group is preferred.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylic acid esters and other (meth)propylene containing chain aliphatic skeletons Acid esters; (meth)acrylates containing cyclic aliphatic skeletons such as dicyclopentyl di(meth)acrylate; polyalkylene glycols (meth) such as polyethylene glycol di(meth)acrylates Acrylate; oligopolyester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modified (meth)acrylate; the aforementioned polyalkylene glycol (meth)acrylic acid Polyether (meth)acrylates other than esters; itaconic acid oligomers, etc.

The weight average molecular weight of the aforementioned energy ray curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

The aforementioned energy ray curable compound used for polymerization may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

The energy ray curable resin (G) contained in the resin layer forming composition (III-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio may be arbitrary To choose.

In the resin layer forming composition (III-1), the content of the energy ray curable resin (G) is preferably 1% by mass to 95% relative to the total mass of the aforementioned resin layer forming composition (III-1) % By mass, more preferably 5% by mass to 90% by mass, particularly preferably 10% by mass to 85% by mass.

[Photopolymerization initiator (H)]

When the resin layer forming composition (III-1) contains energy ray curable resin (G), in order to efficiently polymerize the energy ray curable resin (G), it may contain a photopolymerization initiator (H).

Examples of the photopolymerization initiator (H) in the resin layer forming composition (III-1) include the same photopolymerization initiator as the photopolymerization initiator in the first adhesive composition (I-1).

The photopolymerization initiator (H) contained in the resin layer forming composition (III-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of the photopolymerization initiators (H) may be arbitrary To choose.

In the resin layer forming composition (III-1), the content of the photopolymerization initiator (H) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the energy ray curable resin (G) , More preferably 1 part by mass to 10 parts by mass, particularly preferably 2 parts by mass to 5 parts by mass.

[General additives (I)]

The composition (III-1) for forming a resin layer and the thermosetting resin layer may contain a general-purpose additive (I) within a range that does not impair the efficacy of the present invention.

The general additives (I) can be known ones, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred ones include, for example, plasticizers, antistatic agents, antioxidants, and colorants (dyes, pigments) , Gettering agent, etc.

The composition (III-1) for forming a resin layer and the general additives (I) contained in the thermosetting resin layer may be only one type or two or more types. In the case of two or more types, the combination and The ratio can be selected arbitrarily.

The content of the composition (III-1) for forming a resin layer and the general additive (I) of the thermosetting resin layer is not particularly limited, as long as it is appropriately selected according to the purpose.

[Solvent]

The composition (III-1) for forming a resin layer preferably further contains a solvent. The composition (III-1) for forming a resin layer containing a solvent improves the handleability.

The aforementioned solvent is not particularly limited. Preferred ones include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1-butanol, etc. Alcohols such as alcohols; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds), etc. .

The solvent contained in the composition (III-1) for forming a resin layer may be only one type or two or more types. In the case of two or more types, the combination and the ratio can be arbitrarily selected.

The solvent contained in the composition (III-1) for forming the resin layer is preferably methyl ethyl ketone in terms of allowing the components contained in the composition (III-1) for forming the resin layer to be more uniformly mixed. Wait.

<<Method for manufacturing composition for forming thermosetting resin layer>>

The composition for forming a thermosetting resin layer, such as the composition for forming a resin layer (III-1), can be obtained by blending each component constituting the composition.

The order of addition of each component is not particularly limited, and two or more components may be added at the same time.

When a solvent is used, it can be used in the following ways: mixing the solvent with any compounding component other than the solvent and pre-diluting the compounding component; or not pre-diluting any compounding component other than the solvent, but mixing the solvent with The blending ingredients are mixed.

The method of mixing the ingredients at the time of compounding is not particularly limited, and can be appropriately selected from known methods such as the following methods: the method of mixing by rotating a stirrer or stirring blade; the method of mixing using a mixer; the application of ultrasonic waves Methods of mixing, etc.

Regarding the addition of each component and the temperature and time during mixing, as long as each compounding component does not deteriorate, it is not particularly limited, as long as it is appropriately adjusted, and the temperature is preferably 15°C to 30°C.

◇Method of manufacturing protective film forming sheet

The sheet for forming a protective film can be manufactured by sequentially stacking the respective layers in a corresponding positional relationship. The formation method of each layer is as described above.

For example, when the first support sheet is manufactured, when the first adhesive layer or the first intermediate layer is laminated on the first substrate, by coating the first substrate The above-mentioned first adhesive composition or the first intermediate layer forming composition may be dried or irradiated with energy rays as necessary to laminate the first adhesive layer or the first intermediate layer.

On the other hand, for example, when a thermosetting resin layer is further laminated on the first adhesive layer already laminated on the first substrate, the composition for forming a thermosetting resin layer can be applied to the first adhesive layer It directly forms a thermosetting resin layer. Similarly, when the first adhesive layer is further laminated on the first intermediate layer that has been laminated on the first substrate, the first adhesive composition can be coated on the first intermediate layer to directly form the first adhesive Agent layer. In this way, when any composition is used to form a continuous two-layer laminated structure, the composition can be further coated on the layer formed by the aforementioned composition to form a new layer. Among them, it is preferable to use the aforementioned composition on another release film to form a layer of the post-layer of the two layers in advance, and the exposed surface of the formed layer and the side in contact with the release film are opposite to the exposed surface. The exposed surfaces of the remaining layers formed are bonded together, thereby forming a continuous two-layer laminated structure. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. The release film may be removed as necessary after forming the layered structure.

For example, a protective film forming sheet formed by laminating a first adhesive layer on a first substrate and laminating a thermosetting resin layer on the first adhesive layer (the first support sheet is the first substrate and the second In the case of a protective film forming sheet for a laminate of an adhesive layer, the first adhesive composition is coated on the first substrate, and dried as necessary, thereby preliminarily laminating on the first substrate For the first adhesive layer, a composition for forming a thermosetting resin layer is applied on the release film, and dried as necessary, thereby preliminarily forming a thermosetting resin layer on the release film to expose the thermosetting resin layer The surface is bonded to the exposed surface of the first adhesive layer laminated on the first substrate, and the thermosetting resin is laminated on the first adhesive layer, thereby obtaining a protective film forming sheet.

In addition, for example, when manufacturing a first support sheet in which a first intermediate layer is laminated on a first substrate, and a first adhesive layer is laminated on the aforementioned first intermediate layer, the first substrate is coated with the first support sheet. The composition for forming an intermediate layer is dried as necessary or irradiated with energy rays, thereby pre-laminating the first intermediate layer on the first substrate, and then coating the first adhesive composition on the release film, and drying if necessary, Thus, a first adhesive layer is formed in advance on the release film, and the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer that has been laminated on the first substrate, and the first adhesive layer Laminated on the first intermediate layer, thereby obtaining a first support sheet. In this case, for example, a composition for forming a thermosetting resin layer is further applied to the release film, and dried as necessary, thereby preliminarily forming a thermosetting resin layer on the release film. The exposed surface is bonded to the exposed surface of the first adhesive layer laminated on the first intermediate layer, and the thermosetting resin is laminated on the first adhesive layer, thereby obtaining a protective film forming sheet.

Furthermore, when the first adhesive layer or the first intermediate layer is laminated on the first substrate, it can also be used instead of coating the first adhesive composition or the first intermediate layer on the first substrate as described above. The composition method is used to coat the first adhesive composition or the first intermediate layer forming composition on the release film If necessary, dry or irradiate energy rays to form a first adhesive layer or a first intermediate layer on the release film. In this way, the first adhesive layer or the first intermediate layer is laminated on the first substrate.

In either method, the release film may be removed at any timing after the target build-up structure is formed.

In this way, all layers other than the first base material constituting the protective film forming sheet can be laminated by the method of pre-formed on the release film and pasted on the surface of the target layer, so as long as you choose to use such a step as necessary What is necessary is just to manufacture the sheet|seat for forming a protective film by layer.

In addition, the sheet for forming a protective film is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, a thermosetting resin layer) on the side opposite to the first support sheet. Therefore, a composition for forming a thermosetting resin layer, such as a composition for forming the outermost layer, is applied to the release film (preferably the release-treated surface), and dried as necessary, so that the release film The layer constituting the outermost layer is formed in advance, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the above methods, and the release film is not removed and kept in a bonded state. A sheet for forming a protective film can be obtained.

[Example]

Hereinafter, the present invention will be described in more detail through specific embodiments. However, the present invention is not limited to the examples shown below at all.

The components used to manufacture the composition for forming a thermosetting resin layer are shown below.

. Polymer composition

Polymer component (A)-1: butyl acrylate (hereinafter referred to as "BA") (55 parts by mass), methyl acrylate (hereinafter referred to as "MA") (10 parts by mass), glycidyl methacrylate (Hereinafter referred to as "GMA") (20 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) copolymerized acrylic resin (weight average molecular weight 800,000, glass transfer Temperature -28°C).

. Epoxy resin

Epoxy resin (B1)-1: Liquid bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "YL983U").

Epoxy resin (B1)-2: Multifunctional aromatic epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "EPPN-502H").

Epoxy resin (B1)-3: Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, "EPICLON HP-7200").

. Thermal curing agent

Thermal curing agent (B2)-1: Novolak-type phenol resin (manufactured by Showa Denko Corporation, "BRG-556").

. Curing accelerator

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

. Filler

Filling material (D)-1: spherical silica modified with epoxy group (manufactured by Admatechs, "Admanano YA050C-MKK").

[Manufacturing Example 1]

(Manufacturing of Adhesive Resin (I-2a))

Using 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (80 parts by mass) and HEA (20 parts by mass) as the raw materials of the copolymer, the polymerization reaction was carried out to obtain an acrylic polymer.

Add 2-methacryloxyethyl isocyanate (hereinafter referred to as "MOI") (22 parts by mass, about 80 mol% relative to HEA) to the acrylic polymer, and place it in an air stream at 50°C The addition reaction was carried out for 48 hours, thereby obtaining the target adhesive resin (I-2a).

[Manufacturing Example 2]

(Manufacturing of Adhesive Resin (I-2a))

Use butyl acrylate (hereinafter referred to as "BA") (52 parts by mass), methyl methacrylate (hereinafter referred to as "MMA") (20 parts by mass), and HEA (28 parts by mass) as the raw materials of the copolymer. Polymerization reaction, thereby obtaining an acrylic polymer.

Add 2-methacryloxyethyl isocyanate (hereinafter referred to as "MOI") (28 parts by mass relative to HEA) to the acrylic polymer It is about 90 mol%), and the addition reaction is carried out at 50° C. for 48 hours in an air stream, thereby obtaining the target adhesive resin (I-2a).

[Manufacturing Example 3]

(Manufacturing of Adhesive Resin (I-2a))

Using lauryl acrylate (hereinafter abbreviated as "LA") (80 parts by mass) and HEA (20 parts by mass) as raw materials of the copolymer, the polymerization reaction was carried out to obtain an acrylic polymer.

MOI was added to the acrylic polymer so that the total molar number of isocyanate groups in MOI became 0.8 times the total molar number of hydroxyl groups in HEA, and the addition was carried out at 50°C for 48 hours in an air stream. Reaction, thereby obtaining the target adhesive resin (I-2a).

[Manufacturing Example 4]

(Manufacturing of Adhesive Resin (I-2a))

Using 2EHA (40 parts by mass), vinyl acetate (hereinafter sometimes referred to as "VAc") (40 parts by mass), and HEA (20 parts by mass) as the raw materials of the copolymer, the polymerization reaction is carried out to obtain an acrylic polymer .

MOI was added to the acrylic polymer so that the total molar number of isocyanate groups in MOI became 0.8 times the total molar number of hydroxyl groups in HEA, and the addition was carried out at 50°C for 48 hours in an air stream. Reaction, thereby obtaining the target adhesive resin (I-2a).

[Manufacturing Example 5]

(Manufacturing of Adhesive Resin (I-2a))

Using 2EHA (80 parts by mass) and HEA (20 parts by mass) as raw materials of the copolymer, a polymerization reaction was performed to obtain an acrylic polymer.

MOI was added to the acrylic polymer so that the total molar number of isocyanate groups in MOI became 0.8 times the total molar number of hydroxyl groups in HEA, and the addition was carried out at 50°C for 48 hours in an air stream. Reaction, thereby obtaining the target adhesive resin (I-2a).

[Example 1]

<Manufacturing of Sheet for Forming Protective Film>

(Manufacturing of composition for forming thermosetting resin layer)

Make polymer component (A)-1 (100 parts by mass), epoxy resin (B1)-1 (135 parts by mass), epoxy resin (B1)-2 (90 parts by mass), epoxy resin (B1)- 3 (150 parts by mass), curing accelerator (C)-1 (180 parts by mass), curing accelerator (G)-1 (1 part by mass), and filler (D)-1 (160 parts by mass) are dissolved in In methyl ethyl ketone, stirring was performed at 23° C. to obtain a resin layer forming composition (III-1) having a solid content concentration of 55% by mass as a thermosetting resin layer forming composition.

(Manufacturing of the first adhesive composition)

With respect to the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 1, a toluene diisocyanate trimer adduct containing trimethylolpropane (manufactured by Tosoh), "Coronate L ") (0.5 parts by mass) as an isocyanate-based crosslinking agent, stirred at 23°C to obtain a solid content The first adhesive composition (I-2) with a concentration of 30% by mass was used as the first adhesive composition. In addition, all the blending parts in this "manufacturing of the first adhesive composition" are solid content conversion values.

(Manufacturing of protective film forming sheet)

Apply the above-mentioned peeling treatment surface of a peeling film (manufactured by Lintec Corporation, "SP-PET381031", thickness 38μm) obtained by peeling off one side of a polyethylene terephthalate film made by silicone treatment. The obtained first adhesive composition was heated and dried at 110° C. for 1 minute, thereby forming a first adhesive layer with a thickness of 30 μm on the release film.

Then, on the exposed surface of the first adhesive layer, a polyolefin film (thickness 25μm), an adhesive layer (thickness 2.5μm), and a polyethylene terephthalate film (thickness 50 μm), an adhesive layer (thickness 2.5 μm), and a polyolefin film (thickness 25 μm) are laminated in this order to form a 105 μm-thick laminated film, thereby obtaining a first support sheet.

Apply the above-mentioned peeling treatment surface of a peeling film (manufactured by Lintec Corporation, "SP-PET381031", thickness 38μm) obtained by peeling off one side of a polyethylene terephthalate film made by silicone treatment. The obtained composition for forming a thermosetting resin layer was dried at 100° C. for 2 minutes to produce a thermosetting resin layer with a thickness of 40 μm.

Then, the release film is removed from the first adhesive layer of the first support sheet obtained above, and the heat obtained above is attached to the exposed surface of the first adhesive layer. On the exposed surface of the curable resin layer, a protective film forming sheet in which the first base material, the first adhesive layer, the thermosetting resin layer, and the release film are sequentially laminated in the thickness direction is obtained.

[Comparative Example 1]

(Manufacturing of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 2, toluene diisocyanate trimer adduct containing trimethylolpropane (manufactured by Tosoh), "Coronate L ") (1.0 parts by mass) as an isocyanate-based crosslinking agent, stirred at 23°C to obtain a first adhesive composition (I-2') with a solid content concentration of 30% by mass as the first adhesive composition . In addition, all the blending parts in this "manufacturing of the first adhesive composition" are solid content conversion values.

(Manufacturing of protective film forming sheet)

Except having changed the 1st adhesive composition demonstrated in Example 1 to the 1st adhesive composition of the comparative example 1 obtained above, it carried out similarly to Example 1, and obtained the 1st support sheet.

Apply the above-mentioned peeling treatment surface of a peeling film (manufactured by Lintec Corporation, "SP-PET381031", thickness 38μm) obtained by peeling off one side of a polyethylene terephthalate film made by silicone treatment. The obtained composition for forming a thermosetting resin layer was dried at 100° C. for 2 minutes to produce a thermosetting resin layer with a thickness of 40 μm.

Then, the release film was removed from the first adhesive layer of the first support sheet obtained above, and the exposed surface of the first adhesive layer was attached to the exposed surface of the thermosetting resin layer same as that of Example 1 obtained above , The protective film forming sheet of Comparative Example 1 in which the first substrate, the first adhesive layer, the thermosetting resin layer, and the release film were sequentially laminated in the thickness direction was obtained.

[Example 2]

(Manufacturing of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 3, toluene diisocyanate trimer adduct containing trimethylolpropane (manufactured by Tosoh), "Coronate L ") (1.0 part by mass) as an isocyanate-based crosslinking agent, stirred at 23°C to obtain a first adhesive composition (I-2) with a solid content concentration of 30% by mass as the first adhesive composition. In addition, all the blending parts in this "manufacturing of the first adhesive composition" are solid content conversion values.

(Manufacturing of protective film forming sheet)

Except that the first adhesive composition described in Example 1 was changed to the first adhesive composition of Example 2 obtained above, the same procedure as in Example 1 was carried out to obtain a protective film forming sheet of Example 2.

[Example 3]

(Manufacturing of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 4, toluene diisocyanate trimer adduct containing trimethylolpropane (manufactured by Tosoh), "Coronate L ") (1.0 part by mass) as an isocyanate-based crosslinking agent, stirred at 23°C to obtain a first adhesive composition (I-2) with a solid content concentration of 30% by mass as the first adhesive composition. In addition, all the blending parts in this "manufacturing of the first adhesive composition" are solid content conversion values.

(Manufacturing of protective film forming sheet)

Except having changed the 1st adhesive composition demonstrated in Example 1 to the 1st adhesive composition of Example 3 obtained above, it carried out similarly to Example 1, and obtained the protective film formation sheet of Example 3.

[Example 4]

(Manufacturing of the first adhesive composition)

To the adhesive resin (I-2a) (100 parts by mass) obtained in Production Example 5, toluene diisocyanate trimer adduct containing trimethylolpropane (manufactured by Tosoh), "Coronate L ") (1.0 part by mass) as an isocyanate-based crosslinking agent, stirred at 23°C to obtain a first adhesive composition (I-2) with a solid content concentration of 30% by mass as the first adhesive composition. In addition, all the blending parts in this "manufacturing of the first adhesive composition" are solid content conversion values.

(Manufacturing of protective film forming sheet)

Except having changed the 1st adhesive composition demonstrated in Example 1 to the 1st adhesive composition of Example 4 obtained above, it carried out similarly to Example 1, and obtained the protective film formation sheet of Example 4.

<Evaluation of Sheets for Forming Protective Films>

For the thermosetting resin layer and the first adhesive layer obtained in Example 1 and Comparative Example 1, the contact angles of pure water, diiodomethane, and 1-bromonaphthalene were determined under an environment at a temperature of 23°C and a humidity of 50% Calculate the surface free energy of the dispersive component γ _s ^d , the polar component γ _s ^p , and the hydrogen bond component γ _s ^h based on these, and obtain the surface free energy γ _s ^{total of the respective layer surface based on the sum of each} .

The results are shown in Table 1.

Example 1 and Comparative Example 1 each protective film is formed by a difference γ _s ^total thermosetting resin sheet layer and the first adhesive layer of γ _s ^total as shown in Table 1.

The difference between the contact angle to water of the thermosetting resin layer in each protective film forming sheet of Example 1 and Comparative Example 1 and the contact angle to water of the first adhesive layer is also shown in Table 1.

For the first adhesive layer obtained in Example 1 to Example 4 and Comparative Example 1, a UV (ultraviolet) irradiation device (manufactured by Lintec, RAD-2000m/8) was used at an illuminance of 230mW/cm ² and a light quantity of 760mJ/cm ^{After UV irradiation under the conditions of 2} , the contact angles of pure water, diiodomethane, and 1-bromonaphthalene are determined in an environment of 23°C and 50% humidity, and the dispersion component γ _s ^d and polarity are determined based on these The surface free energy of each of the component γ _s ^p and the hydrogen bonding component γ _s ^h is calculated from the sum of the respective surface free energy γ _s ^total .

The results are shown in Table 2 together with the results of the uncured thermosetting resin layer.

Forming a difference γ _s γ _s ^total of the sum ^total of a UV-curable adhesive layer with a first thermosetting resin layer sheet of Example 1 and Comparative Example 1 each protective film embodiment as shown in Table 2.

The difference between the contact angle of the thermosetting resin layer to water and the contact angle of the first adhesive layer after UV curing in each protective film forming sheet of Comparative Example 1 is also shown in Table 2. Show.

(Table 2)

<Releasability evaluation after UV curing>

After producing the protective film forming sheets of Examples 1 to 4 and Comparative Example 1, one week later, the peelability after UV curing was evaluated in the following procedure.

A sheet for forming a protective film was attached to the circuit surface of a 6-inch bumped semiconductor wafer by thermal lamination at 70°C.

After attaching and returning to room temperature (about 5 minutes later), use a UV irradiation device (manufactured by Lintec, RAD-2000m/8) under the conditions of ^{230mW/cm 2} illuminance and 760mJ/cm ^{2 of light to irradiate} The first adhesive layer is cured. After that, the first support sheet was to be peeled off from the thermosetting resin layer. As a result, for the protective film forming sheets of Examples 1 to 4, the first support sheet composed of the first base material and the first adhesive layer could be removed. A support sheet is easily peeled off at the interface with the thermosetting resin layer (the peelability is "good"). For the protective film forming sheet of Comparative Example 1, the first adhesive layer is maintained and then the thermosetting resin layer In this state, the first substrate is peeled off, and the first adhesive layer locally undergoes cohesion failure and remains on the surface of the thermosetting resin layer (the peelability is "bad").

Although γ _s ^total difference of the first adhesive layer of the heat-curable resin gamma] _s ^total layer with UV-curable or thermosetting resin layer on the first adhesive agent layer after the water contact angle of water with UV curing The difference in the contact angle is not as great as shown in Table 2, but the peelability between the first support sheet and the thermosetting resin layer shows a great difference. _{That is, the difference between the γ s} ^total of the thermosetting resin layer before UV curing but not after UV curing and the γ _s ^total of the first adhesive layer, or the contact angle of the thermosetting resin layer to water before UV curing and The difference in the contact angle of the first adhesive layer to water has a greater impact on the peelability between the first support sheet and the thermosetting resin layer.

In the protective film forming sheets of Examples 1 to 4 and Comparative Example 1, the polymer component (A)-1 mainly composed of butyl acrylate (BA) was used in the thermosetting resin layer. In the first adhesive layer of Examples 1 to 4, the adhesive resin (I-2a) with 2-ethylhexyl acrylate (2EHA) or lauryl acrylate (LA) as the main component is used, so it can The above-mentioned difference in surface free energy is set to 10 mJ/m ² or more. In contrast, the first adhesive layer of Comparative Example 1 uses butyl acrylate (BA) as the main component in the same manner as the thermosetting resin layer. Adhesive resin (I-2a), so the above difference in surface free energy becomes smaller.

It is generally believed that it takes about one week to produce a protective film forming sheet until the adhesive strength and other qualities are stable. Therefore, for the protective film forming sheet of Comparative Example 1 where the difference between the surface free energy of the thermosetting resin layer and the surface free energy of the first support sheet is small, it can be considered that component movement occurs at the interface between the two. Then the force increased abnormally, resulting in poor peeling.

For the protective film forming sheet of Example 1 where the difference between the surface free energy of the thermosetting resin layer and the surface free energy of the first support sheet is large, it can be considered that there is no component movement at the interface between the two, and the adhesive force is stable. The easy peelability of the interface between the first support sheet and the thermosetting resin layer becomes excellent.

(Industrial availability)

The present invention can be used to manufacture semiconductor chips with bumps in the connection pads used in the flip chip mounting method, and the like.

1‧‧‧Sheet for forming protective film

11‧‧‧First substrate

12‧‧‧curable resin layer

13‧‧‧First adhesive layer

13a‧‧‧The surface of the first adhesive layer

101‧‧‧First support film

101a‧‧‧The surface of the first support piece

Claims (2)

A sheet for forming a protective film is formed by laminating a thermosetting resin layer on the first adhesive layer of a first support sheet formed by laminating at least a first substrate and a first adhesive layer; and, the aforementioned The thermosetting resin layer is a layer used to form a protective film on the surface of the semiconductor wafer by attaching it to the bumpy surface of the semiconductor wafer and thermally curing it; The difference between the surface free energy before thermal curing and the surface free energy of the surface on the thermosetting resin layer side of the first adhesive layer is 10 mJ/m ² or more. The sheet for forming a protective film according to claim 1, wherein the contact angle of the side surface of the first support sheet of the thermosetting resin layer to water before heat curing, and the thermosetting property of the first adhesive layer The difference in the contact angle to water on the side surface of the resin layer is 30° or more.

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