KR20240017845A - laminated film - Google Patents

Abstract

A laminated film capable of improving work efficiency in the manufacturing process of a semiconductor device is provided. The laminated film of the present invention includes a first separator, a first adhesive layer including a low-adhesive adhesive layer, a base material, a second adhesive layer including a peelable adhesive layer, and a second separator laminated in this order. It is a laminated film, and has a 180° peeling peeling force of the first and second separators to the first and second adhesive layers, F(1), F(2), and a 180° peeling adhesive force of the second adhesive layer to the glass plate, P(2). ), 180° peeling adhesive force P'(2) (N/50mm) after 5 minutes at 160°C satisfies the following equation.
F(2)≤F(1)
P(2)≥F(1)
P'(2)/P(2)<1.20
P'(2)<1.00

Description

laminated film

The present invention relates to laminated films.

In the manufacturing process of a semiconductor device, a semiconductor wafer is generally separated into pieces by dicing while temporarily fixed on a dicing tape, and the separated semiconductor chips are pushed by a pin member from the dicing tape side on the back side of the wafer. It is picked up by a suction jig called a collet and mounted on a mounting board such as a circuit board (for example, patent document 1).

Japanese Patent Publication No. 2019-9203

However, with advances in micro-processing technology, semiconductor chips are becoming smaller and thinner, and it is becoming easier for semiconductor chips to be damaged when picked up with a collet. In addition, as semiconductor devices are becoming more compact and multi-layered, there is a demand for dense multi-layer mounting of many fine semiconductor chips on a mounting board, and the method of picking them up with a collet and mounting them individually is becoming less efficient. .

As a method to eliminate such damage to the semiconductor chip and deterioration of packaging efficiency, for example, a plurality of electronic components are separated into pieces by dicing on a transfer double-sided adhesive film temporarily fixed to a carrier substrate, and then these are A method of batch transferring to a mounting board is considered.

However, with this method, in a laminated film in which both sides of the double-sided adhesive film for transfer are protected by a separator, an error occurs in the peeling treatment of the surface protection film (separator) on the adhesive side, or the surface protection film is not protected after sticking to the carrier substrate. There are problems that reduce work efficiency, such as lifting from the carrier substrate when peeling the film (separator), difficulty in peeling the double-sided adhesive film for transfer from the carrier substrate when collecting, and adhesive residue being generated. It's easy to happen.

The present invention was made in consideration of the above-described problem, and its purpose is to transfer the semiconductor chip, etc. to the mounting substrate without making a mistake in the peeling process of the separator when receiving the semiconductor chip, etc. by temporarily fixing it to the carrier substrate. To provide a laminated film with excellent reworkability as it does not peel off from the carrier substrate when transferring a semiconductor chip, etc. there is.

As a result of intensive study to achieve the above object, the present inventors have found a surface protection film (first separator), a first adhesive layer for temporarily fixing fine electronic components such as semiconductor chips, a base material, and a temporary fixation to a carrier substrate. It has a second adhesive layer and a surface protection film (second separator) for Specific relationships for F(2), the adhesive force P(2) of the second adhesive layer to the glass plate, and the adhesive force P'(2) of the second adhesive layer to the glass plate after affixing to the glass plate and 5 minutes at 160°C. If a laminated film that meets It was discovered that peeling was easy and adhesive residue could be suppressed when peeling from the carrier substrate after transferring to the mounting substrate. The present invention was completed based on these findings.

That is, the present invention is a laminated film in which a first separator, a first adhesive layer, a substrate, a second adhesive layer, and a second separator are laminated in this order, and the first adhesive layer includes a low-adhesive adhesive layer. and the second adhesive layer includes a peelable adhesive layer, and the temperature is 23°C and 50%R.H. and 180° peeling peeling force F(1) (N/50mm) of the first separator with respect to the first adhesive layer measured under the conditions of a peeling speed of 0.3 m/min, 23° C., 50% R.H. and 180° peeling peeling force F(2) (N/50mm) of the second separator with respect to the second adhesive layer measured under the conditions of a peeling speed of 0.3 m/min, 23° C., 50% R.H. and 180° peeling adhesion P (2) (N/50 mm) of the second adhesive layer to the glass plate measured under the condition of a tensile speed of 0.3 m/min, and 5 at 160°C by attaching the second adhesive layer to the glass plate. After 1 minute, 23℃, 50%R.H. and the 180° peeling adhesive force P'(2) (N/50 mm) of the second adhesive layer to the glass plate measured under the condition of a tensile speed of 0.3 m/min, satisfies the relationship of the following equation.

F(2)≤F(1)

P(2)≥F(1)

P'(2)/P(2)<1.20

P'(2)<1.00

It is preferable that the above-mentioned laminated film further satisfies the relationship of the following formula.

F(2)/F(1)<0.80

P(2)/F(1)>1.00

The laminated film was heated at 23°C and 50%R.H. and the 90° gauge peeling force T(1) (N/50mm) of the first adhesive layer with respect to the first separator measured under the condition of a tensile speed of 0.3 m/min, 23° C., 50% R.H. and the 90-degree gauge peeling force T(2) (N/50mm) of the second adhesive layer with respect to the second separator measured under the condition of a tensile speed of 0.3 m/min, and the adhesive force P(2) of the formula below: It is desirable to satisfy the relationship.

T(1)/T(2)>1.05

P(2)/T(1)<1.00

The laminated film of the present invention does not cause errors in the peeling process of the separator when temporarily fixing it to a carrier substrate and receiving a semiconductor chip, etc., and does not peel off from the carrier substrate when transferring a semiconductor chip, etc. to a mounting substrate, and does not peel off from the carrier substrate when transferring a semiconductor chip, etc. When peeling a chip, etc. from the carrier substrate after transferring it to a mounting substrate, it can be peeled off without contamination of adhesive residue, etc., and reworkability is excellent, so work efficiency can be improved in the manufacturing process of a semiconductor device.

1 is a cross-sectional schematic diagram showing one embodiment of the laminated film of the present invention.
FIG. 2 is a cross-sectional schematic diagram showing one embodiment of a first step in a method of mounting electronic components on a substrate using the laminated film shown in FIG. 1.
FIG. 3 is a cross-sectional schematic diagram showing one embodiment of a second process in a method of mounting electronic components on a mounting board using the laminated film shown in FIG. 1.
Figure 4 is a cross-sectional schematic diagram showing the process from temporarily fixing the laminated film of the present invention to a carrier substrate until peeling.

[Laminated film]

The laminated film of the present invention has a laminated structure in which a first separator, a first adhesive layer, a base material, a second adhesive layer, and a second separator are laminated in this order. That is, the laminated film of the present invention has an adhesive surface (adhesive surfaces of the first adhesive layer and the second adhesive layer) of the transfer double-sided adhesive film including the first adhesive layer, the substrate, and the second adhesive layer, It has a laminated structure protected by the first separator and the second separator.

The first adhesive layer includes a low-tack adhesive layer, and the second adhesive layer includes a peelable adhesive layer, and the temperature is 23° C., 50% R.H. and 180° peeling peeling force F(1) (N/50mm) of the first separator with respect to the first adhesive layer measured under the conditions of a peeling speed of 0.3 m/min, 23° C., 50% R.H. and 180° peeling peeling force F(2) (N/50mm) of the second separator with respect to the second adhesive layer measured under the conditions of a peeling speed of 0.3 m/min, 23° C., 50% R.H. and 180° peeling adhesion P (2) (N/50 mm) of the second adhesive layer to the glass plate measured under the condition of a tensile speed of 0.3 m/min, and 5 at 160°C by attaching the second adhesive layer to the glass plate. After 1 minute, 23℃, 50%R.H. and the 180° peeling adhesive force P'(2) (N/50 mm) of the second adhesive layer to the glass plate measured under the condition of a tensile speed of 0.3 m/min satisfies the relationship of the following equation.

F(2)≤F(1)

P(2)≥F(1)

P'(2)/P(2)<1.20

P'(2)<1.00

One embodiment of the laminated film of the present invention may be described below with reference to the drawings, but the laminated film of the present invention is not limited to the embodiment.

Figure 4 is a cross-sectional schematic diagram showing the process from temporarily fixing the laminated film of the present invention to a carrier substrate until peeling.

In Fig. 4(a), the second separator 120 is peeled from the adhesive layer 12 of the laminated film 1 adsorbed on an adsorption stage (not shown). At this time, no lifting occurs at the interface between the first separator 110 and the first adhesive layer 11. After this, the adhesive surface of the second adhesive layer 12 is bonded to the carrier substrate 22 (not shown).

In Figure 4(b), the first separator 110 is peeled from the adhesive layer 11. At this time, no lifting occurs at the interface of the second adhesive layer 22.

In FIG. 4(c), the diced electronic component 21 of FIG. 2 is attached to the first adhesive layer using a double-sided adhesive sheet temporarily fixed to the carrier substrate 22 by the second adhesive layer 12. The process of receiving (11) and the process of transferring the electronic component 21 received by the first adhesive layer 11 in FIG. 3 to the mounting substrate 30 are performed.

In Figure 4(d), the second adhesive layer 12 is peeled off from the carrier base material 22 (not shown). Since the second adhesive layer 12 exhibits excellent reworkability in that it can be peeled off without contamination such as adhesive residue, the carrier substrate 22 can be easily reused.

In the laminated film of the present invention, by setting F(2)≤F(1), peeling of the first separator with respect to the first adhesive layer occurs when the second separator is peeled from the second adhesive layer. It can be difficult.

Here, F(2)/F(1) (ratio of F(2) to F(1)) is 1.00 or less (F(2)/F(1)≤1.00), and preferably 0.90 or less (F (2)/F(1)≤0.90), more preferably less than 0.80 (F(2)/F(1)<0.80), more preferably less than 0.50 (F(2)/F(1)<0.50) )am. In addition, F(2)/F(1) is not particularly limited, but is preferably 0.10 or more (F(2)/F(1) ≥ 0.10), for example.

F(1) is preferably less than 0.50N/50mm (F(1)<0.50) from the viewpoint of workability when peeling off the first separator and balance with the adhesive force P(2) of the second adhesive layer to the carrier substrate. And, more preferably, it is 0.40N/50mm or less (F(1)≤0.40), and even more preferably, it is 0.35N/50mm or less (F(1)≤0.35). In addition, from the viewpoint of separator lifting during transfer sheet processing or transportation, 0.04 N/50 mm or more (F(1) ≥ 0.04) is preferable, more preferably 0.05 N/50 mm or more (F (1) ≥ 0.05), More preferably, it is 0.06N/50mm or more (F(1)≥0.06).

F(2) is preferably less than 0.20N/50mm (F(2)<0.20) from the viewpoint of workability during peeling of the second separator and balance with the peeling force of the first separator F(1), and is more preferred. Preferably it is 0.15N/50mm or less (F(2)≤0.15N), more preferably 0.10N/50mm or less (F(2)≤0.10). Additionally, from the viewpoint of separator lifting during transfer sheet processing or conveyance, 0.01/50mm or more (F(1)≥0.01) is preferable, more preferably 0.02N/50mm or more (F(2)≥0.02), and more preferably 0.02N/50mm or more (F(2)≥0.02). Preferably it is 0.04/50mm or more (F(2)≥0.04).

In the laminated film of the present invention, by setting P(2)≥F(1), it is difficult to prevent peeling of the second adhesive layer from the carrier substrate when peeling the first separator from the first adhesive layer. You can.

Here, P(2)/F(1) (ratio of P(2) to F(1)) is 1.00 or more (P(2)/F(1) ≥ 1.00), preferably greater than 1.00 (P (2)/F(1)>1.00), more preferably 1.20 or more (P(2)/F(1)≥1.20). Additionally, P(2)/F(1) is not particularly limited, but is preferably, for example, 4.50 or less (P(2)/F(1)≤4.50).

P(2) is preferably less than 1.10N/50mm (P(2)<1.10) from the viewpoint of improving reworkability that can be peeled from the carrier substrate without contamination such as adhesive residue, and more preferably 1.00N/50mm or less (P(2)≤1.00), more preferably 0.90N/50mm or less (P(2)≤0.90). Additionally, from the viewpoint of adhesion of the carrier substrate to the second adhesive layer, 0.10/50mm or more (P(2)≥0.10) is preferable, more preferably 0.20N/50mm or more (P(2)≥0.20), More preferably, it is 0.30/50 mm or more (P(2) ≥ 0.30).

For F(1), F(2), and P(2), by satisfying the above relationship, it becomes difficult for mistakes to occur in the separator peeling process when attaching the double-sided adhesive film for transfer to a carrier substrate.

In the second adhesive layer according to the present invention, P'(2)/P(2) (ratio of P'(2) to P(2)) is the ratio when transferring the electronic component to the mounting board and mounting it. From the viewpoint that the adhesive strength of the second adhesive layer to the carrier substrate does not increase even by thermal compression, and peels off well and reworkability is excellent, it is less than 1.20 (P'(2)/P(2)<1.20), Preferably it is 1.0 or less (P'(2)/P(2)≤1.0), more preferably 0.8 or less (P'(2)/P(2)≤0.8). Additionally, P'(2)/P(2) is not particularly limited, but is preferably, for example, 0.01 or more (P'(2)/P(2)≥0.01), and more preferably 0.03 or more ( P'(2)/P(2)≥0.03).

In the second adhesive layer according to the present invention, P'(2) is less than 1.00 N/50 mm ( P'(2)<1.00), preferably 0.6N/50mm or less (P'(2)≤0.6), more preferably 0.4N/50mm or less (P'(2)≤0.4). In addition, P'(2) is not particularly limited, but for example, it is preferably 0.01/50mm or more (P'(2)≥0.01), and more preferably 0.02N/50mm or more (P'(2)≥0.01). 0.02).

With respect to P(2) and P'(2), by satisfying the above relationship, the transfer double-sided adhesive film is difficult to peel off from the carrier substrate when transferring the semiconductor chip, etc. to the mounting substrate, and the semiconductor chip, etc. is not attached to the mounting substrate. After transfer, the double-sided adhesive film for transfer can easily be peeled off from the carrier substrate, making it difficult to generate adhesive residue.

Additionally, in the laminated film of the present invention, 23°C, 50%R.H. and the 90° gauge peeling force T(1) (N/50mm) of the first adhesive layer with respect to the first separator measured under the condition of a tensile speed of 0.3 m/min, 23° C., 50% R.H. and the 90-degree gauge peeling force T (2) (N/50 mm) of the second adhesive layer with respect to the second separator measured under the condition of a tensile speed of 0.3 m/min, and the adhesive force P (2) of the formula below: It is desirable to satisfy the relationship.

T(1)/T(2)>1.05

P(2)/T(1)<1.90

The gauge peel force T(1) refers to the maximum value (maximum stress) of the peel force recorded at the beginning of peeling when peeling the first separator from the first adhesive layer, and the gauge peel force T(2) refers to the maximum value of the peel force recorded at the beginning of peeling when peeling the first separator from the first adhesive layer. means the maximum value of peel force (maximum stress) recorded at the beginning of peeling when peeling from the second adhesive layer.

In the laminated film of the present invention, T(1)/T(2) (ratio of T(1) to T(2)) is the difference between the first and second separators when peeling the second separator from the second adhesive layer. From the viewpoint of making peeling of the first separator from the adhesive layer more difficult to occur, it is preferably greater than 1.05 (T(1)/T(2)>1.05), and more preferably 1.10 or more (T(1) /T(2)≥1.10), more preferably 1.15 or more (T(1)/T(2)≥1.15). Additionally, T(1)/T(2) is not particularly limited, but is preferably, for example, 3.50 or less (T(1)/T(2)≤3.50).

In the laminated film of the present invention, P(2)/T(1) (ratio of P(2) to T(1)) is applied to the carrier substrate when peeling the first separator from the first adhesive layer. From the viewpoint of making it difficult to peel off the second adhesive layer, it is preferably less than 1.90 (P(2)/T(1)<1.90), more preferably 1.50 or less (P(2)/T( 1)≤1.50), more preferably less than 1.00 (P(2)/T(1)<1.00), especially preferably 0.90 or less (P(2)/T(1)≤0.90). Additionally, P(2)/T(1) is not particularly limited, but is preferably, for example, 0.20 or more (P(2)/T(1) ≥ 0.20), and more preferably 0.40 or more (P( 2)/T(1)≥0.40).

T(1) is preferably 0.10N/50mm or more (T(1)≥0.10), more preferably 0.15N/50mm or more (T(1)≥0.15), and even more preferably 0.20N/50mm or more ( T(1)≥0.20). Additionally, T(1) is not particularly limited, but is preferably 1.00/50 mm or less (T(1) ≤ 0.1.00), and more preferably 0.85/50 mm or less (T(1) ≤ 0.85). , more preferably 0.70/50 mm or less (T(1)≤0.70).

T(2) is preferably 0.50N/50mm or less (T(2)≤0.50), more preferably 0.45N/50mm or less (T(2)≤0.45), and even more preferably 0.40N/50mm or less ( T(2)≤0.40). Additionally, T(2) is not particularly limited, but for example, it is preferably 0.10/50mm or more (T(2)≥0.10), and more preferably 0.15N/50mm or more (T(2)≥0.15). .

With respect to T(1), T(2), and P(2), by satisfying the above relationship, it becomes more difficult for errors to occur in the separator peeling process when attaching the double-sided adhesive film for transfer to a carrier substrate.

As above, the peel force and adhesion force are fully configured to satisfy the above relationships for F(1), F(2), P(2), P'(2), T(1), and T(2). By optimizing , work efficiency can be improved in the manufacturing process of a semiconductor device.

The above F(1), F(2), P(2), P'(2), T(1), and T(2) refer to the types of adhesives constituting the first adhesive layer and the second adhesive layer. Adhesion can be adjusted by composition, degree of cross-linking, etc., formation of WBL (Weak Boundary Layer) by mixing light release agents or plasticizers, thickness of the first and second separators, constituent materials, release treatment, etc. .

<First adhesive layer>

In the double-sided adhesive film for transfer according to the present invention, the first adhesive layer is an adhesive layer for receiving and holding the electronic component, and includes a low-adhesive adhesive layer. The configuration in which the first adhesive layer includes a low-adhesive adhesive layer is suitable in that the force applied to the electronic component when receiving can be reduced and damage to the electronic component can be suppressed. Additionally, when the first adhesive layer receives the electronic component in a non-contact manner, for example, the electronic component is peeled from the dicing tape by pressing it with a pin member, and is made to fall on the first adhesive layer. However, there are cases where the dropped electronic component bounces when the first adhesive layer picks it up, making it impossible to pick it up with high precision. When this phenomenon occurs, the positional accuracy of electronic components may decrease and contact defects may occur. The configuration in which the first adhesive layer includes a low-adhesive adhesive layer allows the electronic component to be easily caught by the first adhesive layer without being thrown away when the first adhesive layer receives the electronic component in a non-contact manner, and the electronic component is received with high positional accuracy. It is also suitable in that it can be done. Furthermore, the double-sided adhesive film for transfer is also preferable in that the electronic component can be easily peeled from the first adhesive layer when mounting the received electronic component on a mounting board.

The first adhesive layer can be said to be a low-adhesive adhesive layer by adjusting the type, composition, degree of crosslinking, etc. of the constituting adhesive, or forming a WBL (Weak Boundary Layer) by mixing a light release agent or plasticizer. .

In the laminated film of the present invention, at a frequency of 1 Hz, at 25°C, by AFM-DMA (nano dynamic mechanical analysis (nDMA) of an atomic force microscope (AFM)) of the first adhesive layer. The storage modulus (E'1a) is preferably 50 MPa or less. This configuration is preferable in that the first adhesive layer reliably adheres the received electronic component. If the E'1a is too high, the adhesion of the electronic component to the first adhesive layer may decrease, causing problems such as misalignment or dropping of the electronic component. From the viewpoint of adhesion of the electronic component to the first adhesive layer, E'1a is preferably 40 MPa or less, and more preferably 30 MPa or less. Additionally, it may be 20 MPa or less and 10 MPa or less. On the other hand, from the viewpoint of transferability from the first adhesive layer to the circuit board, E'1a is preferably 0.1 MPa or more. When the E'1a is too low, the adhesion of the electronic component to the first adhesive layer becomes too high, and transferability when mounting on a mounting board may be impaired. From the viewpoint of transferability of electronic components to a mounting board, E'1a is preferably 0.2 MPa or more, and more preferably 0.5 MPa or more.

In the laminated film of the present invention, the storage modulus (E'1b) of the first adhesive layer at 25°C at a frequency of 1 kHz by AFM-DMA is preferably 100 MPa or less. This configuration is preferable in that, when the first adhesive layer receives electronic components in a non-contact manner, the electronic components do not bounce off the surface of the first adhesive layer and can be received with high positional accuracy. If the E'1b is too high, when the electronic component is dropped and picked up without contacting the surface of the first adhesive layer, the electronic component is likely to bounce and deviate from the predetermined position or turn over, causing a decrease in positional accuracy. Lose. From the viewpoint of positional accuracy of the electronic component with respect to the first adhesive layer, E'1b is preferably 90 MPa or less, and more preferably 80 MPa or less. Additionally, it may be 70 MPa or less, 60 MPa or less, 50 MPa or less, 40 MPa or less, 30 MPa or less, and especially 20 MPa or less. On the other hand, from the viewpoint of transferability from the first adhesive layer to the mounting substrate, E'1b is preferably 0.5 MPa or more. When the E'1b is too low, the adhesion of the electronic component to the first adhesive layer increases, and when the electronic component falls, it covers the first adhesive layer, reducing transferability when mounting on a mounting board. This may be damaged. From the viewpoint of transferability to the mounting substrate of electronic components, E'1b is preferably 0.7 MPa or more, and more preferably 1.0 MPa or more.

In the laminated film of the present invention, the frequency by AFM-DMA of the first adhesive layer is 1 Hz, the storage modulus (E'1a) at 25°C is 1 kHz, the frequency by AFM-DMA of the first adhesive layer is 25 It is preferable that the ratio (E'1b/E'1a) of the storage modulus (E'1b) in °C is greater than 1.00. This configuration is preferable because it improves the balance of adhesion of the electronic component to the first adhesive layer, positional accuracy, transferability to the mounting substrate, etc. From the viewpoint of balance between the adhesion of electronic components, positioning accuracy, and transferability to a mounting board, E'1b/E'1a is preferably 1.05 or more, and more preferably 1.10 or more. The upper limit of E'1b/E'1a is not particularly limited, but is preferably 3.00 or less from the viewpoint of the above balance.

In the laminated film of the present invention, it is preferable that the loss modulus (E"1a) of the first adhesive layer at 25°C at a frequency of 1 Hz by AFM-DMA is 7 MPa or less. This configuration is applied to a mounting substrate for electronic components. This is desirable from the viewpoint of excellent transferability. If the E"1a is too high, the adhesion of the electronic component to the first adhesive layer becomes too high, and the transferability when mounted on a mounting board is impaired. There is. From the viewpoint of transferability of electronic components to a mounting substrate, E"1a is preferably 5 MPa or less, and more preferably 3 MPa or less. If E"1a is too low, the adhesion of the electronic component to the first adhesive layer may decrease. As this decreases, problems such as misalignment or dropping of electronic components may occur. From the viewpoint of adhesion of the electronic component to the first adhesive layer, E"1a is preferably 0.01 MPa or more, and more preferably 0.03 MPa or more.

Storage modulus (E'1a) at a frequency of 1 Hz and 25°C, storage modulus (E'1b) at a frequency of 1 kHz and 25°C, and loss modulus at a frequency of 1 Hz and 25°C by AFM-DMA of the first adhesive layer. (E"1a) can be adjusted depending on the type and composition of the constituting adhesive, the degree of crosslinking, etc.

In the laminated film of the present invention, the tack force of the first adhesive layer to the stainless steel plate (5 mm in diameter) is preferably 10 to 250 gf/Φ5 mmSUS. The configuration in which the tack force is 10 gf/Φ5 mmSUS or more is preferable from the viewpoint of adhesion of the electronic component to the first adhesive layer and positional accuracy, and 20 gf/Φ5 mmSUS or more is more preferable. On the other hand, the configuration in which the tack force is 250 gf/Φ5 mmSUS or less is preferable from the viewpoint of transferability to the mounting board of electronic components, and 200 gf/Φ5 mmSUS or less is more preferable.

The tack force of the first adhesive layer to the stainless steel plate (5 mm in diameter) can be adjusted by the type and composition of the constituting adhesive, the degree of crosslinking, and additives such as fatty acid ester or fluorine-based surfactant.

In the laminated film of the present invention, the surface force of the first adhesive layer is preferably -500 to -100 μN. The structure in which the surface force is -500 μN or more is preferable from the viewpoint of adhesion of the electronic component to the first adhesive layer and positional accuracy, and -400 μN or more is more preferable. On the other hand, the configuration in which the surface force is -100 μN or less is preferable from the viewpoint of transferability to the electronic component mounting substrate, and -50 μN or less is more preferable.

The surface force of the first adhesive layer can be adjusted by the type and composition of the constituting adhesive, degree of crosslinking, additives such as fatty acid ester and fluorine-based surfactant, etc.

In the double-sided adhesive film for transfer according to the present invention, the thickness of the first adhesive layer is not particularly limited, but is preferably 1 μm or more, and more preferably 3 μm or more. If the thickness is above a certain level, it is preferable because it makes it easier for the first adhesive layer to receive electronic components with high precision. Additionally, the upper limit of the thickness of the first adhesive layer is not particularly limited, but is preferably 100 μm, and more preferably 75 μm. If the thickness is below a certain level, it is preferable because it becomes easy to transfer the electronic component to the mounting substrate with high precision.

In the laminated film of the present invention, the haze (according to JIS K7136) of the first adhesive layer is not particularly limited, but is preferably 10% or less, and more preferably 5.0% or less. If the haze is 10% or less, excellent transparency is obtained, and for example, when the laminated film is attached to the carrier substrate, the pattern attached on the carrier substrate (for example, a marker indicating the transfer position of the electronic component) can be visually recognized. It is desirable. In addition, the haze can be determined, for example, by forming a first adhesive layer on a separator and leaving it to stand at room temperature (23°C, 50% RH) for at least 24 hours, then peeling off the separator and forming a glass slide (e.g., (total light transmittance 91.8%, haze 0.4%) can be used as a sample and measured using a haze meter (product name "HM-150", manufactured by Murakami Shikisai Gijutsu Kenkyujo Co., Ltd.).

In the laminated film of the present invention, the total light transmittance (according to JIS K7361-1) in the visible light wavelength range of the first adhesive layer is not particularly limited, but is preferably 85% or more, and more preferably 88% or more. am. If the total light transmittance is 85% or more, excellent transparency is obtained, and for example, when the laminated film is attached to the carrier substrate, the pattern attached on the carrier substrate (for example, a marker indicating the transfer position of the electronic component) can be recognized. It is desirable to be able to do so. In addition, the total light transmittance is calculated by, for example, forming a first adhesive layer on a separator, leaving it to stand (23° C., 50% RH) for at least 24 hours, peeling the separator, and measuring the total light transmittance using a slide glass (e.g., 91.8%, haze 0.4%) can be used as a sample and measured using a haze meter (product name "HM-150", manufactured by Murakami Shikisai Gijutsu Kenkyujo Co., Ltd.).

The adhesive constituting the first adhesive layer is not particularly limited and includes, for example, silicone adhesive, urethane adhesive, acrylic adhesive, rubber adhesive, polyester adhesive, polyamide adhesive, epoxy adhesive, and vinyl alkyl ether adhesive. , fluorine-based adhesives, etc. Among these, silicone-based adhesives, urethane-based adhesives, and acrylic adhesives are preferred, and silicone-based adhesives and urethane-based adhesives are preferred because they do not damage the electronic components, allow them to be positioned with high precision, and are easy to control due to their low adhesion from the viewpoint of good transferability to the mounting board. An adhesive is more preferable, and a silicone-based adhesive is even more preferable.

(Silicone-based adhesive)

The silicone-based adhesive is not particularly limited, and any known or common silicone-based adhesive can be used, for example, an addition-type silicone-based adhesive, a peroxide-curing type silicone-based adhesive, or a condensation-type silicone-based adhesive. The silicone-based adhesive may be either a one-component type or a two-component type. Silicone-based adhesives can be used individually or in combination of two or more types.

The addition type silicone-based adhesive is generally an addition reaction (hydrosilylation reaction) of organopolysiloxane having an alkenyl group such as a vinyl group on a silicon atom and an organopolysiloxane having a hydrosilyl group using a platinum compound catalyst such as chloroplatinic acid. It is an adhesive that creates a silicone-based polymer by Peroxide-curable silicone-based adhesives are generally adhesives that produce silicone-based polymers by curing (crosslinking) organopolysiloxane with peroxide. In addition, condensation-type silicone-based adhesives are generally adhesives that produce silicone-based polymers through dehydration or dealcoholization reactions between polyorganosiloxanes having hydrolyzable silyl groups such as silanol groups or alkoxysilyl groups at the ends.

Examples of silicone-based adhesives include silicone-based adhesive compositions containing silicone rubber and silicone resin because they have low adhesiveness and are easy to control.

The silicone rubber is not particularly limited as long as it is a silicone-based rubber component, but for example, organopolysiloxane containing dimethylsiloxane, methylphenylsiloxane, etc. as the main structural unit can be used. In addition, depending on the type of reaction, a silicone-based rubber having an alkenyl group bonded to a silicon atom (organopolysiloxane containing an alkenyl group; in the case of addition reaction type), a silicone-based rubber having at least a methyl group (in the case of peroxide curing type), and a silanol group at the terminal. Alternatively, silicone-based rubber (in the case of condensation type) having a hydrolyzable alkoxysilyl group can be used. In addition, the weight average molecular weight of the organopolysiloxane in the silicone rubber is usually 150,000 or more, but is preferably 280,000 to 1 million, and particularly preferably 500,000 to 900,000.

In addition, the silicone resin is not particularly limited as long as it is a silicone-based resin used in a silicone-based adhesive, but for example, M unit containing the structural unit “R ₃ Si _1/2 ”, M unit containing the structural unit “SiO ₂ ” An organopolysiloxane containing a (co)polymer having at least one unit selected from the group consisting of a Q unit, a T unit containing the structural unit "RSiO _3/2 ", and a D unit containing the structural unit "R ₂ SiO" and silicone resin containing the same. In addition, R in the above structural unit represents a hydrocarbon group or a hydroxyl group. Examples of the hydrocarbon group include aliphatic hydrocarbon groups (alkyl groups such as methyl and ethyl groups), alicyclic hydrocarbon groups (cycloalkyl groups such as cyclohexyl groups, etc.), and aromatic hydrocarbon groups (aryl groups such as phenyl and naphthyl groups). etc. can be mentioned. The ratio (ratio) between the M unit and at least one unit selected from the Q unit, T unit, and D unit is, for example, the former/latter (molar ratio) = 0.3/1 to 1.5/1 (preferably 0.5 /1 to 1.3/1) is preferable. Various functional groups, such as a vinyl group, may be introduced into the organopolysiloxane in such a silicone resin as needed. Additionally, the functional group to be introduced may be a functional group capable of causing a crosslinking reaction. As the silicone resin, MQ resin containing M units and Q units is preferable. The weight average molecular weight of the organopolysiloxane in the silicone resin is usually 1,000 or more, but is preferably 1,000 to 20,000, and 1,500 to 10,000 is particularly suitable.

The mixing ratio of silicone rubber and silicone resin is not particularly limited, but because it is easy to control with low adhesiveness, for example, for 100 parts by weight of silicone rubber, 100 to 220 parts by weight of silicone resin (in particular, 120 parts by weight) to 180 parts by weight) is preferred.

In addition, in the silicone-based adhesive composition containing silicone rubber and silicone resin, the silicone rubber and silicone resin may be simply mixed, or may react with each other to form a condensate (particularly a partial condensate), a crosslinking reactant, or an addition reaction product. It may be written as, etc.

In addition, silicone-based adhesive compositions containing silicone rubber and silicone resin usually contain a crosslinking agent in order to form a crosslinked structure because it is easy to control low adhesiveness. This crosslinking agent is not particularly limited, but siloxane-based crosslinking agents (silicon-based crosslinking agents) and peroxide-based crosslinking agents can be suitably used. Crosslinking agents can be used individually or in combination of two or more types.

As the siloxane-based crosslinking agent, for example, polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule can be suitably used. In such polyorganohydrogensiloxane, various organic groups other than hydrogen atoms may be bonded to the silicon atom to which the hydrogen atom is bonded. Examples of the organic group include alkyl groups such as methyl and ethyl groups; In addition to aryl groups such as phenyl groups, halogenated alkyl groups can be used, but methyl groups are preferred from the viewpoint of synthesis and handling. In addition, the skeletal structure of polyorganohydrogensiloxane may have any of linear, branched, and cyclic skeletal structures, but a linear structure is preferable.

As the peroxide-based crosslinking agent, for example, diacyl peroxide, alkyl peroxy ester, peroxydicarbonate, monoperoxycarbonate, peroxyketal, dialkyl peroxide, hydroperoxide, ketone peroxide, etc. can be used. You can. More specifically, for example, benzoyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- t-butylperoxyhexane, 2,4-dichloro-benzoyl peroxide, di-t-butylperoxy-diisopropylbenzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl Cyclohexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexine-3, etc. can be mentioned.

As an addition-type silicone-based adhesive, for example, product names “KR-3700”, “KR-3701”, “X-40-3237-1”, “X-40-3240”, “X-40-3291-1”, “ X-40-3306” (above, manufactured by Shin-Etsu Chemical Co., Ltd.) is commercially available. In addition, peroxide-curable silicone-based adhesives, for example, under the brand names “KR-100,” “KR-101-10,” and “KR-130” (manufactured by Shinetsu Chemical Co., Ltd.), are commercially available.

The addition-type silicone-based adhesive composition preferably contains a curing catalyst such as a platinum catalyst. As a platinum catalyst, for example, the brand name "CAT-PL-50T" (manufactured by Shin-Etsu Chemical Co., Ltd.), the brand name "DOWSIL NC-25 Catalyst", and "DOWSIL SRX212 Catalyst" (above, manufactured by Dow Toray Co., Ltd.) ), etc. are commercially available. From the viewpoint of balance such as the acceptability of electronic components in the first adhesive layer, positional accuracy, and transferability to the mounting substrate, the content of the curing catalyst is 100% of the silicone-based polymer (including silicone rubber, silicone resin, etc.) as the base polymer. Relative to parts by weight, about 0.1 to 10 parts by weight is preferable.

(Urethane-based adhesive)

The urethane-based adhesive is not particularly limited, and any known or common urethane-based adhesive can be used. A urethane-based adhesive composition containing a polyol, a polyfunctional isocyanate-based compound, and a catalyst is preferred because it is easy to control to low adhesiveness.

As the polyol, any appropriate polyol can be employed as long as it has two or more hydroxyl groups. Examples of such polyols include polyols with two hydroxyl groups (diols), polyols with three hydroxyl groups (triols), polyols with four hydroxyl groups (tetraols), and five hydroxyl groups. Examples include polyol (pentaol) having 6 hydroxyl groups, and polyol (hexanol) having 6 hydroxyl groups. Polyols can be used individually or in combination of two or more types.

The polyol preferably contains a polyol having a number average molecular weight (Mn) of 400 to 20,000. In addition, the content ratio of polyol having a number average molecular weight (Mn) of 400 to 20000 in the total amount of polyol is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and even more preferably 90 to 100%. It is % by weight, particularly preferably 95 to 100 % by weight, and most preferably substantially 100 % by weight. By adjusting the content ratio of the polyol having a number average molecular weight (Mn) of 400 to 20,000 within the above range, for example, a urethane-based adhesive with controlled low adhesiveness can be provided.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol.

The polyester polyol can be obtained, for example, through an esterification reaction between a polyol component and an acid component.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2 -Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, etc.

Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimeric acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecandioic acid, dimer acid, and 2-methyl- 1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4, 4'-biphenyldicarboxylic acid, their acid anhydrides, etc. are mentioned.

Examples of the polyether polyol include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcinol, etc.) , hydroquinone, etc.) as an initiator, and polyether polyol obtained by addition polymerizing alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Specifically, examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of the polycaprolactone polyol include caprolactone-based polyesterdiol obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

Examples of the polycarbonate polyol include polycarbonate polyol obtained by subjecting the polyol component to a polycondensation reaction with phosgene; The polyol component and dicarbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate. polycarbonate polyol obtained by transesterification of esters; Copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; polycarbonate polyols obtained by esterifying the various polycarbonate polyols and carboxyl group-containing compounds; polycarbonate polyols obtained by etherifying the various polycarbonate polyols and hydroxyl group-containing compounds; Polycarbonate polyol obtained by transesterifying the various polycarbonate polyols and ester compounds described above; polycarbonate polyols obtained by transesterification of the above-mentioned various polycarbonate polyols and hydroxyl group-containing compounds; Polyester-based polycarbonate polyol obtained by polycondensation reaction of the various polycarbonate polyols and dicarboxylic acid compounds; and copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the above-mentioned various polycarbonate polyols with alkylene oxide.

Examples of the castor oil-based polyol include castor oil-based polyol obtained by reacting castor oil fatty acid with the polyol component. Specifically, for example, castor oil-based polyol obtained by reacting castor oil fatty acid and polypropylene glycol is mentioned.

As the polyol, it is preferable to use a polyol (triol) having three hydroxyl groups as an essential component from the viewpoint of low adhesiveness and wettability of the first adhesive layer to the electronic component. The polyol (triol) having three hydroxyl groups is preferably contained in an amount of 50 to 100% by weight, and more preferably in an amount of 70 to 100% by weight, based on the total amount of components constituting the polyol.

Examples of the polyfunctional isocyanate compounds include aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate compounds.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene diisocyanate. , 2,4,4-trimethylhexamethylene diisocyanate, etc.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, Hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, etc. are mentioned.

Examples of the aromatic polyisocyanate include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate. , 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, etc.

Among them, aliphatic polyisocyanate and its modified products are preferable. Compared to other isocyanate-based crosslinking agents, aliphatic polyisocyanates and their modified products have a flexible crosslinking structure and are easy to control with low adhesion. As aliphatic polyisocyanate and its modified products, hexamethylene diisocyanate and its modified products are particularly preferable.

The polyfunctional isocyanate-based compound and the polyol have an equivalent ratio (NCO/OH) of the isocyanate group of the polyfunctional isocyanate-based compound and the hydroxyl group of the polyol from the viewpoint of low adhesion and wettability of the first adhesive layer to the electronic component. ) is preferably 1 to 5, more preferably 1.1 to 3, and still more preferably 1.2 to 2.

The urethane-based adhesive composition preferably contains a catalyst such as an iron-based compound and/or a tin-based compound. Specifically, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonato)iron, tris(hexane-2,4-dionato)iron, and tris(heptane-2,4-). Dionato) iron, tris(heptane-3,5-dionato) iron, tris(5-methylhexane-2,4-dionato) iron, tris(octane-2,4-dionato) iron, tris(6) -Methylheptane-2,4-dionato)iron, tris(2,6-dimethylheptane-3,5-dionato)iron, tris(nonane-2,4-dionato)iron, tris(nonane-4, 6-dionato)iron, tris(2,2,6,6-tetramethylheptane-3,5-dionato)iron, tris(tridecane-6,8-dionato)iron, tris(1-phenylbutane) -1,3-dionato) iron, tris(hexafluoroacetylacetonato) iron, tris(ethyl acetoacetate) iron, tris(n-propyl acetoacetate) iron, tris(isopropyl acetoacetate) iron, tris (acetoacetate-n-butyl)iron, tris(acetoacetate-sec-butyl)iron, tris(acetoacetate-tert-butyl)iron, tris(methylpropionylacetate)iron, tris(ethylpropionylacetate)iron, Tris(n-propyl)iron propionylacetate, Tris(isopropylpropionylacetate)iron, Tris(n-butyl)iron propionylacetate, Tris(sec-butyl)iron propionylacetate, Tris(propionyl)iron -tert-butyl) iron acetate, tris(benzyl acetoacetate) iron, tris(dimethyl malonate) iron, tris(diethyl malonate) iron, trimethoxy iron, triethoxy iron, triisopropoxy iron, chloride. Iron-based catalysts such as ferric iron can be mentioned.

The content (usage amount) of the catalyst contained in the urethane-based adhesive composition is preferably 0.002 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, and even more preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of polyol. If it is within this range, the speed of the crosslinking reaction when forming the pressure-sensitive adhesive layer is fast, the pot life of the pressure-sensitive adhesive composition is also long, and this is a preferable aspect.

Furthermore, as a urethane-based adhesive, a urethane-based adhesive composition containing a urethane prepolymer is also preferred because it has low adhesiveness and is easy to control.

Examples of the urethane-based adhesive composition containing a urethane prepolymer include a pressure-sensitive adhesive composition containing polyurethane polyol as a urethane prepolymer and a polyfunctional isocyanate-based compound. Urethane prepolymers can be used individually or in combination of two or more types. Polyfunctional isocyanate-based compounds can be used individually or in combination of two or more types.

Polyurethane polyol as a urethane prepolymer is preferably made by reacting polyester polyol and polyether polyol with an organic polyisocyanate compound in the presence or absence of a catalyst.

As the polyester polyol, any suitable polyester polyol can be used. Examples of such polyester polyol include polyester polyol obtained by reacting an acid component and a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, and polyoxy. Examples of ethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, and polyol components include glycerin, trimethylolpropane, and pentaerythritol. Examples of polyester polyols include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.

As for the molecular weight of polyester polyol, it can be used from low molecular weight to high molecular weight. As the molecular weight of polyester polyol, the number average molecular weight is preferably 500 to 5000. If the number average molecular weight is less than 500, reactivity may increase and gelation may become easy. If the number average molecular weight exceeds 5000, there is a risk that the reactivity will decrease and the cohesive force of the polyurethane polyol itself will decrease. The amount of polyester polyol used is preferably 10 to 90 mol% of the polyol constituting the polyurethane polyol.

As polyetherpolyol, any suitable polyetherpolyol can be used. As such polyether polyol, for example, low molecular weight polyols such as water, propylene glycol, ethylene glycol, glycerin, and trimethylolpropane are used as initiators, and polyols such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are used as initiators. Examples include polyether polyol obtained by polymerizing an oxirane compound. Specific examples of such polyether polyols include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As for the molecular weight of polyether polyol, it can be used from low molecular weight to high molecular weight. As for the molecular weight of polyether polyol, the number average molecular weight is preferably 1000 to 5000. If the number average molecular weight is less than 1000, reactivity may increase and gelation may become easy. If the number average molecular weight exceeds 5000, there is a risk that the reactivity will decrease and the cohesive force of the polyurethane polyol itself will decrease. The amount of polyether polyol used is preferably 20 to 80 mol% in the polyol constituting the polyurethane polyol.

Polyether polyol, if necessary, may contain glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine, and N-amino. It can be used in combination by replacing it with polyhydric amines such as ethylethanolamine, isophoronediamine, and xylylenediamine.

As the polyether polyol, only a difunctional polyether polyol may be used, and some or all of the polyether polyols having a number average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule may be used. As the polyether polyol, if some or all of the polyether polyols have an average molecular weight of 1,000 to 5,000 and have at least 3 or more hydroxyl groups per molecule, the balance between adhesive force and re-peelability can be improved. In such a polyether polyol, if the number average molecular weight is less than 1000, the reactivity may increase and gelation may become easy. In addition, in these polyether polyols, if the number average molecular weight exceeds 5000, there is a risk that the reactivity will decrease and the cohesive force of the polyurethane polyol itself will decrease. The number average molecular weight of this polyether polyol is more preferably 2500 to 3500.

As the organic polyisocyanate compound, any suitable organic polyisocyanate compound can be used. Examples of such organic polyisocyanate compounds include aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, and alicyclic polyisocyanate.

Examples of aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-tolyl. Lendiisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatetoluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'- Diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, etc. are mentioned.

Examples of aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. Isocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. are mentioned.

As aromatic aliphatic polyisocyanate, for example, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4. -diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, etc.

Examples of alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. Isocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatemethyl)cyclohexane, 1 , 4-bis(isocyanate methyl)cyclohexane, etc.

As the organic polyisocyanate compound, a trimethylolpropane adduct, a biuret body reacted with water, a trimer having an isocyanurate ring, etc. can also be used in combination.

As a catalyst that can be used to obtain polyurethane polyol, any suitable catalyst can be used. Examples of such catalysts include tertiary amine compounds and organometallic compounds.

Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecen-7 (DBU).

Examples of organometallic compounds include tin-based compounds and non-tin-based compounds.

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, and dibutyl tin dichloride. Stannous sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate. , tin 2-ethylhexanoate, etc.

Examples of non-tin-based compounds include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; Lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; Cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium-based compounds such as zirconium naphthenate.

When using a catalyst to obtain polyurethane polyol, the reactivity is different in a system where two types of polyol, polyester polyol and polyether polyol, are present. Therefore, in a system with a single catalyst, gelation or the reaction solution becomes cloudy. It is easy for problems such as losing or losing. Therefore, by using two types of catalysts when obtaining polyurethane polyol, the reaction rate, selectivity of the catalyst, etc. become easier to control and these problems can be solved. Combinations of these two types of catalysts include, for example, tertiary amine/organometallic, tin-based/non-tin-based, and tin-based/tin-based, preferably tin-based/tin-based, and more preferably di-based. It is a combination of butyltin dilaurate and tin 2-ethylhexanoate. The mixing ratio, in terms of weight ratio, of tin 2-ethylhexanoate/dibutyltin dilaurate, is preferably less than 1, and more preferably 0.2 to 0.6. If the mixing ratio is 1 or more, there is a risk of gelation becoming easier due to the balance of catalyst activity.

When using a catalyst when obtaining polyurethane polyol, the amount of catalyst used is preferably 0.01 to 1.0% by weight relative to the total amount of polyester polyol, polyether polyol, and organic polyisocyanate compound.

When a catalyst is used to obtain polyurethane polyol, the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. If the temperature exceeds 100°C, control of the reaction rate and crosslinking structure may become difficult, and polyurethane polyol with a predetermined molecular weight may become difficult to obtain.

When obtaining polyurethane polyol, it is not necessary to use a catalyst. In that case, the reaction temperature is preferably 100°C or higher, and more preferably 110°C or higher. Additionally, when obtaining polyurethane polyol without a catalyst, it is preferable to react for 3 hours or more.

Methods for obtaining polyurethane polyol include, for example, 1) adding the entire amount of polyester polyol, polyether polyol, catalyst, and organic polyisocyanate to a flask, 2) adding polyester polyol, polyether polyol, and catalyst to the flask. One example is a method of adding organic polyisocyanate dropwise. As a method of obtaining polyurethane polyol, method 2) is preferable in controlling the reaction.

When obtaining polyurethane polyol, any suitable solvent can be used. Examples of such solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferable.

As the polyfunctional isocyanate-based compound, those described above can be used.

As a method for producing a polyurethane-based resin composition obtained from a composition containing a urethane prepolymer, any suitable production method can be adopted as long as it is a method of producing a polyurethane-based resin composition using a so-called “urethane prepolymer” as a raw material.

(Acrylic adhesive)

The acrylic adhesive is not particularly limited, and known or common acrylic adhesives can be used. For example, an acrylic adhesive composition containing an acrylic polymer as a base polymer can be mentioned because it has low adhesiveness and is easy to control.

The acrylic polymer is a polymer that contains structural units derived from acrylic monomers (monomer components having a (meth)acryloyl group in the molecule) as structural units of the polymer. The acrylic polymer is preferably a polymer that contains the largest proportion by mass of structural units derived from (meth)acrylic acid ester. Additionally, acrylic polymers can be used individually or in combination of two or more types. In addition, in this specification, “(meth)acryl” refers to “acryl” and/or “methacryl” (either or both of “acryl” and “methacryl”), and the same applies to others.

Examples of the (meth)acrylic acid ester include hydrocarbon group-containing (meth)acrylic acid ester. Examples of hydrocarbon group-containing (meth)acrylic acid esters include alkyl (meth)acrylic acid, cycloalkyl (meth)acrylic acid, and aryl (meth)acrylic acid. Examples of the (meth)acrylic acid alkyl ester include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, Isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester (lauryl ester), tridecyl ester, Tetradecyl ester, hexadecyl ester, octadecyl ester, and eicosyl ester can be mentioned. Examples of the (meth)acrylic acid cycloalkyl ester include cyclopentyl ester and cyclohexyl ester of (meth)acrylic acid. Examples of the aryl (meth)acrylic acid include phenyl ester and benzyl ester of (meth)acrylic acid.

The hydrocarbon group-containing (meth)acrylic acid ester can be used individually or in combination of two or more types. Since the basic properties such as adhesion due to the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the first adhesive layer and can be easily controlled to low adhesion, in all monomer components for forming the acrylic polymer, The proportion of hydrocarbon group-containing (meth)acrylic acid ester is preferably 40% by mass or more, and more preferably 60% by mass or more.

The acrylic polymer may contain structural units derived from other monomer components copolymerizable with the hydrocarbon group-containing (meth)acrylic acid ester for the purpose of modifying cohesion, heat resistance, adhesion, etc. Examples of the other monomer components include carboxyl group-containing monomers, acid anhydride monomers, hydroxy group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, functional group-containing monomers such as acrylamide and acrylonitrile, and vinyl. Ester-based monomers, etc. can be mentioned. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride. Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, ( Examples include 8-hydroxyoctyl (meth)acrylic acid, 10-hydroxydecyl (meth)acrylic acid, 12-hydroxylauryl (meth)acrylic acid, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. . Examples of the glycidyl group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and the like. Examples of the sulfonic acid group-containing monomer include styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryl. Royloxynaphthalenesulfonic acid, etc. can be mentioned. Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate. Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl cyclohexane carboxylate, and vinyl benzoate. The other monomer components mentioned above can be used individually or in combination of two or more types. Since the basic properties such as adhesion due to the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the first adhesive layer and can be easily controlled to low adhesion, in all monomer components for forming the acrylic polymer, The total ratio of the other monomer components is preferably 60% by mass or less, more preferably 40% by mass or less.

The acrylic polymer may contain a structural unit derived from a polyfunctional monomer copolymerizable with the monomer component forming the acrylic polymer to form a crosslinked structure in its polymer skeleton. Examples of the multifunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Latex, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy(meth)acrylate ( For example, monomers having a (meth)acryloyl group and other reactive functional groups in the molecule, such as polyglycidyl (meth)acrylate), polyester (meth)acrylate, and urethane (meth)acrylate, etc. there is. The above polyfunctional monomers can be used individually or in combination of two or more types. Since the basic properties such as adhesion due to the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the first adhesive layer and can be easily controlled to low adhesion, the above-described overall monomer components for forming the acrylic polymer The ratio of the polyfunctional monomer is preferably 40% by mass or less, and more preferably 30% by mass or less.

An acrylic polymer is obtained by subjecting one or more monomer components containing an acrylic monomer to polymerization. Examples of polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.

The mass average molecular weight of the acrylic polymer is preferably 100,000 or more, and more preferably 200,000 to 3 million. If the mass average molecular weight is 100,000 or more, the amount of low molecular weight substances in the adhesive layer tends to be small, and contamination of electronic components, etc. can be further suppressed.

The acrylic adhesive composition forming the first adhesive layer may contain a crosslinking agent. For example, the acrylic polymer can be crosslinked to further reduce low molecular weight substances in the first adhesive layer. Additionally, the mass average molecular weight of the acrylic polymer can be increased and controlled to have low adhesion. Examples of the cross-linking agent include polyisocyanate compounds, epoxy compounds, polyol compounds (polyphenol-based compounds, etc.), aziridine compounds, melamine compounds, etc., and isocyanate-based cross-linking agents and/or epoxy-based cross-linking agents are preferred. When using a crosslinking agent, the amount used is preferably about 10 parts by mass or less, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the acrylic polymer.

Examples of the isocyanate-based crosslinking agent include aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates. Examples of aliphatic isocyanates include trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and dimer acid diisocyanate. Examples of alicyclic isocyanates include cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane. Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate. In addition, as an isocyanate-based crosslinking agent, a trimethylolpropane adduct of tolylene diisocyanate (trade name "Coronate L", manufactured by Tosoh Corporation) or an isocyanurate form of hexamethylene diisocyanate (trade name "Coronate HX", Tosoh (product name) Manufacturing Co., Ltd.) can also be mentioned.

As an epoxy-based crosslinking agent (multifunctional epoxy compound), for example, N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N- diglycidylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol dimethyl Glycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether. Dyl ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl)isocyanurate, resorcinol digly Examples include cidyl ether and bisphenol-S-diglycidyl ether, and also epoxy resins having two or more epoxy groups in the molecule. Examples of commercially available epoxy-based crosslinking agents include “Tetrad C” manufactured by Mitsubishi Gas Chemical Co., Ltd.

The adhesive composition constituting the first adhesive layer preferably contains a light release agent. By including a light release agent, a WBL (Weak Boundary Layer) is formed on the surface of the first adhesive layer, and the adhesiveness becomes easy to control with low adhesiveness.

The light release agent is not particularly limited, and known light release agents can be used without limitation, and examples include silicone-based release agents, fluorine-based surfactants, fatty acid esters, etc., which can be used alone or in combination of two or more types. You can use it.

The silicone-based release agent is not particularly limited, but examples include thermosetting silicone-based release agents and ionizing radiation-curable silicone-based release agents. In addition, the silicone-based release agent may be either a non-solvent type that does not contain a solvent, or a solvent type dissolved or dispersed in an organic solvent. In addition, silicone-based release agents can be used individually or in combination of two or more types.

The thermosetting silicone-based release agent is not particularly limited, but preferably contains organohydrogenpolysiloxane and organopolysiloxane having an aliphatic unsaturated group. In addition, the silicone-based release agent is preferably a heat addition reaction-curable silicone release agent that is cured by crosslinking through a heat addition reaction.

The heat addition reaction curable silicone-based release agent is not particularly limited, but includes polysiloxane (polysiloxane containing a Si-H group) having a hydrogen atom (H) bonded to a silicon atom (Si) in the molecule, and a Si-H bond (Si-H bond) in the molecule. A release agent containing a polysiloxane (Si-H group reactive polysiloxane) containing a functional group (Si-H group reactive functional group) having reactivity toward a covalent bond with H is preferably mentioned. In addition, this release agent is cured by crosslinking through addition reaction of Si-H group and Si-H group reactive functional group.

In the above Si-H group-containing polysiloxane, Si to which H is bonded may be either Si in the main chain or Si in the side chain. The Si-H group-containing polysiloxane is preferably a polysiloxane containing two or more Si-H groups in the molecule. Preferred examples of polysiloxane containing two or more Si-H groups include dimethylhydrogensiloxane-based polymers such as poly(dimethylsiloxane-methylsiloxane).

In addition, as the Si-H group reactive polysiloxane, the Si-H group reactive functional group or the side chain containing such a functional group is Si that forms the main chain (skeleton) of the siloxane polymer (for example, Si at the end of the main chain, Si inside the main chain). Polysiloxane in the form of bonded to Si) is preferably mentioned. Among them, polysiloxane in which the Si-H group reactive functional group is directly bonded to Si in the main chain is preferable. Furthermore, preferred examples of the Si-H group reactive polysiloxane include polysiloxanes containing two or more Si-H group reactive functional groups in the molecule.

Examples of the Si-H group-reactive functional group in the Si-H group-reactive polysiloxane include alkenyl groups such as vinyl group and hexenyl group. In addition, examples of the siloxane-based polymer forming the main chain portion of the Si-H group reactive polysiloxane include polydialkylsiloxane such as polydimethylsiloxane, polydiethylsiloxane, and polymethylethylsiloxane (the two alkyl groups are the same). or may be different); polyalkylarylsiloxane; Examples include poly(dimethylsiloxanedimethylsiloxane) and a polymer obtained by polymerizing a plurality of Si-containing monomers. Among them, polydimethylsiloxane is preferable as the siloxane-based polymer forming the main chain portion.

In particular, the heat addition reaction curable silicone-based release agent is a heat addition reaction curable silicone-based release agent containing a polysiloxane containing two or more Si-H groups in the molecule and a polysiloxane containing two or more Si-H group reactive functional groups in the molecule. It is desirable.

The ionizing radiation-curable silicone-based release agent is not particularly limited, but a UV-curable silicone-based release agent that undergoes a crosslinking reaction and hardens when irradiated with ultraviolet rays (UV) is preferably used.

The UV-curable silicone-based release agent is a release agent that is cured by UV irradiation through chemical reactions such as cationic polymerization, radical polymerization, radical addition polymerization, and hydrosilylation reaction. As the UV-curable silicone-based release agent, a UV-curable silicone-based release agent that cures by cationic polymerization is particularly preferable.

The cationic polymerization type UV curable silicone-based release agent is not particularly limited, but includes Si in which at least two epoxy groups form the main chain (skeleton) of the siloxane-based polymer (for example, Si at the end of the main chain, Si inside the main chain) and/ or a release agent containing an epoxy group-containing polysiloxane bonded to Si included in the side chain, respectively, directly or through a divalent group (alkylene group such as methylene group, ethylene group; alkyleneoxy group such as ethyleneoxy group and propyleneoxy group, etc.) It can be mentioned preferably. The bonding modes of at least two of these epoxy groups to Si may be the same or different. That is, a release agent containing polysiloxane containing two or more side chains containing one or two types of epoxy groups is preferably used. Examples of the epoxy group-containing side chain include glycidyl group, glycidoxy group (glycidyloxy group), 3,4-epoxycyclohexyl group, and 2,3-epoxycyclopentyl group. The epoxy group-containing polysiloxane may be linear, branched, or a mixture thereof.

In particular, in the double-sided adhesive film for transfer according to the present invention, from the viewpoint of easy control of the first adhesive layer to have low adhesiveness, it is preferable that the silicone-based adhesive contains a thermosetting silicone-based release agent, and a heat addition reaction-curable silicone-based release agent is included. It is more desirable to do so.

When the first adhesive layer in the double-sided adhesive film for transfer according to the present invention contains a silicone-based adhesive, the content of the silicone-based release agent is not particularly limited, but is 0.5 parts by weight based on 100 parts by weight of the silicone-based polymer that is the base polymer. It is preferable that it is 100 parts by weight or less. When the content is 0.5 parts by weight or more, the effect of easy control of the first adhesive layer to have low adhesiveness becomes easy to obtain, more preferably 1 part by weight or more, and even more preferably 3 parts by weight or more. Moreover, if the content is 100 parts by weight or less, it becomes easy to suppress the problem that sufficient adhesiveness is not obtained and receipt of the electronic component becomes difficult. More preferably, it is 30 parts by weight or less, and even more preferably 25 parts by weight. It is below wealth.

By using the fluorine-based surfactant as a light peeling agent, a light peeling effect can be achieved due to the low surface free energy of the fluorine moiety.

The fluorine-based surfactant is not particularly limited, but examples include fluorine-based oligomers, perfluorobutane sulfonates, perfluoroalkyl group-containing carboxylates, hexafluoropentane trimer derivative-containing sulfonates, and hexafluoropentane trimer derivatives. Examples include carboxylic acid salts containing hexafluoropentane trimer derivatives, quaternary ammonium salts containing hexafluoropentane trimer derivatives, betaine containing hexafluoropentane trimer derivatives, and polyoxyethylene ether containing hexafluoropentane trimer derivatives. Among these, fluorine-based oligomers are preferred. do. Additionally, fluorine-based surfactants can be used individually or in combination of two or more types.

Specific examples of the fluorine-based surfactant include, for example, commercially available products, such as “Megapac F(1)14”, “Megapac F-410” (manufactured by DIC Co., Ltd.), and “Suplon S-211”. , 「Supplon S-221」, 「Supplon S-231」, 「Supplon S-232」, 「Supplon S-233」, 「Supplon S-241」, 「Supplon S-242」, 「 Suplon S-243”, “Suplon S-420” (manufactured by AGC Semichemical Co., Ltd.), brand names “Aftergent 100”, “Aftergent 100C”, “Aftergent 110”, “Aftergent 150” 」, 「Aftergent 150CH」, 「Aftergent 300」, 「Aftergent 310」, 「Aftergent 320」, 「Aftergent 400SW」, 「Aftergent 251」, 「Aftergent 212M」, 「Aftergent 215M」, 「Aftergent 250」, 「Aftergent 209F」, 「Aftergent 222F」, 「Aftergent 245F」, 「Aftergent 208G」, 「Aftergent 218GL」, 「Aftergent 240G」, 「Aftergent 212P」, 「Aftergent 212P」 Examples include “Ptergent 220P,” “Aftergent 228P,” “Aftergent FTX-218,” and “Aftergent DFX-18” (manufactured by Neos Co., Ltd.). These compounds can be used individually or in combination of two or more types.

The weight average molecular weight (Mw) of the fluorine-based oligomer is preferably 3500 or more, more preferably 5000 or more, further preferably 10000 or more, and particularly preferably 20000 or more. If the weight average molecular weight of the fluorine-based oligomer is 3500 or more, it becomes easy to control low adhesion. In addition, a weight average molecular weight of 20000 or more is preferable because foaming can be suppressed when mixing the adhesive (composition) and the appearance after application of the adhesive is excellent. Additionally, the upper limit of the weight average molecular weight (Mw) of the fluorine-based oligomer is preferably 200,000, and more preferably 100,000. By setting the upper limit to 200,000, the fluorine-based oligomer is more likely to be distributed on the surface and the light peeling effect is more easily exhibited, which is preferable.

In addition, the fluorine-based oligomers include, for example, commercially available products under the brand names “Megapac F(2)51,” “Megapac F(2)53,” “Megapac F(2)81,” and “Megapac F-410.” ”, “Mega Park F-430”, “Mega Park F-444”, “Mega Park F-477”, “Mega Park F-510”, “Mega Park F-511”, “Mega Park F-551”, 「Megapack F-552」, 「Megapack F-553」, 「Megapack F-554」, 「Megapack F-555」, 「Megapack F-556」, 「Megapack F-557」, 「Megapack “Megapak F-558”, “Megapak F-559”, “Megapak F-560”, “Megapak F-561”, “Megapak F-562”, “Megapak F-563”, “Megapak F -565”, “Megapak F-568”, “Megapak F-569”, “Megapak F-570”, “Megapak F-571”, “Megapak F-572” (above, DIC Co., Ltd.) manufactured), brand names “Suplon S-611”, “Suplon S-651”, “Suplon S-386” (above, manufactured by AGC Semichemical Co., Ltd.), brand names “Pterzent 610FM”, “Pterzent” 710FL,” “Aftergent 710FM,” “Aftergent 710FS,” “Aftergent 730FL,” and “Aftergent 730LM” (manufactured by Neos Co., Ltd.). These compounds can be used individually or in combination of two or more types.

When the first adhesive layer in the double-sided adhesive film for transfer according to the present invention contains a fluorine-based surfactant, the content of the fluorine-based surfactant is not particularly limited, but is 0.01 parts by weight based on 100 parts by weight of the silicone polymer that is the base polymer. It is preferable that it is more than 5 parts by weight and less than 5 parts by weight. When the content is 0.01 part by weight or more, the effect of easy control of the first adhesive layer to have low adhesiveness becomes easy to obtain, more preferably 0.05 part by weight or more, and even more preferably 0.1 part by weight or more. In addition, if the content is 5 parts by weight or less, it is easier to suppress the problem that sufficient adhesiveness is not obtained and receiving the electronic component becomes difficult, and from the viewpoint of suppressing a decrease in transparency, more preferably 3 parts by weight. or less, and more preferably 2 parts by weight or less.

When the adhesive composition constituting the first adhesive layer contains fatty acid ester, low adhesiveness and wettability of the first adhesive layer to electronic components can be expected.

Examples of the fatty acid ester include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, behenate monoglyceride, cetyl 2-ethylhexanoate, Isopropyl myrstate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl palm fatty acid, methyl laurate, methyl oleate, methyl stearate, myristyl myrstate, octyl myrstate. Dodecyl, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoate triglyceride, butyl laurate, octyl oleate , tridecyl isononanoate, etc. Fatty acid esters can be used individually or in combination of two or more types.

The content of the fatty acid ester contained in the urethane-based adhesive composition is, for example, 1 to 50 parts by weight per 100 parts by weight of polyol from the viewpoint of low adhesion of the first adhesive layer to electronic components, wettability, and contamination to the adherend. part is preferable, 2 to 40 parts by weight is more preferable, and 3 to 30 parts by weight is still more preferable.

When the pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer contains a light release agent, its content (total amount) is, for example, from the viewpoint of low adhesion of the first pressure-sensitive adhesive layer to electronic components, wettability, and contamination resistance to electronic components. For example, with respect to 100 parts by weight of base polymer, 0.1 part by weight or more is preferable, 1 part by weight or more is more preferable, and 3 parts by weight or more is still more preferable. From the viewpoint of preventing coloring of the first adhesive layer, 50 parts by weight or less is preferable, 30 parts by weight or less is more preferable, and 10 parts by weight or less is still more preferable.

The adhesive composition constituting the first adhesive layer preferably contains a deterioration inhibitor such as an antioxidant or ultraviolet absorber. By including a deterioration inhibitor, deterioration such as discoloration during storage of the double-sided adhesive film for transfer according to the present invention can be suppressed, and processability, such as making it easier to cut the double-sided adhesive film for transfer, can be improved.

The ultraviolet absorber is not particularly limited, but examples include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. Absorbents, etc. can be mentioned, and these can be used individually or in combination of two or more types. Among these, triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferred, and triazine-based ultraviolet absorbers having two or less hydroxyl groups per molecule, and benzotriazole-based ultraviolet absorbers having one benzotriazole skeleton per molecule. At least one type of ultraviolet absorber selected from the group consisting of is preferable because it has good solubility in the monomer used to form the acrylic adhesive composition and has a high ultraviolet ray absorption ability around a wavelength of 380 nm.

As a triazine-based ultraviolet absorber having two or less hydroxyl groups per molecule, specifically, 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6- (4-methoxyphenyl)-1,3,5-triazine (trade name “Tinosorb S”, manufactured by BASF), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2 ,4-dibutoxyphenyl)-1,3,5-triazine (trade name “TINUVIN 460”, manufactured by BASF), 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5 -Triazin-2-yl)-5-hydroxyphenyl and [(C ₁₀ -C ₁₆ (mainly C ₁₂ -C ₁₃ )alkyloxy)methyl] oxirane reaction product (trade name “TINUVIN 400”, BASF) manufactured), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxyprop [oxy]phenol), 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycide Reaction product of acid ester (trade name “TINUVIN 405”, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]- Phenol (brand name “TINUVIN 1577”, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy) Ethoxy]-phenol (trade name “ADK STAB LA46”, manufactured by ADEKA), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenyl) Phenyl)-1,3,5-triazine (brand name "TINUVIN 479", manufactured by BASF), etc.

In addition, as a benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-( 1,1,3,3-Tetramethylbutyl)phenol (brand name “TINUVIN 928”, manufactured by BASF), 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (brand name “TINUVIN”) PS", manufactured by BASF), benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C _7-9 branched and straight chain alkyl ) ester compound (brand name "TINUVIN 384-2", manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (brand name) “TINUVIN 900”, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethyl Butyl)phenol (trade name “TINUVIN 928”, manufactured by BASF), methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/ Reaction product of polyethylene glycol 300 (brand name "TINUVIN 1130", manufactured by BASF), 2-(2H-benzotriazol-2-yl)-p-cresol (brand name "TINUVIN P", manufactured by BASF), 2(2H -Benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (trade name “TINUVIN 234”, manufactured by BASF), 2-[5-chloro(2H)-benzotria [Zol-2-yl]-4-methyl-6-(tert-butyl)phenol (trade name “TINUVIN 326”, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-di -tert-pentylphenol (trade name “TINUVIN 328”, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name “TINUVIN 328”, manufactured by BASF) TINUVIN 329", manufactured by BASF), reaction product between methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol 300 (Brand name “TINUVIN 213”, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (Brand name “TINUVIN 571”, manufactured by BASF), 2-[ 2-hydroxy-3-(3,4,5,6-tetrahydrophthalimide-methyl)-5-methylphenyl]benzotriazole (brand name “Sumisorb 250”, manufactured by Sumitomo Chemical Industries, Ltd.), etc. can be mentioned.

In addition, the benzophenone-based ultraviolet absorber (benzophenone-based compound) and oxybenzophenone-based ultraviolet absorber (oxybenzophenone-based compound) include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzo Phenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. I can hear it.

In addition, examples of the salicylic acid ester-based ultraviolet absorbers (salicylic acid ester-based compounds) include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxybenzoate. Iloxy-4-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl -2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4-methylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl2-hydroxy-3-methoxybenzoate , 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (brand name “TINUVIN 120”, manufactured by BASF), etc.

Examples of the cyanoacrylate-based ultraviolet absorber (cyanoacrylate-based compound) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, Alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, etc. can be mentioned.

The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength range of 300 to 400 nm, and more preferably in the wavelength range of 320 to 380 nm.

Examples of the antioxidant include phenol-based, phosphorus-based, sulfur-based and amine-based antioxidants, and at least one selected from these is used. Among these, phenol-based antioxidants are preferable, and hindered phenol-based antioxidants are particularly preferable.

Specific examples of the phenolic antioxidant include monocyclic phenol compounds such as 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl. -4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol , 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2 -Isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL-α-tocopherol, stearylβ-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, etc. as bicyclic phenol compounds, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4' -Butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-thiobis(4-methyl- 6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol] , 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-butylidenebis(2-t-butyl-4-methylphenol), 3,6-deoxy Octamethylene bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) ) propionate], 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylenebis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like as a tricyclic phenol compound, 1,1,3-tris(2-methyl-4-hydroxy-5-t -Butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris[(3,5- di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 1,3 , 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, etc., as a 4-ring phenol compound, tetrakis[methylene-3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate] methane, etc. as phosphorus-containing phenol compounds, bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)calcium, and bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)nickel.

The above anti-deterioration agents can be used individually or in combination of two or more types. The content of the anti-deterioration agent contained in the adhesive composition is, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the first adhesive composition from the viewpoint of suppressing deterioration such as discoloration during storage and processability of the double-sided adhesive film for transfer. It is preferable, 0.03 to 5 parts by weight is more preferable, and 0.1 to 3 parts by weight is still more preferable.

The pressure-sensitive adhesive composition constituting the first pressure-sensitive adhesive layer may contain any appropriate other components within a range that does not impair the effect of the present invention. These other ingredients include, for example, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin substances, softeners, plasticizers, conductive agents, surface lubricants, leveling agents, heat-resistant stabilizers, polymerization inhibitors, lubricants, and solvents. etc. can be mentioned.

<Second adhesive layer>

In the double-sided adhesive film for transfer according to the present invention, the second adhesive layer is an adhesive layer for temporarily fixing to the carrier substrate and includes a peelable adhesive layer. The configuration in which the second adhesive layer includes a peelable adhesive layer is preferable in that the second adhesive layer can be peeled from the carrier substrate without contamination such as adhesive residue and can improve reworkability. do.

The second adhesive layer can be made into a peelable adhesive layer by adjusting the adhesiveness according to the type, composition, degree of crosslinking, etc. of the adhesive, or by lowering the adhesive strength by physical stimulation such as heat or electromagnetic waves such as ultraviolet rays.

The adhesive force of the second adhesive layer can be adjusted by adjusting the type, composition, degree of crosslinking, etc. of the constituting adhesive, or by forming a WBL (Weak Boundary Layer) by mixing a light release agent or plasticizer.

In the double-sided adhesive film for transfer according to the present invention, the thickness of the second adhesive layer is not particularly limited, but is preferably 1 μm or more, and more preferably 3 μm or more. If the thickness is above a certain level, it is preferable because it becomes easier for the second adhesive layer to be stably fixed to the carrier substrate. Additionally, the upper limit of the thickness of the second adhesive layer is not particularly limited, but is preferably 30 μm, and more preferably 20 μm. If the thickness is below a certain level, it becomes easier to peel the second adhesive layer from the carrier substrate, and reworkability improves, which is preferable.

The adhesive constituting the second adhesive layer is not particularly limited, but includes, for example, silicone adhesives, urethane adhesives, acrylic adhesives, rubber adhesives, polyester adhesives, and polyamide adhesives used as the first adhesive layer above. , epoxy-based adhesives, vinyl alkyl ether-based adhesives, and fluorine-based adhesives. Among these, silicone-based adhesives, urethane-based adhesives, and acrylic adhesives are preferred, and urethane-based adhesives and acrylic adhesives are more preferred, and acrylic adhesives are preferred from the viewpoint of being able to be peeled from the carrier substrate without contamination of adhesive residues and the like and improving reworkability. Adhesives are more preferred.

The second adhesive layer in the double-sided adhesive film for transfer according to the present invention is an adhesive layer capable of intentionally reducing the adhesive force by an action from the outside during the use process of the double-sided adhesive film for transfer (adhesive force reduction possible adhesive) layer), or it may be an adhesive layer (adhesion non-reduced adhesive layer) whose adhesive force is reduced most or not at all depending on external action during the use of the double-sided adhesive film for transfer, or it may be a double-sided adhesive layer for transfer according to the present invention. It can be appropriately selected depending on the method or conditions for transferring electronic components using an adhesive film.

When the second adhesive layer is an adhesive layer capable of reducing adhesive strength, in the manufacturing process or use process of the double-sided adhesive film for transfer according to the present invention, the second adhesive layer shows a state in which the adhesive strength is relatively high and a state in which the second adhesive layer exhibits a relatively low adhesive strength. It becomes possible to use states separately. For example, in the process of using the double-sided adhesive film for transfer according to the present invention, the first adhesive layer receives the electronic component, using the state in which the second adhesive layer exhibits relatively high adhesive force, It becomes possible to suppress and prevent the lifting of the double-sided adhesive film for transfer. On the other hand, in the subsequent peeling process of the double-sided adhesive film for transfer according to the present invention from the carrier substrate, reworkability can be improved by reducing the adhesive force of the second adhesive layer.

Examples of the adhesive that forms the adhesive layer capable of reducing adhesive force include radiation-curable adhesives and heat-foamable adhesives. The adhesive that forms the adhesive layer capable of reducing adhesive force can be used individually or in combination of two or more types.

As the radiation-curable adhesive, for example, a type of adhesive that is cured by irradiation of electron beams, ultraviolet rays, α-rays, β-rays, γ-rays, or ) can be used particularly preferably.

Examples of the radiation-curable adhesive include an addition-type radiation-curable adhesive containing a base polymer such as an acrylic polymer and a radiation-polymerizable monomer component or oligomer component having a functional group such as a radiation-polymerizable carbon-carbon double bond. .

As the base polymer, an acrylic polymer similar to that of the first adhesive layer can be used. Since the basic properties such as adhesion due to the hydrocarbon group-containing (meth)acrylic acid ester are appropriately expressed in the second adhesive layer, and the adhesion and peelability are easy to control, it is necessary to use all monomer components for forming the acrylic polymer. The proportion of hydrocarbon group-containing (meth)acrylic acid ester is preferably 40% by mass or more, and more preferably 60% by mass or more.

The acrylic polymer may contain a hydroxy group-containing monomer. When the acrylic polymer in the second adhesive layer contains a hydroxy group-containing monomer, it is easy to obtain appropriate cohesive force in the second adhesive layer. From the viewpoint of achieving appropriate adhesiveness and cohesion in the second adhesive layer, the proportion of the hydroxy group-containing monomer in the acrylic polymer is, for example, 0.1 to 30% by mass, and preferably 0.5 to 20% by mass. am.

The acrylic polymer may contain a carboxyl group-containing monomer. When the acrylic polymer in the second adhesive layer contains a carboxyl group-containing monomer, it is easy to obtain adequate adhesion reliability in the second adhesive layer. From the viewpoint of realizing appropriate adhesion reliability in the second adhesive layer, the ratio of the carboxyl group-containing monomer in the acrylic polymer is, for example, 0.1 to 30% by mass, and preferably 0.5 to 20% by mass.

The acrylic polymer may contain a vinyl ester monomer. When the acrylic polymer in the second adhesive layer contains a vinyl ester monomer, it is easy to obtain appropriate cohesion in the second adhesive layer. From the viewpoint of realizing appropriate cohesion in the second adhesive layer, the proportion of vinyl ester monomer in the acrylic polymer is, for example, 0.1 to 60% by mass, and preferably 0.5 to 50% by mass.

The acrylic adhesive composition forming the second adhesive layer may contain a crosslinking agent. For example, the acrylic polymer can be crosslinked to further reduce low molecular weight substances in the second pressure-sensitive adhesive layer. Additionally, by increasing the mass average molecular weight of the acrylic polymer, low adhesion and peelability can be controlled. Examples of the cross-linking agent include polyisocyanate compounds, epoxy compounds, polyol compounds (polyphenol-based compounds, etc.), aziridine compounds, melamine compounds, etc., and isocyanate-based cross-linking agents and/or epoxy-based cross-linking agents are used. In this case, the amount used is preferably about 10 parts by mass or less, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the acrylic polymer.

A crosslinking accelerator may be used in the acrylic adhesive composition forming the second adhesive layer. The type of crosslinking accelerator can be appropriately selected depending on the type of crosslinking agent used. In addition, in this specification, a crosslinking accelerator refers to a catalyst that increases the speed of the crosslinking reaction by a crosslinking agent. Examples of such crosslinking accelerators include tin (Sn) such as dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, tetra-n-butyltin, and trimethyltin hydroxide. ) containing compounds; Examples include amines such as N,N,N',N'-tetramethylhexanediamine and triethylamine, and N-containing compounds such as imidazole. Among them, Sn-containing compounds are preferable. The use of these crosslinking accelerators is particularly effective when a hydroxyl group-containing monomer is used as the parentomer and an isocyanate-based crosslinking agent is used as the crosslinking agent. The amount of the crosslinking accelerator contained in the adhesive composition can be, for example, about 0.001 to 0.5 parts by mass (preferably about 0.001 to 0.1 parts by mass) with respect to 100 parts by mass of the acrylic polymer.

Examples of the radiation polymerizable monomer component include urethane (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipenta. Erythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, etc. can be mentioned. Examples of the radiation-polymerizable oligomer component include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based, and those with a molecular weight of about 100 to 30,000 are preferable. The content of the radiation-curable monomer component and the oligomer component in the radiation-curable adhesive forming the second adhesive layer is, for example, 5 to 500 parts by mass, preferably 40 to 150 parts by mass, with respect to 100 parts by mass of the base polymer. That's about it. Additionally, as an addition-type radiation-curable adhesive, for example, one disclosed in Japanese Patent Application Laid-Open No. 60-196956 may be used.

Examples of the radiation-curable adhesive include an intrinsic type radiation-curable adhesive containing a base polymer having a radiation-polymerizable functional group such as a carbon-carbon double bond at the polymer side chain or at the terminal of the polymer main chain. Using such an intrinsic type radiation-curable adhesive tends to suppress unintended changes in adhesive properties over time due to movement of low molecular weight components within the formed second adhesive layer.

As the base polymer contained in the internal-type radiation-curable adhesive, an acrylic polymer is preferable. As a method of introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer, for example, a raw material monomer containing a monomer component having a first functional group is polymerized (copolymerized) to obtain an acrylic polymer, and then the acrylic polymer is obtained. A method of subjecting a compound having a reactive second functional group and a radiation-polymerizable carbon-carbon double bond to a condensation reaction or addition reaction with an acrylic polymer while maintaining the radiation-polymerizability of the carbon-carbon double bond is included.

Combinations of the first functional group and the second functional group include, for example, a carboxyl group and an epoxy group, an epoxy group and a carboxyl group, a carboxyl group and an aziridyl group, an aziridyl group and a carboxyl group, a hydroxy group and an isocyanate group, an isocyanate group and a hydroxy group, etc. Among these, from the viewpoint of ease of reaction tracking, a combination of a hydroxy group and an isocyanate group, and a combination of an isocyanate group and a hydroxy group are preferable. Among them, producing a polymer having a highly reactive isocyanate group is highly technically difficult, and on the other hand, from the viewpoint of ease of production and availability of an acrylic polymer having a hydroxy group, the first functional group is a hydroxy group and the second functional group is an isocyanate group. A combination is desirable. Compounds having an isocyanate group and a radiopolymerizable carbon-carbon double bond, that is, isocyanate compounds containing a radiopolymerizable unsaturated functional group include, for example, methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, and m-isopropenyl. -α,α-dimethylbenzyl isocyanate, etc. can be mentioned. In addition, the acrylic polymer having a hydroxy group includes structural units derived from the above-mentioned hydroxy group-containing monomers and ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. You can hear things like:

The radiation-curable adhesive preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include α-ketol-based compounds, acetophenone-based compounds, benzoin ether-based compounds, ketal-based compounds, aromatic sulfonyl chloride-based compounds, photoactive oxime-based compounds, benzophenone-based compounds, and thioxic acid. Tone-based compounds, camphorquinone, halogenated ketone, acylphosphine oxide, acylphosphonate, etc. can be mentioned. Examples of the α-ketol-based compounds include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2- Methyl-2-hydroxypropiophenone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned. Examples of the acetophenone-based compounds include methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 2-methyl-1-[4-(methylthio). -phenyl]-2-morpholinopropan-1-one, etc. can be mentioned. Examples of the benzoin ether-based compounds include benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether. Examples of the ketal-based compound include benzyldimethylketal. Examples of the aromatic sulfonyl chloride-based compound include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime-based compound include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of the benzophenone-based compounds include benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone. Examples of the thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone. Oxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. can be mentioned. The content of the photopolymerization initiator in the radiation-curable adhesive is, for example, 0.05 to 20 parts by mass with respect to 100 parts by mass of the base polymer.

The heat-foamable adhesive is an adhesive that contains a component (foaming agent, heat-expandable microsphere, etc.) that foams or expands when heated. Examples of the foaming agent include various inorganic and organic foaming agents. Examples of the inorganic foaming agent include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and azides. Examples of the organic blowing agent include salt fluoroalkane such as trichloromonofluoromethane and dichloromonofluoromethane; Azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate; Hydrazine-based compounds such as paratoluenesulfonylhydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 4,4'-oxybis(benzenesulfonylhydrazide), and allylbis(sulfonylhydrazide); Semicarbazide compounds such as p-toluylenesulfonylsemicarbazide and 4,4'-oxybis(benzenesulfonylsemicarbazide); triazole-based compounds such as 5-morpholyl-1,2,3,4-thitriazole; and N-nitroso-based compounds such as N,N'-dinitrosopentamethylenetetramine and N,N'-dimethyl-N,N'-dinitrosoterephthalamide. Examples of the thermally expandable microspheres include microspheres in which a substance that is easily gasified and expanded by heating is encapsulated in the shell. Examples of substances that easily gasify and expand by heating include isobutane, propane, and pentane. Heat-expandable microspheres can be produced by encapsulating a substance that easily gasifies and expands when heated into a shell-forming material by a coacervation method, an interfacial polymerization method, or the like. As the shell-forming material, a material that exhibits thermal meltability or a material that can be ruptured by the action of thermal expansion of the encapsulating material can be used. Examples of such substances include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.

Examples of the non-adhesion-reducing type adhesive layer include a pressure-sensitive adhesive layer. In addition, the pressure-sensitive adhesive layer includes a pressure-sensitive adhesive layer formed from the radiation-curable adhesive described above with respect to the adhesive layer capable of reducing adhesive force, which is cured in advance by radiation irradiation and has a constant adhesive force. The adhesive that forms the non-adhesion-reduced adhesive layer can be used individually or in combination of two or more types. Additionally, the entire second adhesive layer may be a non-reduced adhesive force adhesive layer, or a portion may be a non-reduced adhesive force adhesive layer. For example, when the second adhesive layer has a single-layer structure, the entire second adhesive layer may be a non-reduced adhesive layer, a specific portion of the second adhesive layer may be a non-reduced adhesive layer, and other The portion may be an adhesive layer capable of reducing adhesive force. In addition, when the second adhesive layer has a laminated structure, all of the adhesive layers in the laminated structure may be non-reduced adhesive force adhesive layers, and some of the adhesive layers in the laminated structure may be non-reduced adhesive layers.

An adhesive layer formed from a radiation-curable adhesive (a non-irradiated radiation-curable adhesive layer) is cured in advance by irradiation with radiation (a radiation-curable adhesive layer that has been irradiated), even if the adhesive strength is reduced by radiation. , it exhibits adhesiveness due to the polymer component it contains, and is capable of exhibiting the minimum necessary adhesive force for the double-sided adhesive film for transfer according to the present invention. When using a radiation-cured adhesive layer that has been irradiated, in the direction of expansion of the surface of the second adhesive layer, the entire second adhesive layer may be a radiation-cured adhesive layer that has been irradiated, and a portion of the second adhesive layer may be a radiation-cured adhesive layer that has been irradiated. It may be a radiation-curing adhesive layer, or the other portion may be a radiation-curing adhesive layer that has not been irradiated with radiation. In addition, in this specification, “radiation-curable pressure-sensitive adhesive layer” refers to a pressure-sensitive adhesive layer formed from a radiation-curable pressure-sensitive adhesive, including an unirradiated radiation-curable pressure-sensitive adhesive layer having radiation hardening properties and a radiation-curing pressure-sensitive adhesive layer after the pressure-sensitive adhesive layer is cured by radiation irradiation. Both complete radiation-curable adhesive layers are included.

As the adhesive forming the pressure-sensitive adhesive layer, a known or commonly used pressure-sensitive adhesive can be used, and an acrylic adhesive containing an acrylic polymer as a base polymer can be preferably used. When the second pressure-sensitive adhesive layer contains an acrylic polymer as a pressure-sensitive adhesive, the acrylic polymer is preferably a polymer that contains the structural unit derived from (meth)acrylic acid ester as the largest structural unit in terms of mass ratio. As the acrylic polymer, for example, an acrylic polymer described as an acrylic polymer that can be contained in the above-described addition type radiation-curable adhesive can be employed.

<Description>

The base material in the double-sided adhesive film for transfer according to the present invention is an element that functions as a support in the first adhesive layer or the second adhesive layer. Examples of the substrate include plastic substrates (particularly plastic films). The substrate may be a single layer or a laminate of the same or different types of substrates.

Resins constituting the plastic substrate include, for example, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymerization polypropylene, block copolymerization polypropylene, homopolypropylene, polybutene, and polymethyl. Pentene, ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer. polyolefin resin, etc.; Polyurethane; Polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT); polycarbonate; polyimide; polyetheretherketone; polyetherimide; Polyamides such as aramid and wholly aromatic polyamide; polyphenyl sulfide; fluororesin; polyvinyl chloride; polyvinylidene chloride; cellulose resin; Silicone resin, etc. can be mentioned. The double-sided adhesive film for transfer according to the present invention exhibits good heat resistance that is difficult to cause expansion or contraction due to heat when transferring and mounting the received electronic components by heat compression (for example, 150°C) on a mounting board, and is mounted with high precision. From the viewpoint of being able to do so, the base material contains heat-resistant resins such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), and polyetheretherketone (PEEK) as a main component. It is preferable to do so, and it is more preferable to contain polyimide as a main component. In addition, the main component of the base material is the component that occupies the largest mass ratio among the constituent components. The above resins can be used individually or in combination of two or more types. When the second adhesive layer is a radiation-curing adhesive layer as described above, the substrate preferably has radiation transparency.

When the base material is a plastic film, the plastic film may be unoriented or oriented in at least one direction (uniaxial direction, biaxial direction, etc.), but non-orientation is preferable because it is difficult to exhibit heat shrinkability.

The surface of the substrate on the side of the first adhesive layer and/or the second adhesive layer is subjected to, for example, corona discharge treatment, plasma treatment, sand mat treatment, or ozone exposure treatment for the purpose of increasing adhesion to the adhesive layer and retention properties. , physical treatment such as flame exposure treatment, high-pressure electric shock treatment, ionizing radiation treatment, etc.; Chemical treatment such as chromic acid treatment; Coating agent (undercoat agent); Surface treatment such as adhesion facilitation treatment by silicone primer treatment may be performed. Additionally, in order to impart antistatic ability, in addition to providing a conductive vapor deposition layer containing metals, alloys, oxides thereof, etc. on the surface of the substrate, a conductive polymer such as PEDOT-PSS may be coated. Surface treatment to increase adhesion is preferably performed on the entire surface of the adhesive layer side of the substrate.

From the viewpoint of ensuring the strength for the base material to function as a support in the double-sided adhesive film for transfer according to the present invention, the thickness of the base material is preferably 5 μm or more, more preferably 10 μm or more, even more preferably is 15 μm or more, particularly preferably 20 μm or more. Furthermore, from the viewpoint of realizing appropriate flexibility in the double-sided adhesive film for transfer according to the present invention, the thickness of the base material is preferably 200 μm or less, more preferably 180 μm or less, and still more preferably 150 μm or less. am.

<Separator>

The adhesive layer surface (adhesive surfaces of the first adhesive layer and the second adhesive layer) of the double-sided adhesive film for transfer according to the present invention is protected by a release liner (separator) until use. The separator is used as a protective material for the adhesive layer, and is peeled off when the adhesive film is attached to the adherend.

As the separator, common release paper and the like can be used. Specifically, for example, a base material having a release layer of a release treatment agent on at least one surface, as well as a fluorine-based polymer (e.g., polytetrafluoroethylene, Low-adhesion substrates containing (polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.) or non-polar A low-adhesion substrate containing a polymer (e.g., olefin resin such as polyethylene, polypropylene, etc.) can be used.

As the separator, for example, a separator in which a release layer is formed on at least one side of the separator base material can be suitably used. Examples of such separator substrates include polyester films (polyethylene terephthalate films, etc.), olefin resin films (polyethylene films, polypropylene films, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon films), and rayon films. In addition to plastic base films (synthetic resin films) and papers (fine paper, Japanese paper, kraft paper, glassine paper, synthetic paper, top coat paper, etc.), these are multi-layered (2 to 3 layers) by laminating or co-extruding, etc. complex), etc.

The peeling treatment agent constituting the peeling layer is not particularly limited, but for example, a silicone-based peeling treatment agent, a fluorine-based peeling treatment agent, a long-chain alkyl-based peeling treatment agent, a fatty acid amide-based peeling treatment agent, etc. can be used. Among these, the silicone-based peeling treatment agent may be used. I am desirable. The peeling treatment agent can be used individually or in combination of two or more types. Additionally, since the first adhesive layer is composed of a low-adhesive adhesive layer, it is also possible to use a base material that has not been treated with a release treatment agent as a separator.

The thickness of the peeling layer for the first separator is preferably 10 to 2000 nm, more preferably 20 to 500 nm, and even more preferably from the viewpoint of keeping F(1) and T(1) within the numerical ranges described above. is 30 to 150 nm, particularly preferably 40 to 80 nm.

The thickness of the release layer for the second separator is preferably 10 to 2000 nm from the viewpoint of ensuring that F(2), P(2), P'(2), and T(2) are within the numerical ranges described above, More preferably, it is 30 to 500 nm, more preferably 50 to 250 nm, and particularly preferably 70 to 150 nm.

Moreover, it is preferable that the thickness of the peeling layer on the first separator is less than the thickness of the peeling layer on the second separator.

In order to prevent adverse effects on electronic components, the separator may have an antistatic layer formed on at least one side of the separator base material. The antistatic layer may be formed on one side of the separator (the peeled surface or the untreated side), or may be formed on both sides of the separator (the peeled surface and the untreated side).

Examples of antistatic agents contained in the antistatic resin include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as primary, secondary, and tertiary amino groups, sulfonates, sulfate esters, and phosphones. Anionic antistatic agents having anionic functional groups such as acid salts and phosphate esters, amphoteric antistatic agents such as alkylbetaines and their derivatives, imidazoline and its derivatives, alanine and its derivatives, amino alcohols and their derivatives, glycerin and its derivatives. Derivatives, nonionic antistatic agents such as polyethylene glycol and derivatives thereof, and further ion conductive polymers obtained by polymerizing or copolymerizing monomers having the above cationic, anionic, and zwitterionic ionic conductive groups. These compounds can be used individually or in combination of two or more types.

The thickness of the first separator is preferably 1 to 150 μm, more preferably 5 to 100 μm, and even more preferably 10 μm from the viewpoint of keeping F(1) and T(1) within the numerical ranges described above. to 80㎛.

The thickness of the second separator is preferably 10 to 150 ㎛, more preferably from the viewpoint of keeping F(2), P(2), P'(2), and T(2) within the numerical ranges described above. is 15 to 100㎛, more preferably 20 to 80㎛.

The method for producing the laminated film according to the present invention varies depending on the composition of the adhesive composition, etc., is not particularly limited, and known forming methods can be used, for example, methods (1) to (4) below. can be mentioned.

(1) The adhesive composition is applied (applied) on a substrate to form a composition layer, and the composition layer is cured (for example, by heat curing or curing by irradiation of active energy rays such as ultraviolet rays) to form an adhesive layer. How to Make Adhesive Film

(2) The adhesive composition is applied (applied) on a separator to form a composition layer, and the composition layer is cured (for example, by heat curing or curing by irradiation of active energy rays such as ultraviolet rays) to form an adhesive layer. A method of producing an adhesive film by transferring the adhesive layer onto the substrate.

(3) A method of producing an adhesive film by applying the adhesive composition on a substrate and drying it to form an adhesive layer.

(4) A method of manufacturing an adhesive film by applying the adhesive composition on a separator, drying it to form an adhesive layer, and then transferring the adhesive layer onto a substrate.

As the curing method in the above (1) to (4), a heat curing method is preferable because it is excellent in productivity and can form a homogeneous and smooth surface adhesive layer.

As a method of applying (coating) the adhesive composition on a predetermined surface, a known coating method can be adopted, and is not particularly limited, but examples include roll coat, kiss roll coat, gravure coat, reverse coat, and roll. Examples include brush coating, spray coating, deep roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, and extrusion coating using a die coater.

The thickness (total thickness) of the double-sided adhesive film for transfer according to the present invention is not particularly limited, but is preferably 10 μm or more, and more preferably 15 μm or more. If the thickness is above a certain level, it is preferable because it makes it easier for the first adhesive layer to receive electronic components with high precision. Additionally, the upper limit of the thickness (total thickness) of the double-sided adhesive film for transfer according to the present invention is not particularly limited, but is preferably 500 μm, and more preferably 300 μm. If the thickness is below a certain level, it is preferable because it becomes easy to transfer the electronic component to the mounting substrate with high precision.

The double-sided adhesive film for transfer according to the present invention is suitably used in a method of mounting electronic components on a mounting substrate. The method of mounting electronic components on a mounting board using the double-sided adhesive film for transfer according to the present invention preferably includes the following steps.

A process in which the first adhesive layer of the double-sided adhesive film for transfer receives the diced electronic components (first process)

A process of transferring the electronic component received by the first adhesive layer to a mounting board (second process)

Figure 2 is a cross-sectional schematic diagram showing one embodiment of the first step in the method of mounting electronic components on a mounting board using the double-sided adhesive film for transfer according to the present invention.

In Fig. 2(a), the double-sided adhesive film 1 for transfer is adhered to the carrier substrate 22 on the adhesive surface of the second adhesive layer 12. The surface of the carrier substrate 22 bonded to the second adhesive layer 12 may be provided with a marking pattern for arranging electronic components. Since the double-sided adhesive film 1 for transfer has high transparency, the marking pattern attached to the carrier substrate 22 can be visually recognized.

On the upper part of the adhesive surface of the first adhesive layer 11 of the transfer double-sided adhesive film 1, a plurality of electronic components 21 separated by dicing are adhered to the dicing tape 20, It is arranged opposite to the adhesive surface of the first adhesive layer 11 and spaced apart from it.

In FIG. 2(b), the electronic component 21 is pushed against the pin member 23 from the side of the dicing tape 20 to which the electronic component 21 is not adhered, and the electronic component 21 is removed. 1 It is brought close to the adhesive surface of the adhesive layer 11, and the adhesive surface of the first adhesive layer 11 is received. Receiving may be performed by bringing the electronic component 21 into contact with the first adhesive layer 11, or may be performed non-contactly. When receiving in a non-contact manner, the electronic component 21 is pushed until the electronic component 21 is peeled from the dicing tape 20 and dropped on the adhesive surface of the electronic component 21. When receiving by contacting, the adhesive surface of the first adhesive layer 11 has low adhesiveness, so the stress applied when the electronic component 21 is received is weak, so damage to the electronic component 21 can be suppressed. In the case of non-contact reception, the adhesive surface of the first adhesive layer 11 has low adhesiveness, so the fallen electronic component 21 can be caught with high positional accuracy. Additionally, the electronic component 21 may be peeled from the dicing tape 20 by irradiating radiation such as ultraviolet rays or a laser beam instead of the pin member 23.

The electronic components 21 may be received individually or in batches of a plurality of them. Figure 2 (c) is a cross section showing the form in which all the electronic components 21 of the dicing tape 20 are received on the adhesive surface of the first adhesive layer 11 of the double-sided adhesive film 1 for transfer. This is a schematic diagram.

Figure 3 is a cross-sectional schematic diagram showing the second step in the method of mounting electronic components on a mounting board using the double-sided adhesive film for transfer according to the present invention.

As shown in Figure 3 (a), the first adhesive layer of the double-sided adhesive film 1 for transfer is opposed to and spaced apart from the circuit surface 31 (circuit pattern not shown) of the mounting substrate 30 (circuit pattern not shown). The electronic components 21 arranged are placed on the adhesive surface of 11). Next, as shown in (b) of FIG. 4, electronic components arranged on the circuit surface 31 of the mounting board 30 and the adhesive surface of the first adhesive layer 11 of the double-sided adhesive film 1 for transfer. (21) is brought close to bring the electronic component 21 and the circuit surface 31 of the mounting board 30 into contact.

The transfer of the electronic component 21 to the circuit surface 31 of the mounting board 30 may be performed by thermal compression (for example, 150° C. for 1 minute). The substrate 10, first adhesive layer 11, and/or second adhesive layer 12 constituting the double-sided adhesive film 1 for transfer have excellent heat resistance, and therefore do not expand, contract, or expand by heat compression. Since the adhesive force is difficult to change, the electronic component 21 can be transferred to the circuit surface 31 of the mounting board 30 with high precision.

Next, as shown in FIG. 3(c), the transfer double-sided adhesive film 1 and the mounting substrate 30 are spaced apart, so that the electronic component 21 is peeled from the first adhesive layer 11 and mounted. It is transferred to the circuit surface 31 of the substrate 30. Since the first adhesive layer 11 is composed of a low-adhesive adhesive layer, the electronic component 21 can be easily peeled off and efficiently mounted on the mounting board 30 without damaging the electronic component 21. there is.

After the electronic component 21 is mounted on the mounting board 30, the transfer double-sided adhesive film 1 in FIG. 3(c) may be peeled from the carrier board 22 (not shown). Since the second adhesive layer 12 is composed of a peelable adhesive layer, it can be peeled off without adhesive residue and has excellent reworkability, so the carrier substrate 22 can be easily reused.

The electronic component to be mounted on the mounting board is not particularly limited, but can be suitably used for fine and thin semiconductor chips or LED chips.

Example

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples at all.

<Preparation Example 1> Preparation of acrylic copolymer (1)

In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and condenser, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 95 parts by weight, acrylic acid (manufactured by Toa Kose Co., Ltd.): 5 parts by weight, and 2 as a polymerization initiator. , 2'-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries): 0.2 parts by weight, ethyl acetate: 156 parts by weight were added, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was brought to around 63°C. The polymerization reaction was maintained for 10 hours to prepare a solution (solid content: 40% by weight) of acrylic copolymer (1) with a weight average molecular weight of 700,000.

<Preparation Example 2> Preparation of acrylic copolymer (2)

In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas introduction tube, and condenser, 80% acrylic acid (AA) (manufactured by Osaka Yuki Chemical Co., Ltd.): 2.8 parts by weight, 2-ethylhexyl acrylate (2EHA) (Nippon) (manufactured by Shokubai Co., Ltd.): 44 parts by weight, vinyl acetate: 35.2 parts by weight (manufactured by Denka Co., Ltd.), and toluene: 20 parts by weight were added and stirred gently while nitrogen gas was introduced and stirred for 1 hour. After that, 0.2 parts by weight of Naifer BW (manufactured by Nichiyu Co., Ltd.) was added dropwise as a polymerization initiator diluted with 96 parts by weight of toluene, and the liquid temperature in the flask was maintained at around 40°C. After that, the liquid temperature in the flask was raised to 60°C to perform a polymerization reaction for 8 hours, and then the temperature was raised to 95°C and stirred for 4 hours to prepare a solution (solid content: 35% by weight) of the acrylic copolymer (2) with a weight average molecular weight of 560,000. It was prepared.

<Manufacture Example 3> Manufacture of separator (1)

Silicone mold release agent (KS-847, manufactured by Shin-Etsu Chemical Co., Ltd.): 100 parts by weight, catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.): 3.0 parts by weight diluted in toluene to 1.0 weight%, and subjected to silicone-based peeling treatment. I got the liquid. The obtained silicone-based peeling treatment liquid was applied as a release layer to the surface of a base film (thickness 50 μm, product name “Diafoil T100-50S”, manufactured by Mitsubishi Chemical Corporation) with a wire bar so that the thickness after drying was 50 nm, The separator (1) was cured and dried under the conditions of a drying temperature of 130°C and a drying time of 3 minutes (peeling treatment A), and a laminate of [peeling layer (thickness 50 nm, mold release treatment A)]/[base layer]. Manufactured.

<Manufacture Example 4> Manufacture of separator (2)

A base film (25 μm thick, product name “Diafoil T100-25”, manufactured by Mitsubishi Chemical Co., Ltd.) was used, and the peeling layer was applied in the same manner as in Production Example 3, except that the thickness after drying was 100 nm. A separator (2) containing a laminate of [release layer (thickness 100 nm, mold release treatment B)]/[base layer] was manufactured. Additionally, a separator used as a second separator was manufactured by arbitrarily changing the thickness of the base film as shown in Table 1.

<Manufacture Example 5> Manufacture of separator (3)

In the same manner as in Production Example 3, except that the catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was used at 1.0 parts by weight, [release layer (thickness 50 nm, mold release treatment C)]/[base layer] was laminated. A separator (3) containing a sieve was manufactured.

<Example 1>

100 parts by weight of silicone-based adhesive (addition reaction silicone-based adhesive, brand name “X-40-3306”, manufactured by Shin-Etsu Chemical Co., Ltd.), platinum-based catalyst 1 (brand name “CAT-PL-50T”, manufactured by Shin-Etsu Chemical Co., Ltd.) (Note) 1.4 parts by weight of silicone-based release agent 1 (addition reaction type silicone-based release agent mainly containing dimethylpolysiloxane, brand name "KS-776A" and manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the total solid content was added. It was diluted with toluene to reach 25% by weight and mixed with a disper to prepare a silicone-based adhesive composition.

Adhesive thickness after drying the silicone-based adhesive composition on the silicone primer-treated side of the base film (polyester film with one side treated with silicone primer, thickness 75㎛, product name “Diafoil MRF#75”, manufactured by Mitsubishi Juicy Co., Ltd.) It was applied to a thickness of 10㎛, cured and dried under the conditions of a drying temperature of 120°C and a drying time of 5 minutes. In this way, a film having a silicone-based adhesive layer on the silicone primer-treated layer of the base film was obtained.

The silicone-based adhesive layer, as a first separator, is bonded to and protected with the release layer side of the separator 1 manufactured in Production Example 3, and [first separator layer]/[silicone-based adhesive layer]/[base film layer] is laminated. A laminate (1) having a structure was obtained.

Next, to the solution of the acrylic copolymer (1) obtained in Production Example 1, 6 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent was added in terms of solid content, based on 100 parts by weight of the solid content. The acrylic adhesive composition (1) diluted with ethyl acetate so that the total solid content was 25% by weight and stirred in a disper was placed on the release layer side of the second separator (separator (2)) so that the thickness after drying with a fountain roll was 5. It was applied to a thickness of ㎛, cured and dried under the conditions of a drying temperature of 130°C and a drying time of 30 seconds. In this way, the acrylic adhesive layer 1 was formed on the second separator.

Next, the base film side (silicon primer-untreated side) of the above-obtained laminate 1 is bonded to the surface of the acrylic adhesive layer 1, and [first separator layer]/[silicone-based adhesive layer (first adhesive) layer)]/[base film layer]/[acrylic adhesive (1) layer (second adhesive layer)]/[second separator layer] A laminated film was obtained.

<Example 2>

The adhesive thickness after drying of the silicone-based adhesive of the first adhesive layer was set to 25 ㎛, and for the second separator, instead of the separator 2, the base film in the separator 2 was replaced with a base film (thickness 38 ㎛, product name “Diamer”). A laminated film was obtained in the same manner as in Example 1, except that a separator changed to "Foil T100C38" (manufactured by Mitsubishi Chemical Co., Ltd.) was used.

<Example 3>

The adhesive thickness after drying of the silicone-based adhesive of the first adhesive layer was set to 50 ㎛, and for the second separator, instead of the separator 2, the base film in the separator 2 was replaced with a base film (thickness 50 ㎛, product name “Diamond”). A laminated film was obtained in the same manner as in Example 1, except that a separator changed to "Foil T100-50S" (manufactured by Mitsubishi Chemical Co., Ltd.) was used.

<Example 4>

The adhesive thickness after drying of the silicone-based adhesive of the first adhesive layer was set to 75 ㎛, and for the second separator, the base film in the separator 2 instead of the separator 2 was used as a base film (thickness 75 ㎛, product name “Dyer”). A laminated film was obtained in the same manner as in Example 1, except that a separator changed to "Foil T100-75S" (manufactured by Mitsubishi Chemical Co., Ltd.) was used.

<Example 5>

A laminated film was obtained in the same manner as in Example 1, except that the adhesive thickness after drying of the silicone-based adhesive in the first adhesive layer was 50 μm, and the separator 2 was used for the first separator.

<Example 6>

A laminated film was obtained in the same manner as in Example 5, except that the adhesive thickness after drying of the silicone-based adhesive in the first adhesive layer was 75 μm.

<Example 7>

The adhesive thickness after drying of the silicone-based adhesive of the first adhesive layer was set to 25 ㎛, a separator (3) was used as the first separator, and an acrylic adhesive (2) was used instead of the acrylic adhesive (1) for the first adhesive layer. A laminated film was obtained in the same manner as in Example 1 except for what was used.

<Example 8>

A laminated film was obtained in the same manner as in Example 7, except that the adhesive thickness after drying of the silicone-based adhesive in the first adhesive layer was 50 μm.

<Example 9>

A laminated film was obtained in the same manner as in Example 7, except that the adhesive thickness after drying of the silicone-based adhesive in the first adhesive layer was 75 μm.

<Comparative Example 1>

A laminated film was obtained in the same manner as in Example 1, except that the separator 2 was used as the first separator.

<Comparative Example 2>

A laminated film was obtained in the same manner as in Example 2 except that the separator 2 was used as the first separator.

<Evaluation>

The following evaluation was performed on the double-sided adhesive films for transfer obtained in Examples and Comparative Examples. The results are shown in Table 2.

<Measurement of peeling peel force F(1) of the first separator with respect to the first adhesive layer>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 50 mm and a length of 100 mm, and were used as samples for evaluation.

The separator of the second adhesive layer was peeled off, and the surface of the second adhesive layer was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 23°C and 50% R.H. at 0.25 MPa and 0.3 m/min. After bonding with a roller, using a universal tensile tester (product name "TCM-1kNB", manufactured by Minebea Co., Ltd.), the first separator is separated from the first adhesive layer at a peeling angle of 180 degrees and a peeling speed of 0.3 m/min. By peeling, the peeling peeling force F(1) was measured.

<Measurement of peeling peeling force F(2) of the second separator with respect to the second adhesive layer>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 50 mm and a length of 100 mm, and were used as samples for evaluation.

The separator of the first adhesive layer was peeled off, and the surface of the first adhesive layer was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 23°C and 50% R.H. at 0.25 MPa and 0.3 m/min. After bonding with a roller, using a universal tensile tester (product name "TCM-1kNB", manufactured by Minebea Co., Ltd.), the second separator is separated from the second adhesive layer at a peeling angle of 180 degrees and a peeling speed of 0.3 m/min. By peeling, the peeling peeling force F(2) was measured.

<Measurement of peeling adhesive force P(2) of the second adhesive layer to the carrier substrate>

The double-sided transfer films of Examples and Comparative Examples were cut to a width of 50 mm and a length of 100 mm, and were used as samples for evaluation.

In an environment of 23°C and 50% R.H., the surface of the second adhesive layer from which the separator of the evaluation sample was peeled was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 0.25 MPa and 0.3 m/min. After sticking with a roller and curing for 30 minutes, a universal tensile tester (product name "TCM-1kNB", manufactured by Minebea Co., Ltd.) was used to remove the second adhesive from the glass plate at a peeling angle of 180 degrees and a tensile speed of 0.3 m/min. By peeling off the layer, the peeling adhesion P(2) was measured.

<Measurement of peeling adhesive force P'(2) of the second adhesive layer to the glass plate at 160°C after 5 minutes>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 50 mm and a length of 100 mm, and were used as samples for evaluation.

In an environment of 23°C and 50% R.H., the surface of the second adhesive layer from which the separator of the evaluation sample was peeled was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 0.25 MPa and 0.3 m/min. It was attached with a roller and cured for 30 minutes.

Next, it was heated in an air-circulating constant temperature oven at 160°C for 5 minutes, then left to cool in an environment of 23°C and 50% R.H. for 30 minutes, and then tested using a universal tensile tester (product name “TCM-1kNB”, manufactured by Minebea Co., Ltd.). The adhesive force P'(2) was measured by peeling the second adhesive layer from the glass plate at a peeling angle of 180 degrees and a tensile speed of 0.3 m/min.

<Measurement of the measured peeling force T(1) of the first separator with respect to the first adhesive layer>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 50 mm and a length of 100 mm using a small-head paper cutter, and were used as samples for evaluation.

The separator of the second adhesive layer was peeled off, and the surface of the second adhesive layer was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 23°C and 50% at 0.25 MPa and 0.3 m/min. After bonding with a roller, in an environment of 23°C and 50% R.H., a rubber-based adhesive tape (product name “NO.315”, 19 mm width, manufactured by Nitto Denko Co., Ltd.) is applied to the center of the width direction of the back of the surface protection film with a hand roller. It was compressed. Under the same environment, the first separator is peeled from the first adhesive layer under the conditions of a tensile speed of 0.3 m/min and a peeling angle of 90 degrees, and the maximum stress applied at the beginning of peeling is measured as the peeling force T(1) [N/50mm]. It was recorded.

<Measurement of the measured peeling force T(2) of the second separator with respect to the second adhesive layer>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 50 mm and a length of 100 mm using a small-head paper cutter, and were used as samples for evaluation.

The separator of the second adhesive layer was peeled off, and the surface of the second adhesive layer was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 23°C and 50% R.H. at 0.25 MPa and 0.3 m/min. After bonding with a roller, in an environment of 23°C Compress with roller. Under the same environment, the second separator is peeled from the second adhesive layer under the conditions of a tensile speed of 0.3 m/min and a peeling angle of 90 degrees, and the maximum stress applied at the beginning of peeling is measured as the peeling force T (2) [N/50 mm]. It was recorded.

<Evaluation of the peelability of the first separator>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 10 mm and a length of 10 mm, and were used as samples for evaluation.

The separator of the second adhesive layer was peeled off, and the surface of the second adhesive layer was placed on a glass plate (product name “S200423”, manufactured by Matsunami Glass Kogyo Co., Ltd.) at 23°C and 50% R.H. at 0.25 MPa and 0.3 m/min. After bonding with a roller, an acrylic adhesive tape (product name "NO.31B", manufactured by Nitto Denko Co., Ltd.) pressed with a hand roller to the right angle part of the evaluation sample was used as a handle, and was held at 23°C and 50%R.H. , the first separator was peeled from the first adhesive layer at a peeling angle of 180 degrees and a peeling speed of 0.3 m/min, and the peelability of the first separator was evaluated according to the following standards.

(Evaluation standard)

○ (good): No lifting occurs at the interface between the second adhesive layer and the glass plate, and the first separator is peeled off.

△ (possible): The first separator is peeled off, but lifting occurs at the interface between the second adhesive layer and the glass plate.

× (impossible): Before peeling off the first separator, the second adhesive layer and the glass plate are peeled off.

<Evaluation of peelability of second separator>

The double-sided adhesive films for transfer of Examples and Comparative Examples were cut to a width of 10 mm and a length of 10 mm, and were used as samples for evaluation.

The evaluation sample was placed on the adsorption stage with the first separator side facing down and fixed by suction. An acrylic adhesive tape (product name "NO.31B", manufactured by Nitto Denko Co., Ltd.) pressed to the right angle of the fixed evaluation sample with a hand roller was used as a handle, and at 23°C and 50% R.H., the peeling angle was 180 degrees, The second separator was peeled from the second adhesive layer at a peeling speed of 0.3 m/min, and the peelability of the second separator was evaluated according to the following standards.

(Evaluation standard)

○ (good): Peeling occurs without lifting at the interface between the first adhesive layer and the first separator.

△ (possible): Peeled, but lifting occurred at the interface between the first adhesive layer and the first separator.

× (not possible): Before peeling, the first adhesive layer and the first separator are peeled off.

<Glass rework>

The sample after measuring the peeling adhesive force P'(2) of the second adhesive layer to the glass plate at 160°C after 5 minutes was visually observed, and reworkability was judged according to the following standards.

(Evaluation standard)

◎ (Excellent): No damage such as glass breakage or adhesive residue is observed on the glass plate.

○ (Good): For the glass plate, almost no damage such as glass breakage or adhesive residue is visible.

× (No): Glass plate is damaged, adhesive residues, etc. are visible.

1 laminated film
10 listed
11 First adhesive layer
12 Second adhesive layer
110 first separator
120 second separator
20 dicing tape
21 electronic components
22 carrier substrate
23 pin member
30 mounting board
31 Circuit side

Claims (3)

It is a laminated film in which a first separator, a first adhesive layer, a substrate, a second adhesive layer, and a second separator are laminated in this order, wherein the first adhesive layer includes a low-adhesive adhesive layer, and the second adhesive layer includes a low-adhesive adhesive layer. The adhesive layer includes a peelable adhesive layer,
180° peeling peeling force F(1) (N/50mm) of the first separator with respect to the first adhesive layer measured under the conditions of 23°C, 50%RH and peeling speed of 0.3m/min,
180° peeling peeling force F(2) (N/50mm) of the second separator with respect to the second adhesive layer measured under the conditions of 23°C, 50%RH, and peeling speed of 0.3m/min,
180° peeling adhesion P(2) (N/50mm) of the second adhesive layer to the glass plate measured under the conditions of 23°C, 50%RH and a tensile speed of 0.3m/min, and
After attaching the second adhesive layer to a glass plate and 5 minutes at 160°C, the 180° peeling adhesive force of the second adhesive layer to the glass plate is measured under the conditions of 23°C, 50%RH, and a tensile speed of 0.3 m/min. A laminated film in which P'(2)(N/50mm) satisfies the relationship of the following equation.
F(2)≤F(1)
P(2)≥F(1)
P'(2)/P(2)<1.20
P'(2)<1.00 The laminated film according to claim 1, which further satisfies the relationship of the following equation.
F(2)/F(1)<0.80
P(2)/F(1)>1.00 The method of claim 1 or 2, wherein the 90° gauge peeling force T(1)(N) of the first adhesive layer with respect to the first separator is measured under the conditions of 23° C., 50%RH, and a tensile speed of 0.3 m/min. /50mm),
The 90° gauge peel force T(2) (N/50mm) of the second adhesive layer against the second separator measured under the conditions of 23°C, 50%RH and a tensile speed of 0.3m/min, and
A laminated film in which the adhesive force P(2) satisfies the relationship of the following equation.
T(1)/T(2)>1.05
P(2)/T(1)<1.00