TW201739619A - Release film for manufacturing process with excellent performance and appearance, the applications thereof and the method of manufacturing resin-sealed semiconductor using the same can be easily released without the effect of metal mold structure or release dosage - Google Patents

Abstract

The invention provides a release film for a manufacturing process, which can be used for forming a finished product after resin packaging, and can be easily released without the effect of metal mold structure or release dosage, for a finished product without any apparent wrinkles or defects. The release film comprises a release layer 1A, a heat-resistant resin layer 1B, and a laminated thin film of the release layer 1A'. The contact angle of the release layer 1A (and the laminated thin film of the release layer 1A') relative to water ranges from 90 degrees to 130 degrees. The tensile elastic rate of the laminated thin film at 120DEG C is from 75MPa to 500MPa, or, from 75MPa to 500MPa at 170DEG C. The release film for a manufacturing process comprises the release film for a manufacturing process, or a release layer 2A, a heat-resistant resin layer 2B, and a laminated thin film of the release layer 2A'. The contact angle of the release layer 2A (and the laminated thin film of the release layer 2A') relative to water ranges from 90 degrees to 130 degrees. The heat-resistant resin layer 2B comprises a layer 2B1 containing high-molecular anti-static agent. The tensile elastic rate of the laminated thin film at 120DEG C ranges from 75MPa to 500MPa, or from 75MPa to 500MPa at 170DEG C.

Description

Release film for process with good appearance performance, use thereof, and manufacturing method of resin-packaged semiconductor using the same

The present invention relates to a release film for a process which can effectively suppress the appearance defects of a molded article, in particular, a poor appearance due to wrinkles, and is preferably a release film for a semiconductor package process, in particular, a semiconductor is disposed in a metal mold. When a resin is injection-molded, such as a wafer, a release film for a process such as a semiconductor wafer and the inner surface of a metal mold, and a method of producing a resin-encapsulated semiconductor using the same.

In recent years, with the miniaturization and weight reduction of semiconductor packages and the like, it has been considered to reduce the amount of use of the encapsulating resin. Therefore, even if the amount of use of the encapsulating resin is reduced, in order to strongly bond the interface between the semiconductor wafer and the like and the resin, it is desirable to reduce the amount of the release agent contained in the encapsulating resin. Therefore, as a method of obtaining the release property between the encapsulating resin and the metal mold after the hardening molding, the inner surface of the metal mold and the semiconductor wafer are used. A method of disposing a release film between.

As such a release film, a fluorine-based resin film having excellent release property and heat resistance (for example, Patent Documents 1 and 2) and a poly-4-methyl-1-pentene resin film (for example, Patent Document 3) are proposed. Wait. However, when the spacer film is mounted on the inner surface of the metal mold, wrinkles are likely to occur, and the wrinkles are transferred to the surface of the molded article, which causes a problem of poor appearance.

Therefore, a laminated release film having a release layer and a heat-resistant layer has been proposed. The release film is a film which is released from the release layer and which suppresses wrinkles or poor appearance by the heat-resistant layer. The most representative of these proposals is the relationship between the storage modulus and the storage elastic modulus between the release layer and the heat-resistant layer (see, for example, Patent Documents 4 and 5). For example, in Patent Document 4, a laminated release film having a low storage elastic modulus of a release layer and a high storage elastic modulus of a heat-resistant layer, more specifically, a release layer of 175 ° C is described. The storage elastic modulus E' is 45 MPa or more and 105 MPa or less, and the storage elastic modulus E' of the heat-resistant layer at 175 ° C is a release film for a semiconductor packaging process of 100 MPa or more and 250 MPa or less.

Further, such a release film for a process can be used not only in a semiconductor package process but also in a molding process of a reflector for a light-emitting element such as a light-emitting diode (see, for example, Patent Document 6).

Further, charging of the release film also causes a defective appearance of the molded article. The release film used in the semiconductor sealing process is generally easy to be charged because it is a resin film as described above. For example, when the release film is taken out, static electricity is generated during peeling of the release film, and it is stored in a manufacturing environment. Foreign matter such as dust adheres to the charged release film, which causes the shape of the molded article to be abnormal (such as adhesion of foreign matter) or contamination of the metal mold. In particular, in a packaging device for a semiconductor wafer, as a resin for encapsulation, a particle resin is used, and a shape abnormality or a metal mold contamination caused by dust generated from the particulate resin adheres to the release film, and the appearance thereof Bad, has reached the point where it cannot be ignored.

Further, in recent years, in order to reduce the thickness of the package or to improve the heat dissipation property, the semiconductor wafer is flip-chip bonded, and the package in which the back surface of the wafer is exposed gradually increases. This project is called Molded Under Film (MUF) engineering. In the MUF project, in order to protect and shield the semiconductor wafer, the release film and the semiconductor wafer are packaged in direct contact. At this time, the release film is easily charged, and the semiconductor wafer is destroyed by charging-releasing at the time of peeling.

Therefore, various proposals have been made to prevent charging of the package film. For example, Patent Document 7 discloses a release film including a first thermoplastic resin layer that is in contact with a curable resin at the time of formation, a second thermoplastic resin layer that is in contact with the mold, and a first thermoplastic resin layer and a first thermoplastic resin layer. An intermediate layer disposed between the thermoplastic resin layers, wherein the intermediate layer is a layer containing a polymer-based antistatic agent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP 2001-310336 A

[Patent Document 2] JP 2002-110722 A

[Patent Document 3] JP 2002-361643 A

[Patent Document 4] JP 2010-208104 A

[Patent Document 5] International Publication WO 2015/133630 A1

[Patent Document 6] JP 2014-14928 A

[Patent Document 7] International Publication WO 2015/133630 A1

However, with the development of the technical field, the level required for the release film for a process such as a release film for a semiconductor packaging process is also increasing year by year, and it is required to suppress wrinkles in a worse process condition. The release film for the process, in particular, a release film for a process which is strongly required to have a release property, a wrinkle suppression, and a metal mold follow-up balance at a higher level.

In addition, it is required to release a release film for a process which is inferior in appearance of a molded article in a worse process condition, and in particular, strongly suppresses release property, suppresses appearance defects, and balances of metal molds at a very high level. The process uses a release film.

In view of the above, the first object of the present invention is to provide a release film for a process, which is a molded article which can be encapsulated by a resin, and which can be easily released from the influence of a metal mold structure or a release amount. Further, it is possible to obtain a molded article having no appearance defects such as wrinkles or defects.

In view of the above, the second invention of the present invention is to provide a release film for a process, which is a molded article capable of encapsulating a resin, and does not cause The metal mold structure or the influence of the release amount can be easily released, and a molded article having no appearance defects such as wrinkles or defects, abnormal shapes (such as foreign matter adhesion) can be obtained.

As a result of intensive review to solve the above problems, the present inventors have found that the rate of change in the thermal dimensionality of the release film for a process at a specific temperature, in particular, the TD direction of the laminated film constituting the release film for process (film) In the plane of the film, the thermal dimension change rate is hereinafter appropriately controlled with respect to the linear direction in the longitudinal direction of the film production, which is also referred to as "horizontal direction", and the wrinkles are suppressed when mounted on the inner surface of the metal mold. It is quite important to complete the first invention of the present invention.

As a result of the intensive review of the above-mentioned problems, the present inventors have found that the tensile modulus of the release film for a process at a specific temperature is appropriately controlled, and the heat-resistant resin layer constituting the laminated film is provided. The layer containing the polymer-based charged agent is very important for suppressing the appearance defect, and thus the second invention of the present invention has been completed.

That is, the first invention of the present invention and its aspects correspond to the descriptions of [1] to [21] below.

[1]

A release film for a process, comprising a release film of a release layer 1A and a heat resistant resin layer 1B, wherein the contact angle of the release layer 1A with respect to water is 90° to 130°; The tensile modulus of the laminated film at 120 ° C is from 75 MPa to 500 MPa.

[2]

The release film for a process according to the above aspect, wherein the thermal film dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 120 ° C is 3% or less.

[3]

The release film for a process according to the above aspect, wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and a longitudinal (MD) direction. The sum of the thermal dimensional change rates from 23 ° C to 120 ° C is 6% or less.

[4]

A release film for a process comprising a release film of a release layer 1A and a heat resistant resin layer 1B, wherein a contact angle of the release layer 1A with respect to water is 90° to 130°; The tensile modulus at °C is from 75 MPa to 500 MPa.

[5]

The release film for a process according to the above [4], wherein the thermal film dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 170 ° C is 4% or less.

[6]

The release film for a process according to the above [4], wherein the laminated film has a thermal dimension from 23 ° C to 170 ° C in the transverse (TD) direction. The rate of change and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction are 7% or less.

[7]

The release film for a process according to any one of the above aspects, wherein the heat-resistant resin layer 1B has a thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of 3 %the following.

[8]

The release film for a process according to the above [7], wherein the heat-resistant resin layer 1B has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 120 ° C is 6% or less.

[9]

The release film for a process according to any one of the above aspects, wherein the heat-resistant resin layer 1B has a thermal dimensional change rate from 3% to 170° C in the transverse (TD) direction of 3%. the following.

[10]

The release film for a process according to the above [9], wherein the heat-resistant resin layer 1B has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 170 ° C is 5% or less.

[11]

The release film for a process according to any one of the above aspects, wherein the release layer 1A comprises: a fluororesin, a 4-methyl-1-pentene (co)polymer, and Tree selected from the group consisting of polystyrene resins fat.

[12]

The process release film according to any one of the above aspects, wherein the heat resistant resin layer 1B comprises a stretched film.

[13]

The release film for a process according to [12], wherein the stretched film is selected from the group consisting of an extended polyester fiber film, a stretched polyamide film, and an extended polypropylene film.

[14]

The release film for a process according to any one of the above aspects, wherein the heat-resistant resin layer 1B is heated by the differential scanning calorimetry (DSC) based on JIS K7221. The heat of crystal melting in the project is 20 J/g or more and 100 J/g or less.

[15]

The release film for a process according to any one of the above aspects, wherein the laminated film further has a release layer 1A', and the release layer 1A, the heat resistant resin layer 1B, The order of the release layer 1A' is contained; the contact angle of the release layer 1A' with respect to water is 90 to 130.

[16]

The release film for a process according to [15], wherein at least one of the release layer 1A and the release layer 1A' comprises: a fluororesin, a 4-methyl-1-pentene (total) A resin selected from the group consisting of a polymer and a polystyrene resin.

[17]

The release film for a process according to any one of [1] to [16] is used for a packaging process by a thermosetting resin.

[18]

The release film for a process according to any one of [1] to [17] is used for a semiconductor packaging process.

[19]

The release film for process according to any one of [1] to [17] is used for a fiber reinforced plastic molding process or a plastic lens forming process.

[20]

A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming an inner surface of the molding die as in any one of [1] to [16] The release film for a semiconductor package process is disposed such that the release layer 1A faces the semiconductor device; after the mold is molded, the semiconductor device and the semiconductor package process are separated Between the types of films, the encapsulation resin is injected into the forming process.

[twenty one]

A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming a semiconductor according to [15] or [16] on the inner surface of the molding die a release film for packaging process to make the release layer 1A' and the aforementioned half A process in which the conductor device is disposed to face each other; and after the mold is molded, the package resin is injected into the molding process between the semiconductor device and the release film for the semiconductor package process.

Further, in the present case, the term "semiconductor device" also includes the concept of a semiconductor element (wafer).

Further, the second invention of the present invention and its aspects correspond to the descriptions of [22] to [46] below.

[twenty two]

A release film for a process comprising a release film 2A and a heat resistant resin layer 2B, wherein the release layer 2A has a contact angle with respect to water of 90° to 130°; and the heat resistant resin layer 2B contains The layer 2B1 of the polymer antistatic agent; the tensile modulus of the laminated film at 120 ° C is 75 MPa to 500 MPa.

[twenty three]

The release film for a process according to the above aspect, wherein the thermal film dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 120 ° C is 3% or less.

[twenty four]

The release film for a process according to the above [22], wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and a longitudinal (MD) direction. Heat from 23 ° C to 120 ° C The sum of dimensional change rates is below 6%.

[25]

A release film for a process comprising a release film 2A and a heat resistant resin layer 2B, wherein the release layer 2A has a contact angle with respect to water of 90° to 130°; and the heat resistant resin layer 2B contains The layer 2B1 of the polymer antistatic agent; and the tensile modulus of the laminated film at 170 ° C is 75 MPa to 500 MPa.

[26]

The release film for a process according to the above aspect, wherein the laminate film has a thermal dimensional change ratio of from 4 ° C to 170 ° C in the transverse (TD) direction of 4% or less.

[27]

The process release film according to the above [25], wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and a longitudinal (MD) direction. The sum of the thermal dimensional change rates from 23 ° C to 170 ° C is 7% or less.

[28]

The process release film according to any one of the aspects of the invention, wherein the heat resistant resin layer 2B comprises a layer 2B1 containing a polymer antistatic agent and an adhesive layer containing an adhesive. 2B2.

[29]

The release film for a process according to any one of [22] to [27], wherein The heat resistant resin layer 2B includes a polymer antistatic agent and an adhesive layer 2B3 containing a binder.

[30]

The release film for a process according to any one of the aspects of the present invention, wherein the heat-resistant resin layer 2B has a thermal dimensional change rate from 3% to 120° C in the transverse (TD) direction of 3%. the following.

[31]

The release film for a process according to [30], wherein the heat-resistant resin layer 2B has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 120 ° C is 6% or less.

[32]

The release film for a process according to any one of the above aspects, wherein the heat-resistant resin layer 2B has a thermal dimensional change rate of from 3% to 170° C in the transverse (TD) direction of 3%. the following.

[33]

The release film for a process according to [32], wherein the heat-resistant resin layer 2B has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 170 ° C is 5% or less.

[34]

The release film for a process according to any one of the above aspects, wherein the release layer 2A comprises: a fluororesin, a 4-methyl-1-pentene (co)polymer, and Tree selected from the group consisting of polystyrene resins fat.

[35]

The release film for a process according to any one of the above aspects, wherein the heat resistant resin layer 2B comprises a stretched film.

[36]

The release film for a process according to [35], wherein the stretched film is selected from the group consisting of an extended polyester fiber film, a stretched polyamide film, and an extended polypropylene film.

[37]

The release film for a process according to any one of the above-mentioned items, wherein the heat-resistant resin layer 2B has a first temperature increase measured by differential scanning calorimetry (DSC) based on JIS K7221 The heat of crystal melting in the project is 20 J/g or more and 100 J/g or less.

[38]

The process release film according to any one of the above aspects, wherein the release layer 2A has a surface specific resistance of 1 × 10 ¹³ Ω/□ or less.

[39]

The release film for a process according to any one of the above aspects, wherein the laminated film further has a release layer 2A', and the release layer 2A, the heat resistant resin layer 2B, The order of the aforementioned release layer 2A' is contained; the contact angle of the release layer 2A' with respect to water is from 90 to 130.

[40]

The release film for a process according to [39], wherein the release layer is At least one of 2A and the release layer 2A' includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co)polymer, and a polystyrene resin.

[41]

The release film for a process according to the above [39], wherein the release layer 2A' has a surface specific resistance of 1 × 10 ¹³ Ω/□ or less.

[42]

The release film for a process according to any one of [22] to [41] is used for a packaging process by a thermosetting resin.

[43]

The release film for a process according to any one of [22] to [42] is used for a semiconductor packaging process.

[44]

The release film for the process described in any one of [22] to [42] is used for a fiber reinforced plastic forming process or a plastic lens forming process.

[45]

A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming an inner surface of the molding die as in any one of [22] to [43] The release film for a semiconductor package process, wherein the release layer 2A is disposed to face the semiconductor device; after the mold is molded, the semiconductor device and the semiconductor package process are separated In between the film, the encapsulating resin is injected into the formed engineering.

[46]

A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming an inner surface of the molding die as in any one of [39] to [41] The release film for a semiconductor package process is disposed such that the release layer 2A' faces the semiconductor device; after the mold is molded, the semiconductor device and the semiconductor package process are used. Between the release films, the encapsulation resin is injected into the forming process.

Further, in the present case, the term "semiconductor device" also includes the concept of a semiconductor element (wafer).

In the release film for process of the first aspect of the present invention, since the high-grade release property, wrinkle suppression, and metal mold followability which were not achieved by the prior art are used, the release film can be used to form the semiconductor. A molded article obtained by a resin package such as a wafer can be more easily released, and a molded article having no appearance defects such as wrinkles or defects can be produced with high productivity.

In the release film for process of the second aspect of the present invention, since the high-level release property, the suppression of the appearance defect, and the followability of the mold which are not achieved by the prior art are obtained, the release film can be used to form the semiconductor. Wafer The molded article obtained by the resin encapsulation or the like can be easily released, and a molded article having no appearance defects such as wrinkles or defects, abnormal shapes (such as foreign matter adhesion), can be produced with high productivity. The release film for process of the second invention of the present invention is particularly preferably used in a packaging device using a pellet resin as a resin for encapsulation.

1, 1-2, 1-3‧‧‧ release film

2‧‧‧Upper metal mold

3‧‧‧ attracting mouth

4‧‧‧Packaging resin

4-2‧‧‧ semiconductor package

5‧‧‧Under metal mold

6‧‧‧Semiconductor wafer

7‧‧‧Substrate

8‧‧‧Forming metal mold

10, 20, 22‧‧‧ release film

12‧‧‧Heat Resin Layer 1B, 2B

14‧‧‧Adhesive layer

16, 16A‧‧‧ Release layer 1A, 2A

16B‧‧‧ Release layer 1A’, 2A’

24, 26‧‧‧ Roll

28‧‧‧Forming metal mold

30‧‧‧上模

32‧‧‧Down

34‧‧‧Semiconductor wafer

34A‧‧‧Substrate

36‧‧‧Encapsulated resin

40, 44‧‧‧ semiconductor package

Fig. 1 is a schematic view showing an example of a release film for a process of the present invention.

Fig. 2 is a schematic view showing another example of the release film for a process of the present invention.

FIG. 3 is a schematic view showing an example of a method of producing a resin-packaged semiconductor using the release film for a process of the present invention.

FIG. 4A is a schematic view showing an example of a method of producing a resin-packaged semiconductor using the release film for a process of the present invention.

4B is a schematic view showing an example of a method of producing a resin-encapsulated semiconductor using the release film for a process of the present invention.

FIG. 5 is a schematic view showing an example of a resin-encapsulated semiconductor obtained by using the method for producing a resin-packaged semiconductor of FIGS. 4A and 4B.

[Embodiment]

Process release film

The release film for process of the first invention of the present invention comprises the following four aspects.

(1-1st aspect)

A release film for a process comprising a release film of a release layer 1A and a heat resistant resin layer 1B, wherein a contact angle of the release layer 1A with respect to water is 90° to 130°; The tensile modulus at °C is from 75 MPa to 500 MPa.

(Section 1-2)

A release film for a process comprising a release film of a release layer 1A and a heat resistant resin layer 1B, wherein a contact angle of the release layer 1A with respect to water is 90° to 130°; The tensile modulus at °C is from 75 MPa to 500 MPa.

(Section 1-3)

A release film for a process comprising a laminated film laminated in the order of a release layer 1A, a heat resistant resin layer 1B, and a release layer 1A', wherein the release layer 1A and the release layer 1A' are opposed to each other The contact angle of water is from 90 to 130, and the tensile modulus of the laminated film at 120 ° C is from 75 MPa to 500 MPa.

(section 1-4)

A release film for a process comprising a laminated film laminated in the order of a release layer 1A, a heat resistant resin layer 1B, and a release layer 1A', wherein the release layer 1A and the release layer 1A' are opposed to each other Water contact angle The laminated elastic film has a tensile modulus at 75 ° C of 75 MPa to 500 MPa of from 90 ° to 130 °.

As is apparent from the above-described aspects, the release film for a process according to the first aspect of the invention (hereinafter referred to as a "release film") includes a release layer 1A having a release property to a molded article or a metal mold. And a laminated film of the release layer 1A' which is suitable for the film and the heat-resistant resin layer 1B which supports the release layer.

In the release film for process of the first aspect of the invention, when a resin such as a semiconductor element is encapsulated inside the molding die, it is placed on the inner surface of the molding die. In this case, it is preferable to arrange the release layer 1A of the release film (or the release layer 1A' when the release layer 1A' is present) on the resin-molded semiconductor element or the like (molded article). By disposing the release film of the first invention of the present invention, it is possible to easily separate the resin-packaged semiconductor element or the like from the metal mold.

The contact angle of the release layer 1A with respect to water is 90° to 130°, and since such a contact angle is obtained, the wettability of the release layer 1A is lowered, and it is not fixedly attached to the hardened encapsulating resin or the surface of the metal mold, and it is easy to The molded article is released.

The contact angle of the release layer 1A with respect to water is preferably from 95 to 120, more preferably from 98 to 115, still more preferably from 100 to 110.

As described above, since the release layer 1A (the release layer 1A' as the case may be) is disposed on the molded article side, generation of wrinkles of the release layer 1A (the release layer 1A' according to the case) in the resin sealing process can be suppressed. Better. Wrinkles produced in the release layer 1A (as the case of the release layer 1A') In this case, the wrinkles generated are transferred to the molded article, which increases the possibility that the appearance of the molded article is poor.

In the first invention of the present invention, in order to achieve the above object, a release film constituting a release film for a process is used, and a release layer 1A (and a release layer 1A' as needed) is used, and the release layer is supported. The heat-resistant resin layer 1B is laminated with a film, and the tensile modulus exhibits a laminated film of a specific value.

That is, a laminated film including the release layer 1A (and the release layer 1A' as needed) and the heat resistant resin layer 1B supporting the release layer has a tensile modulus at a temperature of 120 ° C of 75 MPa. 500 MPa, or its tensile modulus at 170 ° C is 75 MPa to 500 MPa. Further, the laminated film has a tensile modulus at 75 ° C of 75 MPa to 500 MPa, and a tensile modulus at 170 ° C of preferably 75 MPa to 500 MPa.

Since the tensile modulus of the laminated film at 120 ° C is 75 MPa to 500 MPa, or the tensile modulus at 170 ° C is 75 MPa to 500 MPa, the wrinkle of the release layer in the resin sealing process or the like can be effectively suppressed. The fold is generated. The tensile modulus at a specific temperature of the laminated film constituting the release film for a process exhibits the above specific value, and the mechanism for suppressing the occurrence of wrinkles of the release layer is not necessarily clearly explained, but it is presumed and processed. In the state of being heated, the tensile modulus of elasticity is equal to or greater than a certain value, and the deformation due to the occurrence of wrinkles is suppressed, and the deformation of the dispersion is made to have a tensile modulus of elasticity of a certain value or less. When it exceeds 500 MPa, the followability of the metal mold is deteriorated, and it is difficult to fill the sealing resin at the end portion, and there is a high possibility that appearance defects such as resin defects occur.

The laminated film of the release film for process of the first invention of the present invention has a tensile modulus at 120 ° C of preferably 80 MPa to 400 MPa, more preferably 85 MPa to 350 MPa, more preferably 88 MPa to 300 MPa, and 90 MPa to 280 MPa. good.

The laminated film of the release film for process of the first invention of the present invention preferably has a tensile modulus at 70 ° C of 80 MPa to 400 MPa, more preferably 85 MPa to 350 MPa, more preferably 88 MPa to 300 MPa, and more preferably 90 MPa to 280 MPa. 95MPa to 200MPa is more preferable, and 105MPa to 170MPa is particularly preferable.

The laminated film of the release film for process of the first invention of the present invention has a tensile modulus at 120 ° C and a tensile modulus at 170 ° C in the above preferred range because of its freedom of processing. It is more widely recommended for its wide range of uses and uses.

Further, the laminated film including the release layer 1A (and the release layer 1A' as needed) and the heat resistant resin layer 1B supporting the release layer has a TD direction (lateral direction) of from 23 ° C to 120 ° C. The thermal dimensional change rate is 3% or less, or the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is preferably 4% or less. Further, the laminated film has a TD direction (lateral direction) from 23 ° C to 120 ° C The thermal dimensional change rate is 3% or less, and the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is preferably 4% or less.

The thermal dimensional change rate from 23 ° C to 120 ° C in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C to 170 ° C in the TD direction (lateral direction). When the rate is 4% or less, wrinkles of the release layer in the resin sealing process or the like can be more effectively suppressed. In the embodiment, the laminated film constituting the release film for the process is not necessarily clearly described as being more effective by using the specific value of the thermal dimensional change rate in the transverse (TD) direction. The mechanism for suppressing the occurrence of wrinkles of the release layer, but presumably with the thermal expansion of the release layer 1A (or the release layer 1A') caused by heating/cooling during the process by using a laminated film having a small thermal expansion/contraction. / Shrinkage can be suppressed to be related.

In the laminated film of the release film for a process of the present embodiment, the thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (lateral direction) is preferably 2.5% or less, more preferably 2.0% or less, and 1.5%. The following is even better. On the other hand, in the laminated film, the thermal dimensional change rate from 23 ° C to 120 ° C in the TD direction (lateral direction) is preferably -5.0% or more.

In the laminated film of the release film for a process of the present embodiment, the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is preferably 3.5% or less, more preferably 3.0% or less, and 2.0%. The following is even better. On the other hand, in the laminated film, the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is preferably -5.0% or more.

Contains release layer 1A (and suitable release layer) 1A'), and a laminated film of the heat-resistant resin layer 1B which supports the release layer, which is the film size change film in the TD direction (lateral direction) and the MD direction in the film release film of the first invention of the present invention. The longitudinal direction of the longitudinal direction. The sum of the thermal dimensional change rates of the "longitudinal direction" is also preferably a specific value or less.

That is, the sum of the thermal dimensional change rates from 23 ° C to 120 ° C in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction are 6% or less is preferable. On the other hand, the laminated film has a thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (lateral direction) and 23 ° C to 120 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates is preferably -5.0% or more.

The rate of change in thermal dimensionality from 23 ° C to 120 ° C in the transverse (TD) direction of the laminated film including the release layer 1A (and the release layer 1A' as needed) and the heat-resistant resin layer 1B, and the longitudinal The sum of the thermal dimensional change rates from 23 ° C to 120 ° C in the (MD) direction is 6% or less, and wrinkles generated when mounted on the inner surface of the metal mold can be more effectively suppressed.

Further, the thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction of the laminated film including the release layer 1A (and the release layer 1A' as needed) and the heat-resistant resin layer 1B is The sum of the thermal dimensional change rates from 23 ° C to 170 ° C in the longitudinal (MD) direction is preferably 7% or less. On the other hand, the laminated film has a TD direction (lateral direction) of from 23 ° C to 170 ° C. The sum of the thermal dimensional change rate and the thermal dimensional change ratio from 23 ° C to 170 ° C in the longitudinal (MD) direction is preferably -5.0% or more.

The thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the laminated film is less than 7% from the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction. It is possible to more effectively suppress wrinkles generated when mounted on the inner surface of the metal mold.

Release layer 1A

The release layer 1A constituting the release film for process of the first invention of the present invention has a contact angle with respect to water of from 90 to 130, preferably from 95 to 120, more preferably from 98 to 115, and furthermore. Good for 100° to 110°. It is selected from the group consisting of fluororesin, 4-methyl-1-pentene (co)polymer, and polystyrene resin because of the excellent release property of the molded article and the ease of handling. The resin is preferred.

The fluororesin which can be used for the release layer 1A may also contain a resin composed of tetrafluoroethylene. It may also be a single polymer of tetrafluoroethylene, and a copolymer with other olefins may also be used. Examples of other olefins also include ethylene. A copolymer comprising tetrafluoroethylene and ethylene is preferable as a monomer constituent unit. In such a copolymer, a ratio of constituent units derived from tetrafluoroethylene is 55 to 100% by mass, which is derived from ethylene. The proportion of the constituent units is preferably from 0 to 45% by mass.

The 4-methyl-1-pentene (co) copolymer which can be used for the release layer 1A may be a single polymer of 4-methyl-1-pentene, and may also be 4-methyl-1-pentyl A copolymer of an alkene and an olefin having 2 to 20 carbon atoms (hereinafter referred to as "an olefin having 2 to 20 carbon atoms").

4-methyl-1-pentene, co-linked with olefins having 2 to 20 carbon atoms In the case of a polymer, an olefin having 2 to 20 carbon atoms copolymerized with 4-methyl-1-pentene can impart flexibility to 4-methyl-1-pentene. Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, and 1- Hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene, and the like. These olefins may be used alone or in combination of two or more.

In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, the ratio of constituent units derived from 4-methyl-1-pentene is 96 to 99% by mass. The ratio of the constituent units derived from the olefin having 2 to 20 carbon atoms other than the above is preferably 1 to 4% by mass. Since the content of the constituent unit derived from the olefin having 2 to 20 carbon atoms is small, the copolymer can be cured, that is, the storage elastic modulus E' can be increased, which is advantageous in suppressing wrinkles such as sealing work. On the other hand, since the content of the constituent unit derived from the olefin having 2 to 20 carbon atoms is large, the copolymer can be softened, that is, the storage elastic modulus E' can be lowered, which contributes to the improvement of the mold followability.

The 4-methyl-1-pentene (co)polymer can be usually produced by a known method by a person skilled in the art. For example, it is produced by a method using a conventional catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. The 4-methyl-1-pentene (co)polymer is preferably a (co)polymer having high crystallinity. The crystalline copolymer may be any of a copolymer having an isotactic structure or a copolymer having a syndiotactic structure, and in particular, from the viewpoint of physical properties, a copolymer having an isotactic structure is preferable, and it is preferable to start It is also easy. Further, the 4-methyl-1-pentene (co)polymer can be formed into a film shape, and if it has strength against temperature or pressure at the time of molding the metal mold, it is stereoregular or molecular weight. There are also no special restrictions. The 4-methyl-1-pentene copolymer may be, for example, a commercially available copolymer such as TPX (registered trademark) manufactured by Mitsui Chemicals, Inc.

The polystyrene resin which can be used for the release layer 1A contains a single polymer and a copolymer of styrene, and the structural unit derived from styrene contained in the polymer is at least 60% by weight or more, preferably 80. More preferably, the weight % or more.

The polystyrene-based resin may be isotactic polystyrene or syndiotactic polystyrene, but isotactic polystyrene is preferred from the viewpoints of transparency, ease of handling, and the like, and release property, heat resistance, and the like. From the point of view, syndiotactic polystyrene is preferred. The polystyrene may be used alone or in combination of two or more.

The release layer 1A preferably has heat resistance capable of withstanding the temperature of the mold at the time of molding (typically 120 to 180 ° C). From the related viewpoint, the release layer 1A preferably contains a crystalline resin having a crystalline component, and the crystalline resin preferably has a melting point of 190 ° C or higher, more preferably 200 ° C or higher and 300 ° C or lower.

Since the release layer 1A is crystalline, for example, the fluororesin preferably contains at least a constituent unit derived from tetrafluoroethylene, the 4-methyl-1-pentene (co)polymer preferably contains at least 4 The constituent unit derived from -methyl-1-pentene preferably contains at least syndiotactic polystyrene in the polystyrene resin. Since the crystal component is contained in the resin constituting the release layer 1A, wrinkles are less likely to occur in the resin sealing process or the like, and it is suitable to suppress the appearance defect caused by the wrinkle transfer molded article.

The resin containing the above-mentioned crystalline component constituting the release layer 1A has a crystal heat of fusion of 15 J/g or more and 60 J/ in the first temperature rising process measured by differential scanning calorimetry (DSC) based on JIS K7221. Preferably, g is more preferably 20 J/g or more and 50 J/g or less. When it is 15 J/g or more, it is found that the heat resistance and the release property of the hot stamping such as the resin sealing process can be more effectively obtained, and the dimensional change rate can be suppressed, so that the occurrence of wrinkles can be prevented. On the other hand, when the heat of crystal melting is 60 J/g or less, the release layer 1A has a suitable hardness, and sufficient followability to the mold of the film can be obtained in a resin sealing process or the like, and there is no risk of film breakage.

The release layer 1A may further contain another resin in addition to the fluororesin, the 4-methyl-1-pentene copolymer, and/or the polystyrene resin. At this time, the hardness of the other resin is preferably higher. Examples of other resins include polyamine-6, polyamine-66, polyethylene terephthalate, and polyethylene terephthalate. Therefore, when the release layer 1A contains a large amount of a soft resin (for example, when a 4-methyl-1-pentene copolymer contains a large amount of an olefin having 2 to 20 carbon atoms), it is also contained. The resin having a relatively high hardness can harden the release layer 1A, and is advantageous for suppressing wrinkles in a sealing process or the like.

The content of the other resin is preferably from 3 to 30% by mass based on the resin component constituting the release layer 1A. When the content of the other resin is 3% by mass or more, a substantial effect can be obtained by the addition, and the content is 30% by mass or less, and the release property to the mold or the molded article can be maintained.

Further, in addition to the fluororesin, the 4-methyl-1-pentene (co)polymer, and/or the polystyrene resin, the release layer 1A may be in the film without impairing the object of the first invention of the present invention. A conventionally known additive such as a heat stabilizer, a weathering stabilizer, a rust preventive agent, a copper-resistant stabilizer, or an antistatic agent is blended in the resin. The content of the additives may be, for example, 0.0001 to 10 parts by weight based on 100 parts by weight of the fluororesin, the 4-methyl-1-pentene copolymer, and/or the polystyrene resin.

The thickness of the release layer 1A is not particularly limited as long as it has sufficient release property with respect to the molded article, and is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer 1A can have a concavo-convex shape as necessary, whereby the release property can be improved. The method of providing the unevenness on the surface of the release layer 1A is not particularly limited, but a general method such as imprinting can be employed.

Release layer 1A'

The release film for process of the first invention of the present invention may further have a release layer 1A' in addition to the release layer 1A and the heat resistant resin layer 1B. In other words, the release film for process of the first invention of the present invention may be a laminated film comprising a release layer 1A, a heat resistant resin layer 1B, and a release layer 1A'.

The release film 1A' constituting the process release film of the first invention of the present invention may have a contact angle with respect to water of from 90 to 130, preferably from 95 to 120, more preferably from 98 to 115. More preferably, it is 100° to 110°. therefore, The excellent material, composition, physical properties and the like of the release layer 1A' are the same as those of the above-mentioned release layer 1A.

The release film for the process may be the same as the release layer 1A and the release layer 1A' when a laminated film including the release layer 1A, the heat resistant resin layer 1B, and the release layer 1A' is laminated. Layers can also be layers of different compositions.

The release layer 1A and the release layer 1A' are preferably the same or substantially the same from the viewpoint of prevention of bending, or ease of handling due to the same release property on any surface, and the like. From the viewpoint of optimally designing the relationship between the process of the release layer 1A and the release layer 1A', for example, from the release property of the release layer 1A from the metal mold, the release layer 1A is made. From the viewpoint of good peelability of the molded article, etc., it is preferable to make the release layer 1A and the release layer 1A' different.

When the release layer 1A and the release layer 1A' are different from each other, the release layer 1A and the release layer 1A' may be made of the same material, but the thickness and the like may be different, and the material and other components may be used. different.

Heat resistant resin layer 1B

The heat-resistant resin layer 1B constituting the release film for process of the first aspect of the present invention supports the release layer 1A (and, as the case may be, the release layer 1A'), and has a function of suppressing wrinkles caused by the mold temperature or the like.

In the release film for a process of the first aspect of the invention, the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 1B is 3% or less, or the transverse direction (TD) of the heat resistant resin layer 1B. Directions from 23 The thermal dimensional change rate from °C to 170 °C is preferably 3% or less. In the heat-resistant resin layer 1B, the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction is 3% or less and the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction. More preferably 3% or less.

The thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 1B is 3% or less, or the thermal size from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 1B. The rate of change is 3% or less, and wrinkles generated when mounted on the inner surface of the metal mold can be more effectively suppressed.

As the heat-resistant resin layer 1B, the above-described specific value indicating the rate of change in the thermal dimension in the transverse (TD) direction is not necessarily able to clearly explain the mechanism for suppressing the occurrence of wrinkles in the release layer, but it is presumed and With the heat-resistant resin layer 1B having a small thermal expansion/contraction, the thermal expansion/contraction of the release layer 1A (or the release layer 1A') caused by the heating/cooling during the process can be suppressed from being correlated.

Any resin layer containing an unstretched film may be used in the heat resistant resin layer 1B, but it is particularly preferable to contain an extended film.

The elongation film has a tendency to become low or become a negative number due to the influence of the elongation during the production process, because the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction is 3% or less. Further, since the thermal dimensional change rate of the heat-resistant resin layer 1B in the transverse (TD) direction from 23 ° C to 170 ° C is easily 3% or less, it can be suitably used as the heat-resistant resin layer 1B.

The thermal dimensional change ratio of the heat-resistant resin layer 1B in the transverse (TD) direction from 23 ° C to 120 ° C is preferably 2% or less, more preferably 1.5% or less, and 1%. More preferably, on the other hand, -10% or more is preferred.

The thermal dimensional change ratio of the heat-resistant resin layer 1B in the transverse (TD) direction from 23 ° C to 170 ° C is preferably 2% or less, more preferably 1.5% or less, still more preferably 1% or less, and on the other hand, -10%. The above is preferred.

In the release film for a process of the first aspect of the invention, the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 1B is from 23 ° C to 120 ° C in the longitudinal (MD) direction. The ratio of the thermal dimensional change rate is 6% or less, or the thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 1B, and from 23 ° C to 170 ° C in the longitudinal (MD) direction. The sum of the thermal dimensional change rates up to 5% is preferable. The thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 1B is less than 6% or less from the thermal dimensional change ratio from 23 ° C to 120 ° C in the longitudinal (MD) direction. Further, the thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 1B and the thermal dimensional change ratio from 23 ° C to 170 ° C in the longitudinal (MD) direction are More than 5% is better. Since the thermal dimensional change rate in the transverse (TD) direction of the heat resistant resin layer 1B and the thermal dimensional change rate in the longitudinal (MD) direction are within the above range, it is possible to more effectively suppress the mounting to the inner surface of the metal mold. Wrinkles are produced.

The thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of the heat-resistant resin layer 1B is -3.0% or more from the thermal dimensional change ratio from 23 ° C to 120 ° C in the longitudinal (MD) direction. It is preferably 5.0% or less, more preferably -2.0% or more and 4.5% or less.

The transverse (TD) direction of the heat resistant resin layer 1B is from 23 ° C to 120 ° C. The thermal dimensional change rate and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction are preferably -15.5% or more and 5.0% or less, more preferably -10.0% or more and 4.5% or less.

From the viewpoint of making the sum of the thermal dimensional change rate in the transverse (TD) direction of the heat resistant resin layer 1B and the thermal dimensional change rate in the longitudinal (MD) direction within the above range, it is advantageous to use the stretched film, and it is suitable for the use of the stretched film. It is more advantageous to control the extension conditions.

The above stretched film may be a one-axis stretch film or a biaxially stretch film. In the case of a one-axis stretch film, it may be a longitudinal extension or a lateral extension, but at least it is desirable to be able to extend in the transverse (TD) direction.

The method and apparatus for obtaining the above-mentioned stretched film are not particularly limited, and may be extended by a conventional method in the art. For example, it can be extended by a heating roller or a tenter type stretching machine.

As the above-mentioned stretched film, a stretched film selected from the group consisting of a stretched polyester fiber film, a stretched polyamide film, and an extended polypropylene film is preferably used. The stretched film is relatively easy to reduce the thermal expansion coefficient in the transverse (TD) direction or to be a negative number, and the mechanical properties are suitable for the use of the first invention of the present invention, and it is easier to start at a low cost as heat resistance. The stretched film in the resin layer 1B is particularly suitable.

The stretch film is preferably a stretched polyethylene terephthalate (PET) film or a stretched polybutylene terephthalate (PBT) film, and a biaxially oriented polyethylene terephthalate (PET) film is more preferable.

The polyamine which constitutes the extended polyamide film is not particularly limited, but polyamine-6, polyamine-66 or the like is preferably used.

As the stretched film, a one-axis stretched polypropylene film, a biaxially stretched polypropylene film, or the like can be preferably used.

The stretching ratio is not particularly limited. In order to appropriately control the rate of change in the thermal size, suitable mechanical properties can be achieved, and suitable values can be appropriately set. However, for example, when the polyester fiber film is stretched, the longitudinal direction and the transverse direction are together. The range of 2.7 to 8.0 times is preferable. When the polyimide film is extended, it is preferably in the range of 2.7 to 5.0 times in the longitudinal direction and the transverse direction, and when the polypropylene film is stretched, when the polypropylene film is biaxially stretched. It is preferably in the range of 5.0 to 10.0 times in the longitudinal direction and the transverse direction, and in the case of the one-axis stretching polypropylene film, it is preferably in the range of 1.5 to 10.0 times in the longitudinal direction.

The heat-resistant resin layer 1B has heat resistance which is resistant to the mold temperature at the time of molding (typically 120 to 180 ° C) from the viewpoint of controlling the strength of the film or controlling the rate of change in the thermal size to a suitable range. From the related viewpoint, the heat resistant resin layer 1B preferably contains a crystalline resin having a crystalline component, and the crystalline resin preferably has a melting point of 125 ° C or more, more preferably a melting point of 155 ° C or more and 300 ° C or less, and further preferably. It is 185 or more and 210 ° C or less, and particularly preferably 185 or more and 205 ° C or less.

As described above, the heat resistant resin layer 1B preferably contains a crystalline resin having a crystalline component. As the crystalline resin contained in the heat-resistant resin layer 1B, for example, a crystalline resin such as one or all of a polyester resin, a polyamide resin, or a polypropylene resin can be used. Specifically, polyterephthalic acid or polybutylene terephthalate is used in polyester fiber resin, in polyamine Polyamide 6 or polyamide 66 is used in the resin, and isotactic polypropylene is preferably used in the polypropylene resin.

When the heat resistant resin layer 1B contains the crystal component of the crystalline resin described above, wrinkles are less likely to occur in the resin sealing process or the like, and it is more advantageous to suppress the appearance defect caused by the wrinkle transfer molded article.

The resin constituting the heat-resistant resin layer 1B is preferably 20 J/g or more and 100 J/g or less in the first heat-rise project measured by differential scanning calorimetry (DSC) based on JIS K7221, 25 J. /g or more and 65 J/g or less is more preferable, 25 J/g or more and 55 J/g or less are more preferable, and 28 J/g or more and 50 J/g or less are more preferable, and 28 J/g or more and 40 J/g or less are more preferable. 28J/g or more and 35J/g or less are even better. When it is 20 J/g or more, the heat resistance and the release property of the hot stamping molding such as the resin sealing process can be more effectively found, and the dimensional change rate can be suppressed only, so that the occurrence of wrinkles can be prevented. On the other hand, when the heat of the crystal melting heat is 100 J/g or less, the heat-resistant resin layer 1B can be given a suitable hardness, and the resin can be sufficiently adhered to the mold of the film, such as a resin sealing process, and the film is not damaged. risk. Further, in the present embodiment, the heat of crystal melting is a heat amount indicating the obtained vertical axis in the first temperature rising process measured by differential scanning calorimetry (DSC) based on JIS K7221 (J). /g) A numerical value obtained from the sum of the peak areas having peaks at 120 ° C or higher in the graph of the relationship with the temperature of the horizontal axis (° C.).

The heat of crystal melting of the heat resistant resin layer 1B can be adjusted in accordance with heating, cooling conditions, or elongation conditions at the time of film production.

The thickness of the heat-resistant resin layer 1B is not particularly limited as long as the film strength can be ensured, but it is usually 1 to 100 μm, preferably 5 to 50 μm.

Layer other than this

The release film for process of the first aspect of the invention may have a layer other than the release layer 1A, the heat resistant resin layer 1B, and the release layer 1A' as long as it does not contradict the object of the first invention. For example, an adhesive layer may be provided between the release layer 1A (or the release layer 1A') and the heat resistant resin layer 1B as necessary. The material for the adhesive layer is not particularly limited as long as it can strongly bond the release layer 1A and the heat-resistant resin layer 1B, and does not peel off in the resin sealing process and the release process.

For example, when the release layer 1A (or the release layer 1A') comprises a 4-methyl-1-pentene copolymer, the adhesive layer is preferably a modified 4-methyl group modified by grafting with an unsaturated carboxylic acid or the like. A -1-pentene-based copolymer resin, an olefin-based adhesive resin formed of a 4-methyl-1-pentene-based copolymer and an α-olefin-based copolymer. When the release layer 1A (or the release layer 1A') contains a fluororesin, the adhesive layer is preferably an adhesive such as a polyester-based, acrylic-based or fluororubber-based adhesive. The thickness of the adhesive layer is not particularly limited as long as it improves the adhesion between the release layer 1A (or the release layer 1A') and the heat resistant resin layer 1B, but is, for example, 0.5 to 10 μm.

The total thickness of the release film for a process according to the first aspect of the invention is not particularly limited, but is, for example, preferably 10 to 300 μm, more preferably 30 to 150 μm. If the total thickness of the release film is within the above range, It is preferable that the handleability when using the roll is good and the amount of waste of the film is small.

Hereinafter, a preferred embodiment of the release film for a process according to the first invention of the present invention will be described more specifically. FIG. 1 is a schematic view showing an example of a release film for a three-layer structure. As shown in FIG. 1, the release film 10 has a heat resistant resin layer 12 and a release layer 16 formed on one surface thereof via an adhesive layer 14.

The release layer 16 is the aforementioned release layer 1A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer 1B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the encapsulating resin in the packaging process; and the heat resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the metal mold in the packaging process.

2 is a schematic view showing an example of a release film for a process having a five-layer structure. Components having the same functions as those of Fig. 1 will be given the same reference numerals. As shown in FIG. 2, the release film 20 has a heat resistant resin layer 12, and a release layer 16A and a release layer 16B which are formed on the both surfaces thereof via the adhesive layer 14. The release layer 16A is the above-mentioned release layer 1A, the heat resistant resin layer 12 is the above-mentioned heat resistant resin layer 1B, the release layer 16B is the above-mentioned release layer 1A', and the adhesive layer 14 is the aforementioned adhesive layer.

The composition of the release layers 16A and 16B may be the same or different from each other. The thickness of the release layers 16A and 16B may also be the same or different from each other. However, if the release layers 16A and 16B have the same composition and thickness, they will have a symmetrical structure, and it is preferable that the release film is hard to be bent by itself. In particular, the release film of the first invention of the present invention is packaged. In the process, stress is generated by heating, and therefore it is preferable to suppress bending. Therefore, after the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12, it is preferable that either of the molded article and the inner surface of the mold can obtain good release property.

Method for manufacturing release film for process

The release film for process of the first invention of the present invention can be produced by any method. For example, (1) a method of manufacturing a release film for a process by laminating a release layer 1A and a heat resistant resin layer 1B by co-extrusion molding (co-extrusion formation method), and (2) becoming a heat resistant resin On the film of the layer 1B, a molten resin which is a resin of the release layer 1A or the adhesive layer is applied/dried, or a resin solution in which the resin which becomes the release layer 1A or the adhesive layer is dissolved in a solvent is applied/dried, A method of producing a release film for a process (coating method), (3) a film which is a release layer 1A, a film which is a heat resistant resin layer 1B, and a film (layer) of the film are laminated A method of using a release film for a process (layering) or the like.

In the method of (3), as a method of laminating the respective resin films, various conventional lamination methods such as extrusion lamination, dry lamination, thermal lamination, and the like can be employed.

The dry layer method uses an adhesive to laminate each resin film. As the adhesive, a conventional adhesive which is an adhesive for dry lamination can be used. For example, a polyvinyl acetate-based adhesive; a separate polymer or copolymer of acrylate (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or an acrylate and other monomers can be used. Acrylic acid Polyacrylate adhesive formed by copolymer of ester, acrylonitrile, styrene, etc.; cyanoacrylate adhesive; ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid) An ethylene copolymer-based adhesive formed by a copolymer such as methacrylic acid or the like; a cellulose-based adhesive; a polyester-based adhesive; a polyamide-based adhesive; and a polyimide-based adhesive An ammonia resin-based adhesive formed by a urea resin or a melamine resin; a phenol resin-based adhesive; an epoxy-based adhesive; a polyol (polyether polyol, polyester polyol, etc.) and isocyanate and/or Or a polyurethane-based adhesive cross-linked with isocyanurate; a reactive (meth)acrylic adhesive; a rubber system formed of neoprene, nitrile rubber, styrene-butadiene rubber, or the like Adhesive; inorganic binder composed of organic lanthanum binder; alkali metal citrate, low melting point glass; other adhesives. The resin film laminated by the method of (3) can be used commercially, or can be manufactured by a conventional manufacturing method. The resin film may also be subjected to surface treatment such as corona treatment, atmospheric piezoelectric slurry treatment, vacuum plasma treatment, and primer coating treatment. The method for producing the resin film is not particularly limited, and a known production method can be used.

(1) The co-extrusion molding method is less likely to cause defects such as a foreign matter jam or the like, or a bending of the release film between the resin layer which is the release layer 1A and the resin layer which becomes the heat-resistant resin layer 1B. (3) The layering method is a manufacturing method suitable for the use of the stretched film in the heat resistant resin layer 1B. At this time, it is preferable to form a suitable adhesive layer at the interface between the films as necessary. After the adhesion between the films is improved, the interface between the films may be subjected to a surface treatment such as corona discharge treatment.

The release film for the process can be extended in one or two axes as necessary, thereby increasing the film strength of the film.

The coating means in the coating method of the above (2) is not particularly limited, and for example, various coating machines such as a roll coater, a die coater, and a spray coater can be used. The means for melting and extruding is not particularly limited, and for example, an extruder having a T-shaped mold or an expanded mold can be used.

Manufacturing process

In the release film for a process according to the first aspect of the invention, a semiconductor wafer or the like can be placed in a mold, and when a resin is injection-molded, it can be disposed between a semiconductor wafer or the like and the inner surface of the mold. According to the release film for a process of the first aspect of the invention, it is possible to effectively prevent the release of the mold from the mold, the occurrence of burrs, and the like.

The resin used in the above production process may be any of a thermoplastic resin and a thermosetting resin, but thermosetting resins have been widely used in the technical field, and particularly, an epoxy-based thermosetting resin is preferable.

As the above-mentioned manufacturing process, the packaging of the semiconductor wafer is the most representative, but it is not limited thereto, and the first invention of the present invention can also be applied to a fiber reinforced plastic molding process, a plastic lens forming process, and the like.

3, FIG. 4A and FIG. 4B are schematic diagrams showing an example of a method of producing a resin-packaged semiconductor using the release film of the first invention of the present invention.

As shown in Fig. 3a, the release film 1 of the first invention of the present invention is taken from a roll shape. The roll is supplied into the forming mold 2 by the rolls 1-2 and the rolls 1-3. Next, the release film 1 is placed on the inner surface of the upper mold 2. If necessary, the inner surface of the upper mold 2 may be evacuated to closely adhere the release film 1 to the inner surface of the upper mold 2. In the lower mold 5 of the molding apparatus, a semiconductor wafer 6 disposed on a substrate is disposed, and a sealing resin is dispensed on the semiconductor wafer 6, or a liquid encapsulating resin is injected to cover the semiconductor wafer 6, and the arrangement is arranged. The encapsulating resin 4 is housed between the upper metal mold 2 and the lower metal mold 5 of the release film 1 which is attracted and adhered to the air. Next, as shown in FIG. 3b, the upper mold 2 and the lower mold 5 are sandwiched between the release film 1 of the first invention of the present invention to close the mold, and the sealing resin 4 is cured.

By the mold hardening, as shown in FIG. 3c, the encapsulating resin 4 is fluidized in the metal mold, and the encapsulating resin 4 flows into the space portion and is filled in such a manner as to surround the side surface of the semiconductor wafer 6, and then the upper metal mold 2 and the lower side are made. The metal mold 5 is opened, and the packaged semiconductor wafer 6 is taken out. After the mold is opened and the molded article is taken out, the release film 1 is repeatedly used in plural times, and a new release film is supplied, followed by molding with a resin.

The release film of the first invention of the present invention is closely adhered to the upper metal mold and interposed between the metal mold and the encapsulating resin to prevent adhesion of the resin to the mold due to resin molding, and does not contaminate the resin of the mold. The molding surface is molded and the molded article is easily released.

Further, a new release film may be supplied for resin molding every time the resin molding operation is performed, or a new release film may be supplied for resin molding at a plurality of resin molding operations.

The encapsulating resin may be a liquid resin, and may be a resin which is solid at normal temperature. However, a sealing material which becomes liquid or the like at the time of resin encapsulation can be suitably used. As the encapsulating resin material, specifically, an epoxy type (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolac type epoxy resin, etc.) can be mainly used as an encapsulating resin other than epoxy resin. A polyimide-based resin (a bismaleimide-based resin) or a siloxane-based resin (a thermosetting-added type) can be used as a sealing resin, and is often used by a user. Further, the resin encapsulating conditions differ depending on the encapsulating resin to be used, but may be, for example, a curing temperature of 120 to 180 ° C, a molding pressure of 10 to 50 kg/cm ² , and a curing time of 1 to 60 minutes. Make the appropriate settings.

The process of disposing the release film 1 on the inner surface of the molding die 8 and the order of the process of disposing the semiconductor wafer 6 in the molding die 8 are not particularly limited, and may be performed simultaneously. After the semiconductor wafer 6 is placed, The release film 1 may be disposed, and the semiconductor wafer 6 may be disposed after the release film 1 is disposed.

Therefore, since the release film 1 has the release layer 1A having high release property (and the release layer 1A' which is required), the semiconductor package 4-2 is easily released. Further, the release film 1 has good flexibility, has good followability to the shape of the metal mold, and is not easily wrinkled by the heat of the molding die 8. Therefore, the wrinkles are not transferred to the resin package surface of the packaged semiconductor package 4-2, and no resin-filled portion (resin defect) is formed, and a packaged semiconductor package having a good appearance can be obtained 4- 2.

In addition, it is not limited to the solid package as shown in FIG. In the compression molding method in which the resin material 4 is pressurized and heated, a transfer molding method of encapsulating a resin material in a flow state to be described later may be employed.

4A and 4B are schematic views showing an example of a method of producing a resin-packaged semiconductor using the release film of the first invention of the present invention, that is, a transfer molding method.

As shown in FIG. 4A, the release film 22 of the first invention of the present invention is supplied from a roll-shaped roll to the forming mold 28 by a roll 24 and a roll 26 (Engineering a). Next, the release film 22 is placed on the inner surface 30A of the upper mold 30 (engineering b). If necessary, the upper mold inner surface 30A may be evacuated to closely adhere the release film 22 to the upper mold inner surface 30A. Next, in the molding die 28, a semiconductor wafer 34 (a semiconductor wafer 34 fixed to the substrate 34A) to be encapsulated is placed, and a sealing resin material 36 (engineering c) is placed, and the mold is closed (engineering d).

Next, as shown in FIG. 4B, the encapsulating resin material 36 is post-injected into the forming mold 28 under a predetermined heating and pressing condition (Engineering e). The temperature (forming temperature) of the molding die 28 at this time is, for example, 165 to 185 ° C, the molding pressure is, for example, 7 to 12 MPa, and the molding time is, for example, about 90 seconds. Next, after holding for a certain period of time, the upper mold 30 and the lower mold 32 are opened, and the resin-encapsulated semiconductor package 40 and the release film 22 are simultaneously or sequentially released (engineering f).

Next, as shown in FIG. 5, in the obtained semiconductor package 40, the desired semiconductor package 44 can be obtained by removing the remaining resin portion 42. The release film 22 can be used as it is in the resin package of other semiconductor wafers, but the roller is operated at the end of each molding. It is preferable to feed the film and supply the new release film 22 to the forming metal mold 28.

The process of disposing the release film 22 on the inner surface of the molding die 28 and the order of the process of disposing the semiconductor wafer 34 in the molding die 28 are not particularly limited, and may be performed simultaneously. After the semiconductor wafer 34 is placed, The release film 22 may be disposed, and the semiconductor wafer 34 may be disposed after the release film 22 is disposed.

Therefore, since the release film 22 has the release layer 1A having high release property (and the release layer 1A' which is required), the semiconductor package 40 is easily released. Further, since the release film 22 has moderate flexibility, it has a good followability to the shape of the metal mold, and is not easily wrinkled by the heat of the molding die 28. Therefore, the wrinkles are not transferred to the resin package surface of the semiconductor package 40, and a portion (resin defect) in which the resin is not filled is not formed, and the semiconductor package 40 having a good appearance can be obtained.

The release film of the first invention of the present invention is not limited to a process of encapsulating a semiconductor element resin, and is a process of molding and releasing various molded articles by using a molding die, for example, fiber reinforced plastic molding and release molding, plastic lens molding, and It is also preferable to use it in a release type project or the like.

Process release film

The release film for process of the second invention of the present invention comprises the following four aspects.

(2-1st aspect)

A release film for a process, comprising a laminated film comprising a release layer 2A and a heat resistant resin layer 2B, wherein The contact angle of the release layer 2A with respect to water is 90° to 130°; the heat resistant resin layer 2B comprises a layer 2B1 containing a polymer-based antistatic agent; and the tensile modulus of the laminate film at 120° C. is 75 MPa. To 500MPa.

(2-2 aspect)

A release film for a process comprising a release film 2A and a heat resistant resin layer 2B, wherein the release layer 2A has a contact angle with respect to water of 90° to 130°; and the heat resistant resin layer 2B contains The layer 2B1 of the polymer antistatic agent; and the tensile modulus of the laminated film at 170 ° C is 75 MPa to 500 MPa.

(2-3th aspect)

A release film for a process comprising a laminated film laminated in the order of a release layer 2A, a heat resistant resin layer 2B, and a release layer 2A', wherein the release layer 2A and the release layer 2A' are opposite to each other The contact angle of water is 90° to 130°: the heat-resistant resin layer 2B contains the layer 2B1 containing a polymer-based antistatic agent; and the tensile modulus of the laminated film at 120 ° C is 75 MPa to 500 MPa.

(section 2-4)

A release film for process, comprising a release layer 2A, a heat resistant tree a laminated film in which the grease layer 2B and the release layer 2A' are sequentially laminated, wherein the contact angle of the release layer 2A and the release layer 2A' with respect to water is 90 to 130; the heat resistant resin layer 2B The layer 2B1 containing a polymer-based antistatic agent is contained; and the tensile modulus at 170 ° C of the laminated film is 75 MPa to 500 MPa.

As is apparent from the above-described aspects, the release film for a process according to the second aspect of the present invention (hereinafter, referred to simply as "release film") includes a release layer 2A having a release property to a molded article or a metal mold. And a laminated film of the release layer 2A' which is required and a heat-resistant resin layer 2B which supports the release layer, and the heat-resistant resin layer 2B contains the layer 2B1 containing a polymeric antistatic agent.

In the release film for process of the second aspect of the invention, when a resin such as a semiconductor element is encapsulated inside the molding die, it is placed on the inner surface of the molding die. In this case, it is preferable to arrange the release layer 2A of the release film (or the release layer 2A' when the release layer 2A' is present) on the resin-molded semiconductor element or the like (molded article). By disposing the release film of the second invention of the present invention, it is possible to easily separate the resin-packaged semiconductor element or the like from the metal mold.

The contact angle of the release layer 2A with respect to water is 90° to 130°, and since such a contact angle is obtained, the wettability of the release layer 2A is lowered, and it is not fixedly attached to the hardened encapsulating resin or the surface of the metal mold, and it is easy to The molded article is released.

The contact angle of the release layer 2A with respect to water is preferably from 95 to 120, more preferably from 98 to 115, still more preferably from 100 to 110.

As described above, since the release layer 2A (the release layer 2A' as the case may be) is disposed on the molded article side, from the viewpoint of the appearance of the molded article, the release layer 2A in the resin sealing process can be suppressed (depending on the situation) The generation of wrinkles of the type layer 2A') is preferred. When the wrinkles are generated in the release layer 2A (the release layer 2A' as the case may be), the wrinkles generated are transferred to the molded article, which increases the possibility of occurrence of poor appearance of the molded article.

In the second aspect of the present invention, in order to achieve the above object, a release film constituting a release film for a process is used, and a release layer 2A (and a release layer 2A' as needed) is used, and the release layer is supported. The heat-resistant resin layer 2B is a laminated film, and the tensile modulus represents a laminated film having a specific value, and the heat-resistant resin layer 2B contains the layer 2B1 containing a polymer-based antistatic agent. That is, a laminated film comprising the release layer 2A (and the release layer 2A' as needed) and the heat resistant resin layer 2B supporting the release layer has a tensile modulus at a temperature of 120 ° C of 75 MPa. 500 MPa, or its tensile modulus at 170 ° C is 75 MPa to 500 MPa.

The laminated film which exhibits the above specific value by combining the tensile modulus and the heat resistant resin layer containing the polymer-based antistatic agent are not necessarily clearly described as being able to effectively suppress the occurrence of appearance defects of the molded article. However, it is presumed that the tensile modulus of the laminated film is such that wrinkles are suppressed by the above-mentioned specific values, and the static electricity suppressed by the layer containing the polymer-based antistatic agent is suppressed. The multiplication effect of the absorption of foreign matter such as powder. That is to say, foreign matter such as powder can cause wrinkles. By suppressing the absorption of foreign matter, it is possible to suppress the occurrence of wrinkles more effectively, and it is possible to suppress the agglomeration of foreign matter more effectively by suppressing the occurrence of wrinkles from the point where wrinkles become agglomerates of foreign matter. There is a certain relationship between the growth and the suppression of the appearance defects of high-grade molded articles that have not been predicted in the prior art.

Further, the surface specific resistance value in the release layer 2A (and the release layer 2A' which is required for the film) of the laminated film is preferably 1 × 10 ¹³ from the viewpoint of preventing adhesion of dust or the like in semiconductor manufacturing engineering. Ω/□ or less, more preferably 5 × 10 ¹² Ω / □ or less, still more preferably 1 × 10 ¹² Ω / □ or less, and even more preferably 5 × 10 ¹¹ Ω / □ or less.

The surface specific resistance value in the release layer 2A (and the release layer 2A' which is required) of the laminated film can be measured, for example, by the method described in the examples of the present invention.

As described above, the laminated film including the release layer 2A (and the release layer 2A' as needed) and the heat resistant resin layer 2B supporting the release layer has a tensile modulus at a temperature of 120 ° C of 75 MPa to 500 MPa. Or, its tensile modulus at 170 ° C is 75 MPa to 500 MPa. Further, the laminated film has a tensile modulus at 75 ° C of 75 MPa to 500 MPa, and a tensile modulus at 170 ° C of preferably 75 MPa to 500 MPa.

Since the tensile modulus of the laminated film at 120 ° C is 75 MPa to 500 MPa, or the tensile modulus at 170 ° C is 75 MPa to 500 MPa, the wrinkle of the release layer in the resin sealing process or the like can be effectively suppressed. The fold is generated. The specific temperature of the laminated film constituting the release film for the process The tensile modulus of elasticity exhibits the above-described specific value, and although the mechanism for suppressing the occurrence of wrinkles of the release layer is not necessarily clearly explained, it is presumed that the film has a certain value or more in a heated state during the process. The modulus of elasticity, while suppressing the deformation caused by the generation of wrinkles, is related to the dispersion deformation due to the tensile modulus of elasticity below a certain value. When it exceeds 500 MPa, the followability of the metal mold is deteriorated, and it is difficult to fill the sealing resin at the end portion, and there is a high possibility that appearance defects such as resin defects occur.

The laminated film of the release film for process of the second invention of the present invention has a tensile modulus at 120 ° C of preferably 80 MPa to 400 MPa, more preferably 85 MPa to 350 MPa, more preferably 88 MPa to 300 MPa, and 90 MPa to 280 MPa. good.

The laminated film of the release film for process of the second invention of the present invention preferably has a tensile modulus at 70 ° C of 80 MPa to 400 MPa, more preferably 85 MPa to 350 MPa, more preferably 88 MPa to 300 MPa, and more preferably 90 MPa to 280 MPa. 95MPa to 200MPa is more preferable, and 105MPa to 170MPa is particularly preferable.

The laminated film of the release film for process of the second invention of the present invention has a tensile modulus at 120 ° C and a tensile modulus at 170 ° C in the above preferred range because of the freedom of processing. Wide range of uses and uses Especially recommended.

Further, the laminated film including the release layer 2A (and the release layer 2A' as needed) and the heat resistant resin layer 2B supporting the release layer has a TD direction (lateral direction) of from 23 ° C to 120 ° C. The thermal dimensional change rate is 3% or less, or the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is 4% or less. Further, in the laminated film, the thermal dimensional change rate from 23 ° C to 120 ° C in the TD direction (lateral direction) is 3% or less, and the thermal dimensional change from 23 ° C to 170 ° C in the TD direction (lateral direction) is obtained. The rate is preferably 4% or less.

The thermal dimensional change rate from 23 ° C to 120 ° C in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C to 170 ° C in the TD direction (lateral direction). When the rate is 4% or less, it is preferable to more effectively suppress wrinkles of the release layer in the resin sealing process or the like. In the embodiment, the laminated film constituting the release film for the process is not necessarily clearly described as being more effective by using the specific value of the thermal dimensional change rate in the transverse (TD) direction. The mechanism for suppressing the occurrence of wrinkles of the release layer, but presumably with the thermal expansion of the release layer 2A (or the release layer 2A') caused by heating/cooling during the process by using a laminated film having a small thermal expansion/contraction. / Shrinkage can be suppressed to be related.

In the laminated film of the release film for a process of the present embodiment, the thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (lateral direction) is preferably 2.5% or less, more preferably 2.0% or less, and 1.5%. The following is even better. On the other hand, the laminated film has a TD direction (lateral direction) The thermal dimensional change rate from 23 ° C to 120 ° C is preferably -5.0% or more.

In the laminated film of the release film for a process of the present embodiment, the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is preferably 3.5% or less, more preferably 3.0% or less, and 2.0%. The following is even better. On the other hand, in the laminated film, the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (lateral direction) is preferably -5.0% or more.

The laminated film comprising the release layer 2A (and the release layer 2A' as needed) and the heat-resistant resin layer 2B supporting the release layer, which is the release film of the process of the second invention of the present invention, has a TD direction (transverse direction) The sum of the thermal dimensional change rate in the direction and the MD direction (longitudinal direction in film production, hereinafter also referred to as "longitudinal (MD) direction) is preferably a specific value or less.

That is, the sum of the thermal dimensional change rates from 23 ° C to 120 ° C in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction are 6% or less is preferable. On the other hand, the laminate film has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 ° C to 120 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates is preferably -5.0% or more.

The rate of change in thermal dimensionality from 23 ° C to 120 ° C in the transverse (TD) direction of the laminated film including the release layer 2A (and the release layer 2A' as needed) and the heat-resistant resin layer 2B, and the longitudinal The sum of the thermal dimensional change rates from 23 ° C to 120 ° C in the (MD) direction is 6% or less, and wrinkles generated when mounted on the inner surface of the metal mold can be more effectively suppressed.

In addition, the release layer 2A is included (and the release layer is suitable for it) 2A') and the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the laminated film of the heat resistant resin layer 2B, and the thermal size from 23 ° C to 170 ° C in the longitudinal (MD) direction The sum of the rate of change is preferably 7% or less. On the other hand, the laminated film has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 ° C in the longitudinal (MD) direction. The sum of the thermal dimensional change rates up to 170 ° C is preferably -5.0% or more.

The thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the laminated film is less than 7% from the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction. It is possible to more effectively suppress wrinkles generated when mounted on the inner surface of the metal mold.

Release layer 2A

The release layer 2A constituting the release film for process of the second invention of the present invention has a contact angle with respect to water of 90 to 130, preferably 95 to 120, more preferably 98 to 115, and still more Good for 100° to 110°. The resin selected from the group consisting of fluororesin, 4-methyl-1-pentene (co)polymer, and polystyrene resin, because of its excellent release property and ease of handling. Preferably.

The fluororesin which can be used for the release layer 2A is the same as that described for the release layer 1A.

Further, the 4-methyl-1-pentene (co)polymer which can be used for the release layer 2A is the same as that described for the release layer 1A.

In addition, the polystyrene resin which can be used for the release layer 2A is related to The same as that described for the release layer 1A.

The release layer 2A preferably has heat resistance capable of withstanding the temperature of the mold at the time of molding (typically 120 to 180 ° C). From the related viewpoint, the release layer 2A is preferably a crystalline resin containing a crystalline component, and the crystalline resin preferably has a melting point of 190 ° C or higher, more preferably 200 ° C or higher and 300 ° C or lower.

Since the release layer 2A has crystallinity, for example, the fluororesin preferably contains at least a constituent unit derived from tetrafluoroethylene, the 4-methyl-1-pentene (co)polymer preferably contains at least The constituent unit derived from 4-methyl-1-pentene preferably contains at least a syndiotactic polystyrene in the polystyrene resin. Since the crystal component is contained in the resin constituting the release layer 2A, wrinkles are less likely to occur in the resin sealing process or the like, and it is suitable to suppress the appearance defect caused by the wrinkle transfer molded article.

The resin layer containing the above-described crystalline component constituting the release layer 2A has a crystal heat of fusion of 15 J/g or more and 60 J in the first temperature rising process measured by differential scanning calorimetry (DSC) based on JIS K7221. It is preferably /g or less, more preferably 20 J/g or more and 50 J/g or less. When it is 15 J/g or more, it is found that the heat resistance and the release property of the hot stamping such as the resin sealing process can be more effectively obtained, and the dimensional change rate can be suppressed, so that the occurrence of wrinkles can be prevented. On the other hand, when the heat of crystal melting is 60 J/g or less, the release layer 2A has a suitable hardness, and sufficient followability to the mold of the film can be obtained in a resin sealing process or the like, and there is no risk of film breakage.

Release layer 2A except fluororesin, 4-methyl-1-pentene (total) In addition to the polymer and/or polystyrene resin, other resins may be further included. The resin and its content in other cases are the same as those described for the release layer 1A.

Further, in addition to the fluororesin, the 4-methyl-1-pentene (co)polymer, and/or the polystyrene resin, the release layer 2A may be in the film without impairing the object of the second invention of the present invention. A conventionally known additive such as a heat stabilizer, a weathering stabilizer, a rust preventive agent, a copper-resistant stabilizer, or an antistatic agent is blended in the resin. The content of the additives may be, for example, 0.0001 to 10 parts by weight based on 100 parts by weight of the fluororesin, the 4-methyl-1-pentene copolymer, and/or the polystyrene resin.

The thickness of the release layer 2A is not particularly limited as long as it has sufficient release property from the molded article, and is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer 2A may have a concavo-convex shape as necessary, whereby the release property can be improved. The method of providing the unevenness on the surface of the release layer 2A is not particularly limited, but a general method such as imprinting can be employed.

Release layer 2A'

The release film for process of the second invention of the present invention may further have a release layer 2A' in addition to the release layer 2A and the heat resistant resin layer 2B. In other words, the release film for process of the second invention of the present invention may be a laminated film comprising a release layer 2A, a heat resistant resin layer 2B, and a release layer 2A'.

The release film 2A' constituting the process release film of the second invention of the present invention may have a contact angle with respect to water of from 90 to 130, preferably from 95 to 120, more preferably from 98 to 115. More preferably, it is 100° to 110°. Therefore, the preferred material, constitution, physical properties and the like of the release layer 2A' are the same as those of the above-mentioned release layer 2A.

The release film for the process may be the same as the release layer 2A and the release layer 2A' when a laminated film including the release layer 2A, the heat resistant resin layer 2B, and the release layer 2A' is laminated. Layers can also be layers of different compositions.

From the viewpoint of prevention of bending, ease of handling due to the same release property on any surface, and the like, the release layer 2A and the release layer 2A' are preferably the same or substantially the same, and are preferably From the viewpoint of optimally designing the relationship between the process of the release layer 2A and the release layer 2A', for example, from the release property of the release layer 2A from the metal mold, the release layer 2A is made. The configuration in which the release layer 2A and the release layer 2A' are different from each other is preferable from the viewpoint of good peelability of the molded article.

When the release layer 2A and the release layer 2A' are different from each other, the release layer 2A and the release layer 2A' may be made of the same material, but the thickness or the like may be different, and the material and other components may be used. different.

Heat resistant resin layer 2B

The heat-resistant resin layer 2B constituting the release film for process of the second aspect of the present invention supports the release layer 2A (and, as the case may be, the release layer 2A'), and has a function of suppressing wrinkles caused by the mold temperature or the like.

The heat-resistant resin layer 2B constituting the release film for process of the second invention of the present invention includes the layer 2B1 containing a polymer-based antistatic agent. Here, the term "including" in the layer 2B1 containing the polymer-based antistatic agent means that the entire heat-resistant resin layer 2B is composed of the layer 2B1 containing the polymer-based antistatic agent, The meaning of both of the heat resistant resin layer 2B is composed of the layer 2B1 containing a polymer antistatic agent. Therefore, the heat resistant resin layer 2B may contain a layer other than the layer 2B1 containing the polymer antistatic agent, and may not be included.

The heat-resistant resin layer 2B constituting the release film for a process of the second aspect of the present invention contains a layer 2B1 containing a polymer-based antistatic agent, and has a low surface specific resistance value, which contributes to prevention of charging.

The surface specific resistance of the heat-resistant resin layer 2B is preferably 10 ¹⁰ Ω/□ or less and 10 ⁹ Ω/□ or less from the viewpoint of preventing adhesion to dust or the like of the release layer 2A of the laminated film of the second invention of the present invention. Very good. When the surface specific resistance value is 10 ¹⁰ Ω/□ or less, the antistatic property can be effectively found on the surface of the release film for process of the present invention. Therefore, it is possible to effectively control the adhesion of foreign matter such as dust due to static electricity, for example, in the manufacture of a semiconductor package, even when a part of the semiconductor element is directly in contact with the release film for process, it can be effectively suppressed. The destruction of the semiconductor element caused by the charging-releasing of the release film of the process.

The surface specific resistance value of the heat-resistant resin layer 2B is preferably as low as possible from the viewpoint of preventing adhesion to dust or the like of the release layer 2A of the laminated film of the second invention of the present invention, and the lower limit is not particularly limited. The surface resistance value of the heat resistant resin layer 2B is higher when the conductive property of the polymer antistatic agent is higher, or a higher score The larger the content of the sub-system antistatic agent, the smaller the tendency is.

The surface specific resistance value of the heat resistant resin layer 2B can be measured, for example, by the method described in the examples of the present invention. However, the heat resistant resin layer 2B before lamination was used as a sample.

As the layer other than the layer 2B1 containing the polymer antistatic agent, for example, an adhesive layer 2B2 containing an adhesive is preferably used. In other words, the heat resistant resin layer 2B may include a layer 2B1 containing a polymer antistatic agent and an adhesive layer 2B2 containing a binder.

In this case, the heat resistant resin layer 2B may be composed of a layer 2B1 containing a polymer-based antistatic agent and an adhesive layer 2B2 containing only a binder, and may further include a layer containing a polymer-based antistatic agent. 2B1 and other layers other than the adhesive layer 2B2 containing an adhesive agent may include, for example, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas shielding layer, or the like.

Further, the layer 2B1 containing a polymer antistatic agent may contain an adhesive. That is, the heat resistant resin layer 2B may include the layer 2B3 containing a polymer-based antistatic agent and an adhesive.

In this case, the heat resistant resin layer 2B may be composed only of the layer 2B3 containing the polymer antistatic agent and the binder, or may be other than the layer 2B3 containing the polymer antistatic agent and the binder. The layer may further include a layer 2B1 containing a polymer antistatic agent, an adhesive layer 2B containing an adhesive, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas shielding layer, and the like.

In the release film for process of the second invention of the present invention, the heat-resistant tree The thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the lipid layer 2B is 3% or less, or the thermal dimensional change from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B. The rate is preferably 3% or less. In addition, the heat-resistant resin layer 2B has a thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of 3% or less and a thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction. More preferably 3% or less.

The thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is 3% or less, or the thermal size from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B. The rate of change is 3% or less, and wrinkles generated when mounted on the inner surface of the metal mold can be more effectively suppressed.

As the heat-resistant resin layer 2B, by using the above-described specific value indicating the rate of change in the thermal dimension in the transverse (TD) direction, it is not always possible to clearly explain the mechanism for suppressing the occurrence of wrinkles of the release layer more effectively, but it is presumed that The thermal expansion/contraction of the release layer 2A (or the release layer 2A') caused by the heating/cooling during the process can be suppressed by using the heat-resistant resin layer 2B having a small thermal expansion/contraction.

Any resin layer containing an unstretched film may be used in the heat resistant resin layer 2B, but it is particularly preferable to contain an extended film.

The elongation film has a tendency to become low or become a negative number due to the influence of the elongation during the production process, because the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction is 3% or less. In addition, it is easy to change the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B, and therefore it is suitable for use as the heat resistant resin layer 2B.

The thermal dimensional change ratio of the heat-resistant resin layer 2B in the transverse (TD) direction from 23 ° C to 120 ° C is preferably 2% or less, more preferably 1.5% or less, still more preferably 1% or less, and on the other hand, -10%. The above is preferred.

The thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is preferably 2% or less, more preferably 1.5% or less, still more preferably 1% or less, and on the other hand, -10%. The above is preferred.

In the release film for process of the second aspect of the invention, the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is from 23 ° C to 120 ° C in the longitudinal (MD) direction. The thermal dimensional change rate is 6% or less, or the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B, and from 23 ° C to 170 ° C in the longitudinal (MD) direction. The sum of the thermal dimensional change rates up to 5% is preferable. The thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is 6% or less from the thermal dimensional change ratio from 23 ° C to 120 ° C in the longitudinal (MD) direction. In addition, the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction are More than 5% is better. Since the thermal dimensional change rate in the transverse (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change rate in the longitudinal (MD) direction are within the above range, it is possible to more effectively suppress the mounting to the inner surface of the metal mold. Wrinkles are produced.

The thermal dimensional change ratio of the heat-resistant resin layer 2B from 23 ° C to 120 ° C in the transverse (TD) direction is -3.0% or more from the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction. 5.0% or less is better, - 2.0% or more and 4.5% or less is more preferable.

The thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is -15.5% or more in comparison with the thermal dimensional change ratio from 23 ° C to 170 ° C in the longitudinal (MD) direction. It is preferably 5.0% or less, more preferably -10.0% or more and 4.5% or less.

From the viewpoint of making the sum of the thermal dimensional change rate in the transverse (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change rate in the longitudinal (MD) direction within the above range, it is advantageous to use the stretched film, and it is suitable for the use of the stretched film. It is more advantageous to control the extension conditions.

The details of the above-mentioned stretched film are the same as those described for the heat resistant resin layer 1B.

The heat resistant resin layer 2B has heat resistance which is resistant to the mold temperature at the time of molding (typically 120 to 180 ° C) from the viewpoint of controlling the strength of the film or controlling the rate of change in the thermal dimensionality. From the related viewpoint, the heat resistant resin layer 2B preferably contains a crystalline resin having a crystalline component, and the crystalline resin preferably has a melting point of 125 ° C or more, and a melting point of more preferably 155 ° C or more and 300 ° C or less. It is 185 or more and 210 ° C or less, and particularly preferably 185 or more and 205 ° C or less.

As described above, the heat resistant resin layer 2B preferably contains a crystalline resin having a crystalline component. As the crystalline resin contained in the heat resistant resin layer 2B, for example, a crystalline resin such as one or all of a polyester resin, a polyamide resin, or a polypropylene resin can be used. Specifically, polyterephthalic acid or polybutylene terephthalate is used in the polyester fiber resin, and polyamine 6 or polyamide 66 is used in the polyamide resin, and is used in the polypropylene resin. Isotactic polypropylene is preferred.

When the heat resistant resin layer 2B contains the crystal component of the crystalline resin described above, wrinkles are less likely to occur in the resin sealing process or the like, and it is more advantageous to suppress the appearance defect caused by the wrinkle transfer molded article.

The resin constituting the heat-resistant resin layer 2B is preferably 20 J/g or more and 100 J/g or less in the first heat-rise project measured by differential scanning calorimetry (DSC) based on JIS K7221, and 25 J is preferably 25 J. /g or more and 65J/g or less is more preferable, 25J/g or more and 55J/g or less are more preferable, 28J/g or more and 50J/g or less are more preferable, and 28J/g or more and 40J/g or less are even better. More than 28J/g and 35J/g or less. When it is 20 J/g or more, the heat resistance and the release property of the hot stamping molding such as the resin sealing process can be more effectively found, and the dimensional change rate can be suppressed only, so that the occurrence of wrinkles can be prevented. On the other hand, when the heat of the crystal melting heat is 100 J/g or less, it is possible to impart appropriate hardness to the heat-resistant resin layer 2B, and it is possible to ensure sufficient followability to the mold of the film, such as a resin sealing process, and there is no film breakage. risk. Further, in the present embodiment, the heat of crystal melting is a heat amount indicating the obtained vertical axis in the first temperature rising process measured by differential scanning calorimetry (DSC) based on JIS K7221 (J). /g) A numerical value obtained from the sum of the peak areas having peaks at 120 ° C or higher in the graph of the relationship with the temperature of the horizontal axis (° C.).

The heat of crystal melting of the heat resistant resin layer 2B can be adjusted in accordance with heating, cooling conditions, or elongation conditions at the time of film production.

If the thickness of the heat resistant resin layer 2B can ensure the strength of the film There is no particular limitation, but it is usually from 1 to 100 μm, preferably from 5 to 50 μm.

Layer 2B1 containing a polymeric antistatic agent

In the heat-resistant resin layer 2B constituting the laminate of the second invention of the present invention, a polymer compound having an antistatic function can be used as the polymer-based antistatic agent in the layer 2B1 containing a polymer-based antistatic agent which is suitably used. . For example, it may be a cationic copolymer having a quaternary ammonium base in a pendant group, an anionic compound containing a polystyrenesulfonic acid, or a compound having a polyalkylene oxide chain (polyethylene oxide chain, polypropylene oxide chain) Good.), polyethylene glycol methacrylate copolymer, polyether ester decylamine, polyether amidoxime, polyether ester, ethylene oxide-epichlorohydrin copolymer and other nonionic polymers Π-conjugated conductive polymer. These may be used alone or in combination of two or more.

The side group has a quaternary ammonium salt group in the quaternary ammonium salt-based copolymer, and has an effect of rapid dielectric polarization relaxation caused by additional dielectric polarization and electrical conductivity.

The above copolymer preferably has a carboxyl group while having a quaternary ammonium salt group in its side group. When the carboxyl group is present, the copolymer is crosslinkable, and the layer 2B1 can be formed alone. Further, when used in combination with a binder such as a urethane-based adhesive, the adhesive reacts with the adhesive to form a crosslinked structure, and the adhesion, durability, and other mechanical properties are remarkably improved.

The aforementioned copolymer may further have a hydroxyl group at a pendant group. The hydroxyl group is a functional group in the binder, for example, has an improved adhesion after reacting with an isocyanate group. effect.

The above copolymer can be obtained by copolymerizing each of the above functional group monomers. Specific examples of the monomer having a quaternary ammonium salt group may be a diaminoethyl ester quaternary ammonium compound (containing a negative ion such as a chloride, a sulfate, a sulfonate or an alkylsulfonate as a counter ion). Specific examples of the monomer having a carboxyl group may be (meth)acrylic acid, (meth)acryloyloxyethyl succinic acid, phthalic acid, hexahydrophthalic acid or the like.

It is also possible to copolymerize other monomers other than the above. The other monomer may be a vinyl dielectric such as an alkyl (meth)acrylic acid, a styrene, a vinyl acetate, a vinyl halide or an olefin.

The ratio of the copolymerization unit having each functional group in the aforementioned copolymer can be appropriately set. The proportion of the copolymerization unit having a quaternary ammonium salt group is preferably from 15 to 40 mol% based on the total of the total copolymerization units. When the ratio is 15 mol% or more, the antistatic effect is better. If it exceeds 40 mol%, the hydrophilicity of the copolymer may be too high. The ratio of the unit having a carboxyl group is preferably from 3 to 13 mol% based on the total of the units.

When the copolymer has a carboxyl group in the side group, a crosslinking agent (hardener) may be added to the copolymer. The crosslinking agent may be a bifunctional epoxy compound such as glycerol diglycidyl ether or a trifunctional epoxy compound such as trimethylolpropane triglycidyl ether or trimethylolpropane triazinyl ether. A polyfunctional compound such as an ethyleneimine compound.

In the above copolymer, as a catalyst for ring-opening reaction of the above-mentioned bifunctional or trifunctional epoxy compound, 2-methylimidazole or 2-ethyl group may be added. An imidazole dielectric or other amine such as 4-methylimidazole.

The π-conjugated conductive polymer is a conductive polymer having a main chain of π-conjugated development. As the π-conjugated conductive polymer, a conventional one can be used, for example, a polythiophene, a polypyrrole, a polyaniline, a dielectric body thereof, or the like.

The polymer antistatic agent can be produced by a known method, and can also be used commercially. For example, a commercially available product of a copolymer having a quaternary ammonium salt group and a base group in the side group may be "BONDEIP (BONDEIP, trade name) - PA100 main agent" manufactured by KONISHI Co., Ltd., or the like.

As a preferable aspect of the layer 2B1 containing a polymer type antistatic agent, the following layer (1), layer (4), etc. are mentioned.

Layer (1): A polymer-based antistatic agent has a film forming ability, and the polymer antistatic agent is left as it is, or is dissolved in a solvent and wet-coated, and is formed by drying.

Layer (2): a layer in which a polymer-based antistatic agent has a film forming ability and is meltable, and the polymer-based antistatic agent is melt-coated.

Layer (3): a layer in which a binder has a film forming ability and is meltable, and a composition in which the binder is dispersed or dissolved by the polymer antistatic agent is melt-coated.

Layer (4): A layer having a film forming ability, a composition containing the above-mentioned binder and a polymer-based antistatic agent, or a solution which is dissolved in a solvent and wet-coated, and dried as necessary. However, the equivalent of layer (1) does not correspond to layer (4).

In the layer (1), the polymer-based antistatic agent itself has a film forming energy: the polymer antistatic agent is soluble in a solvent such as an organic solvent, and the solution is wet-coated and dried. , the meaning of forming a film.

In the layer (2), the so-called polymer-based antistatic agent is self-meltable, which means melting by heating. The "film forming energy" and "meltable" of the bonding agent in the layers (3) and (4) have the same meaning.

The polymer antistatic agent in the layer (1) may or may not have crosslinkability. When the polymer antistatic agent has crosslinkability, a crosslinking agent can be used in combination.

The polymer antistatic agent having a film forming ability and crosslinkability may be a copolymer having a quaternary ammonium salt group and a carboxyl group in the side group.

The crosslinking agent may be the same as described above.

The thickness of the layer (1) is preferably from 0.01 to 1.0 μm, particularly preferably from 0.03 to 0.5 μm. When the thickness of the layer (1) is 0.01 μm or more, a sufficient antistatic effect can be easily obtained, and when it is 1.0 μm or less, sufficient adhesion can be easily obtained at the time of lamination.

The polymer antistatic agent in the layer (2) may be a polyolefin resin or the like containing a surfactant or carbon black. As a commercial item, PELECTRON HS (made by Sanyo Chemical Industry Co., Ltd.), etc. can be used. The preferred range of the thickness of the layer (2) is the same as the preferred range of the thickness of the layer (1).

As the binder in the layer (3), it may be a general-purpose thermoplastic resin. The thermoplastic resin is preferably a resin having a functional group which contributes to adhesion when it is bonded at the time of melt molding. As the functional group, it may be carbonyl Base.

The content of the polymer-based antistatic agent in the layer (3) is preferably 10 to 40 parts by mass, particularly preferably 10 to 30 parts by mass, based on the total mass of the layer (3). The preferred range of the thickness of the layer (3) is the same as the preferred range of the thickness of the layer (1).

One example of the composition forming the layer (4) is an adhesive. The adhesive means that the main component and the hardener are contained, and the adhesiveness is achieved by hardening by heating or the like.

In this case, the layer 2B1 containing the polymer-based antistatic agent may correspond to the layer 2B3 containing the polymer-based antistatic agent and the binder.

The adhesive may be a one-component adhesive or a two-component adhesive.

As the adhesive for forming the layer (4) (hereinafter, also referred to as a layer (4) forming adhesive), for example, a polymer-based antistatic agent may be added to an adhesive that does not contain a polymer-based antistatic agent. Agents, etc.

The polymer antistatic agent to be added to the adhesive may have a film forming ability or a film forming ability (for example, a π-conjugated conductive polymer).

As the adhesive which does not contain a polymer type antistatic agent, a conventional adhesive which is an adhesive for dry lamination can be used. For example, a polyvinyl acetate-based adhesive; a separate polymer or copolymer of an acrylate (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or an acrylate and other monomers can be used ( Polyacrylate adhesive formed by copolymer of methyl methacrylate, acrylonitrile, styrene, etc.; cyanopropyl Ethylene ester-based adhesive; ethylene copolymer-based adhesive formed by copolymer of ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc.); cellulose-based adhesive Connecting agent; polyester-based adhesive; polyamine-based adhesive; polyimide-based adhesive; ammonia resin-based adhesive formed by urea resin or melamine resin; phenol resin-based adhesive; Epoxy adhesive; polyol (polyether polyol, polyester polyol, etc.) and isocyanate and / or polyurethane-based adhesive cross-linked with isocyanurate; reactive (meth) acrylic adhesive a rubber-based adhesive formed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc.; formed of an organic bismuth-based adhesive; an alkali metal silicate, a low-melting glass, or the like Inorganic adhesives; other adhesives.

The content of the polymer-based antistatic agent in the layer (4) is preferably such that the surface specific resistance of the layer (4) is preferably 10 ¹⁰ Ω/□ or less, and 10 ⁹ Ω/□ or less. Very good amount.

From the viewpoint of antistatic, the content of the polymer-based antistatic agent in the layer (4) forming adhesive is preferably as large as possible, but the polymer-based antistatic agent is a π-conjugated conductive polymer. When a π-conjugated conductive polymer is added to an adhesive that does not contain a polymer-based antistatic agent, it is used as a layer (4) forming adhesive, and when a layer 2B1 is formed, a polymer-based antistatic agent is used. When the content of the first layer (4) is lowered, the adhesion between the first thermoplastic resin layer 2 and the second thermoplastic resin layer 3 may be insufficient. Therefore, the content of the polymer-based antistatic agent in the adhesive for forming the layer (4) at this time is preferably 40% by mass or less, and preferably 30% by mass or less based on the solid content of the resin which is a binder. . Lower limit 1% by mass is preferred, and 5% by mass is particularly preferred.

The thickness of the layer (4) is preferably 0.2 to 5 μm, particularly preferably 0.5 to 2 μm. When the thickness of the layer (4) is at least the lower limit of the above range, the adhesion between the first thermoplastic resin layer and the second thermoplastic resin layer is good, and the antistatic property is also good. If it is below the upper limit of the above range, productivity is also good.

The polymer-based antistatic layer having the layer 2B1 may be one layer or two or more layers. For example, only one of the layers (1) to (4) may be used, or two or more of them may be used.

As the polymer-based antistatic layer, the layer (1) is preferable at the point of easy production. It is also possible to use either of layer (1) and layer (2) to (4) in combination.

Adhesive layer 2B2

In the heat-resistant resin layer 2B constituting the laminate of the second invention of the present invention, a conventionally known adhesive can be suitably used as the adhesive contained in the adhesive layer 2B2 which is suitably used. From the viewpoint of the production efficiency of the laminate of the second invention of the present invention, it is preferred to use an adhesive for dry lamination. For example, a polyvinyl acetate-based adhesive; a separate polymer or copolymer of an acrylate (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or an acrylate and other monomers can be used ( Polyacrylate adhesive formed by copolymer of methyl methacrylate, acrylonitrile, styrene, etc.; cyanoacrylate adhesive; ethylene and other monomers (vinyl acetate, acrylic acid B) Copolymerization of base, acrylic acid, methacrylic acid, etc. Ethylene copolymer-based adhesive formed by materials; cellulose-based adhesive; polyester-based adhesive; polyamine-based adhesive; polyimide-based adhesive; urea resin or melamine resin An amino resin-based adhesive formed; a phenol resin-based adhesive; an epoxy-based adhesive; a polyol (polyether polyol, polyester polyol, etc.) and an isocyanate and/or an isocyanurate Jointed polyurethane-based adhesive; reactive (meth)acrylic adhesive; rubber-based adhesive formed from neoprene, nitrile rubber, styrene-butadiene rubber, etc.; Adhesives; inorganic binders formed by alkali metal silicates, low-melting glasses, etc.; other adhesives.

Layer 2B3 containing a polymer antistatic agent and an adhesive

In the heat-resistant resin layer 2B constituting the laminate of the second invention of the present invention, a polymer-based antistatic agent contained in the layer 2B3 containing a polymer-based antistatic agent and a binder which is suitably used can be preferably used. The polymer antistatic agent similar to the above described in relation to the layer 2B1 containing a polymer-based antistatic agent, as the binder, preferably the same adhesive as described above for the adhesive layer 2B2 containing the adhesive. Ingredients.

In the layer (4) described above, when the composition of the layer (4) is an adhesive, it is a particularly preferable example of the layer 2B3 containing a polymer-based antistatic agent and an adhesive.

Layer other than this

The release film for process of the second aspect of the present invention may have a release layer 2A and a heat resistant resin layer as long as it does not violate the object of the second invention. 2B, and a layer other than the release layer 2A'. The details of the layers other than the above are the same as those described in the first invention of the present invention.

The total thickness of the release film for a process according to the second aspect of the invention is not particularly limited, but is, for example, preferably 10 to 300 μm, more preferably 30 to 150 μm. When the total thickness of the release film is within the above range, the handleability when used as a roll is good, and the amount of waste of the film is small, which is preferable.

Hereinafter, a preferred embodiment of the release film for a process according to the second invention of the present invention will be described more specifically. FIG. 1 is a schematic view showing an example of a release film for a three-layer structure. As shown in FIG. 1, the release film 10 has a heat resistant resin layer 12 and a release layer 16 formed on one surface thereof via an adhesive layer 14.

The release layer 16 is the aforementioned release layer 2A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer 2B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the encapsulating resin in the packaging process; and the heat resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the metal mold in the packaging process.

2 is a schematic view showing an example of a release film for a process having a five-layer structure. Components having the same functions as those of Fig. 1 will be given the same reference numerals. As shown in FIG. 2, the release film 20 has a heat resistant resin layer 12, and a release layer 16A and a release layer 16B which are formed on the both surfaces thereof via the adhesive layer 14. The release layer 16A is the release layer 2A described above, the heat resistant resin layer 12 is the above-mentioned heat resistant resin layer 2B, the release layer 16B is the release layer 2A' described above, and the adhesive layer 14 is the above-mentioned adhesive layer.

The composition of the release layers 16A and 16B may be the same or different from each other. The thickness of the release layers 16A and 16B may also be the same or different from each other. However, if the release layers 16A and 16B have the same composition and thickness, they will have a symmetrical structure, and it is preferable that the release film is hard to be bent by itself. In particular, in the release film of the second invention of the present invention, stress is generated by heating during the packaging process, and therefore it is preferable to suppress bending. Therefore, after the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12, it is preferable that either of the molded article and the inner surface of the mold can obtain good release property.

Method for manufacturing release film for process

The release film for process of the second invention of the present invention can be produced by any method, but the preferred production method is the same as that described in the first invention of the present invention.

Manufacturing process

In the release film for a process according to the second aspect of the invention, a semiconductor wafer or the like can be placed in a mold, and when a resin is injection-molded, it can be disposed between a semiconductor wafer or the like and an inner surface of the mold. According to the release film for process of the second aspect of the invention, it is possible to effectively prevent the release from the mold, the occurrence of burrs, and the like.

The resin used in the above production process may be any of a thermoplastic resin and a thermosetting resin, but thermosetting resins have been widely used in the technical field, and particularly, an epoxy-based thermosetting resin is preferable.

As the above-mentioned manufacturing process, the packaging of the semiconductor wafer is the most representative, but it is not limited thereto, and the second invention of the present invention can also be applied to a fiber reinforced plastic molding process, a plastic lens forming process, and the like.

The details of the above-described manufacturing process of the release film for process of the second invention of the present invention are the same as those described in the first invention of the present invention.

The release film of the second invention of the present invention is not limited to a process of encapsulating a semiconductor element resin, and is a process of molding and releasing various molded articles using a molding die, for example, fiber reinforced plastic molding and release molding, plastic lens molding and separation. Type engineering or the like can also be preferably used.

[Examples]

Hereinafter, the first invention and the second invention of the present invention will be further described based on the examples, but the first invention and the second invention of the present invention are not limited to the examples.

In the following examples/reference examples, the evaluation of physical properties/characteristics was carried out by the following method.

(thermal dimensional change rate)

The film sample was cut out in the longitudinal (MD) direction and the transverse (TD) direction of the film by a length of 20 mm and a width of 4 mm, respectively, and the distance between the chucks was measured by TMA (thermo-mechanical analysis device, product name: Q400) manufactured by TA Instruments Co., Ltd. 8 mm was applied at 23 ° C for 5 minutes while applying a load of 0.005 N, and then the temperature was raised from 120 ° C at a temperature increase rate of 10 ° C /min from 23 ° C, and the dimensional change in each direction was measured and calculated by the following formula (1). Dimensional change rate.

Thermal dimensional change rate (%) (23 → 120 ° C) = {[(L _{2 -} L ₁ ) / L ₁ ] × 100} ‧ ‧ (1)

L ₁ : sample length (mm) at 23 ° C

L ₂ : sample length (mm) at 120 ° C

Similarly, the temperature was raised from 170 ° C at a temperature increase rate of 10 ° C /min to 23 ° C, and the dimensional change in each direction was measured, and the dimensional change ratio was calculated from the following formula (2).

Thermal dimensional change rate (%) (23 → 170 ° C) = {[(L _{3 -} L ₁ ) / L ₁ ] × 100} ‧ ‧ (2)

L ₁ : sample length (mm) at 23 ° C

L ₃ : sample length (mm) at 170 ° C

Contact angle with respect to water (water contact angle)

The water contact angle of the surface of the release layer A or the like was measured using a contact angle measuring instrument (FACECA-W, manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS R3257.

(tensile modulus)

Method for measuring tensile modulus

The tensile modulus at 23 ° C, 120 ° C, and 170 ° C was determined based on JIS K7127.

Measurement conditions: tensile mode

Measurement direction: longitudinal (MD) direction of the film (film transport direction)

(surface specific resistance value)

A 10 × 10 cm test piece cut out from the obtained release film was stored at a temperature of 23 ° C and a humidity of 50% RH for 24 hours. Thereafter, a digital ultra-high resistance/micro current meter (8340A) and a resistance chamber (R12704) manufactured by Advantest Co., Ltd. were used, and a voltage of 0.10 V, a temperature of 23 ° C, and a humidity of 50% RH were measured.

(ash adhesion test)

Antistatic property of release film Under the environment of 20 ° C and 50% RH, the release film was rubbed with a polyester fiber cloth for 10 times, and the adhesion of ash was investigated.

No attachment: ○

Significant adhesion: ×.

(melting point (Tm), crystal melting heat)

As a differential scanning calorimeter (DSC), Q100 manufactured by TA Instruments Japan Co., Ltd. was used to accurately weigh approximately 5 mg of the polymer sample, based on JIS K7121, and the heating rate was started at 25 ° C under the condition of nitrogen inflow: 50 ml/min. The temperature was raised to 280 ° C at 10 ° C / min to measure the thermal melting curve, and the melting point (Tm) of the sample and the heat of crystal melting were determined from the obtained thermal melting curve.

(release)

The release film for the process produced by each of the examples/reference examples was applied with a tension of 10 N between the upper mold and the lower mold in the manner shown in FIG. After the state is configured, it is vacuum-adsorbed to the parting surface of the upper mold. Next, after encapsulating the semiconductor wafer on the substrate, the semiconductor wafer fixed to the substrate is placed in the lower mold and the mold is closed. At this time, the temperature (forming temperature) of the molding die was set to 120 ° C, the molding pressure was set to 10 MPa, and the molding time was set to 400 seconds. Next, as shown in FIG. 3c, after the semiconductor wafer is encapsulated with a sealing resin, the resin-encapsulated semiconductor wafer (semiconductor package) is released from the release film.

The release property of the release film was evaluated by the following criteria.

◎: The release film was naturally peeled off while the mold was open.

○: Although the release film is not naturally peeled off, it can be easily peeled off by hand stretching (application of tension).

X: The release film adhered closely to the resin package surface of the semiconductor package and could not be peeled off by hand.

(wrinkle)

The state in which the release film of the release film and the resin package surface of the semiconductor package were wrinkled by the above-described work was evaluated by the following criteria.

◎: The release film and the semiconductor package are completely free of wrinkles.

○: The release film was only slightly wrinkled, but was not transferred to the wrinkles of the semiconductor package.

×: The release film needless to say, the semiconductor package also has many wrinkles.

(appearance of molded article)

Release film and semiconductor package after release using the above engineering The appearance of the resin package surface was evaluated by the following criteria.

◎: The release film and the semiconductor package are completely free of wrinkles, and the periphery of the semiconductor package has no burrs at all.

○: The release film and the semiconductor package are completely free of wrinkles or only a little wrinkles, and the periphery of the semiconductor package has only a little burr.

X: It is needless to say that the release film has a large number of wrinkles in the semiconductor package or a large number of burrs on the outer periphery of the semiconductor package.

(metal mold followability)

The metal mold followability of the release film at the time of release by the above-described work was evaluated by the following criteria.

◎: There is no resin defect (portion not filled with resin) in the semiconductor package.

○: There is only a little resin defect at the end of the semiconductor package (except for defects due to wrinkles)

×: There are many resin defects at the end of the semiconductor package (except for defects due to wrinkles)

[Example 1-1]

As the heat-resistant resin layer 1B, a biaxially stretched PET (polyterephthalic acid) film (manufactured by Toray Industries, Inc., product name: Lumirror S10) having a film thickness of 12 μm was used. The thermal dimensional change rate of the biaxially stretched PET film from 23 ° C to 120 ° C was -0.3% in the longitudinal (MD) direction and -0.3% in the transverse (TD) direction. In addition, the melting point of the biaxially stretched PET film At 258 ° C, the heat of crystallization melting was 39.4 J/g.

As the release layers 1A and 1A', a 4-methyl-1-pentene copolymer resin film having no extension was used. Specifically, a slit of a T-die is used by melt-extruding a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals Co., Ltd. at 270 ° C. The width was adjusted to make a film having a thickness of 15 μm without stretching film.

The non-extended 4-methyl-1-pentene copolymer resin film is obtained from the viewpoint of improving the adhesion of the adhesive when the water contact angle of one of the film surfaces is 30° or more according to JIS R3257. Apply a corona treatment to make it 30 or less.

The thermal dimensional change rate of the 4-methyl-1-pentene film from 23 ° C to 120 ° C was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction.

(adhesive)

The adhesive used in the dry lamination process for bonding the respective films uses the following polyurethane-based adhesive A.

[Polyurethane adhesive A]

Main agent: TAKELAC A-616 (manufactured by Mitsui Chemicals, Inc.). Hardener: TAKENATA A-65 (manufactured by Mitsui Chemicals, Inc.). The main agent and the hardener were mixed at a mass ratio (main agent: hardener) of 16:1, and as a diluent, ethyl acetate was used.

(Manufacture of release film)

On one side of the biaxially stretched PET (polyterephthalic acid) film, the polyurethane-based adhesive A was coated with 1.5 g/m ² by gravure coating, and the 4-methyl-1 without extension was applied. After the corona-treated surface of the pentene copolymer resin film is bonded by dry lamination, and then on the side of the biaxially stretched PET (polyterephthalic acid) film of the laminated film, the urethane-based adhesive A is 1.5 g/m ² was applied, and the corona-treated surface of the unstretched 4-methyl-1-pentene copolymer resin film was laminated by dry lamination to obtain a 5-layer structure (release layer 1A/bonding) A release film for the process of the layer/heat resistant resin layer 1B/adhesive layer/release layer 1A').

The dry lamination conditions were as follows: a substrate width of 900 mm, a conveying speed of 30 m/min, a drying temperature of 50 to 60 ° C, a laminating roll temperature of 50 ° C, and a roll pressure of 3.0 MPa.

The thermal dimensional change rate of the release film for this process from 23 ° C to 120 ° C was 2.1% in the longitudinal (MD) direction and 1.5% in the transverse (TD) direction.

The evaluation results of the release property, the wrinkles, and the followability of the metal mold are shown in Table 1-1. The release film naturally exhibits good release property of the release film while the metal mold is open, and any of the release film and the semiconductor package is completely wrinkle-free, that is, the wrinkle can be sufficiently controlled to be expressed in the semiconductor package. Good metal mold followability with no resin defects. In other words, the release film for the process of Example 1-1 is a release film for a process which is excellent in release property, wrinkle suppression, and metal mold followability.

[Example 1-2~1-9]

The release film shown in Table 1-1 was produced in the same manner as in Example 1-1 except that each of the films described in Table 1-1 was used as the release layers 1A and 1A' and the heat-resistant resin layer 1B. Package, release, and evaluate features. The results are shown in Table 1-1.

Although in some cases, the wrinkle suppression or the metal mold followability is inferior to that of Example 1-1, any of the examples is excellent in release property, wrinkle suppression, and metal mold followability with high level balance. Release film for process.

In addition, the details of each film described in the table are as follows.

(1A1) No extension 4MP-1 (TPX) film

A 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. was used to form a non-stretched film having a thickness of 15 μm. (Melting point: 229 ° C, heat of crystal melting: 21.7 J/g)

(1A2) No extension 4MP-1 (TPX) film

A 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: DX818) manufactured by Mitsui Chemicals, Inc. was used to form a non-stretched film having a thickness of 15 μm. (Melting point: 235 ° C, heat of crystal melting: 28.1 J/g)

(1A3) No extension 4MP-1 (TPX) film

A 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. was used to form a non-stretched film having a thickness of 50 μm. (Melting point: 229 ° C, heat of crystal melting: 21.7 J/g)

(1B1) 2-axis extended PET film

Biaxially stretched PET (polyterpene terephthalate) film having a film thickness of 12 μm (manufactured by Toray Industries, Inc., product name: Lumila S10) (melting point: 258 ° C, heat of crystal melting: 39.4 J/g)

(1B2) 2-axis extended nylon film

Biaxially stretched nylon film having a film thickness of 15 μm (manufactured by KOHJIN Film & Chemicals Co., Ltd., product name: BONYL RX) (melting point: 212 ° C, heat of crystal melting: 53.1 J/g)

(1B3) 2-axis extended nylon film

Biaxially stretched nylon film with a film thickness of 15 μm (manufactured by Shinko Co., Ltd., product name: UNILON S330) (melting point: 221 ° C, heat of crystal melting: 60.3 J/g)

(1B4) 2-axis extended polypropylene film

Biaxially oriented polypropylene film with a film thickness of 20 μm (manufactured by Mitsui Chemicals, Ltd., product name: U-2) (melting point: 160 ° C, heat of crystal melting: 93.3 J/g)

(1B5) Unstretched nylon film

Non-stretch nylon film with a film thickness of 20 μm (manufactured by Mitsubishi Plastics Co., Ltd., product name: Dainamiron C) (melting point 220 ° C, heat of crystal melting: 39.4 J/g)

(1B6) 2-axis extended PET film

A 2-axis extended PET film (manufactured by Teijinfilmsolutions Co., Ltd., product name: FT3PE) having a film thickness of 25 μm (melting point: 214 ° C, heat of crystal melting: 40.3 J/g) was used.

(1B7) non-extended polyterephthalic acid film

A polyethylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used to form a non-stretch film having a thickness of 20 μm. (Melting point: 223 ° C, heat of crystal melting: 49.8 J/g)

(1B8) non-extended polyterephthalic acid film

A polyethylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used to form a non-stretch film having a thickness of 20 μm. (Melting point: 219 ° C, heat of crystal melting: 48.3 J/g)

(1B9) non-extended polyterephthalic acid film

A polyethylene terephthalate resin (brand name: 5050) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used to form a non-stretch film having a thickness of 50 μm. (Melting point: 223 ° C, heat of crystal melting: 49.8 J/g)

(1B10) non-extended polyterephthalic acid film

A polyethylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used to form a non-stretch film having a thickness of 50 μm. (Melting point: 219 ° C, heat of crystal melting: 48.3 J/g)

[Reference Example 1-1~1-3]

The films 1A3, 1B9, and 1B10 shown in Table 1-1 were used as separate release films for the process, and packaged and released in the same manner as in Example 1-1, and the properties of the release film for the process were evaluated.

The comprehensive performance of any of the reference examples is not inferior to the embodiment, and in particular, the occurrence of wrinkles cannot be suppressed.

[Table 1]

[Examples 1-10 to 1-14]

In the combination shown in Table 1-2, except that each of the films described in Table 1-2 was used as the release layers 1A and 1A' and the heat-resistant resin layer 1B, a release film for a process was produced in the same manner as in Example 1-1. Package, release, and evaluate features.

As shown in Fig. 4, the release film was placed between the upper mold and the lower mold with a tension of 20 N, and then vacuum-adsorbed to the parting surface of the upper mold. Next, after encapsulating the semiconductor wafer on the substrate, the semiconductor wafer fixed to the substrate is placed in the lower mold and the mold is closed. At this time, the temperature (forming temperature) of the molding die was 170 ° C, the molding pressure was 10 MPa, and the molding time was 100 seconds. Next, as shown in FIG. 3c, after the semiconductor wafer is encapsulated with a sealing resin, the resin-encapsulated semiconductor wafer (semiconductor package) is released from the release film. The results are shown in Table 1-2.

In some cases, the followability of the metal mold is inferior to that of the embodiment 1-1, but any of the examples is a release film for a process which is excellent in release property, wrinkle suppression, and metal mold followability with a good balance of high order. In particular, Examples 1-11 to 1-13 are release films for process release, wrinkle suppression, and metal mold followability.

[Reference Example 1-4~1-6]

The combination shown in Table 1-2 was used except that each of the films described in Table 1-2 was used as the release layers 1A and 1A' and the heat resistant resin layer 1B. The release film for the process was produced in the same manner as in the case of 1-10 to 1-14, and was packaged, released, and evaluated. The results are shown in Table 1-2.

Although the release property and the mold followability are as good as those of the examples, the occurrence of wrinkles cannot be suppressed.

[Reference Example 1-7~1-10]

The films 1A1, 1A2, 1B9, and 1B10 shown in Table 1-2 were used as separate release films for the process, and packaged and separated as in Examples 1-10 to 1-14, and the process was evaluated. The characteristics of the film.

The comprehensive performance of any of the reference examples is not inferior to the embodiment, and in particular, the occurrence of wrinkles cannot be suppressed.

[Table 2]

[Example 2-1]

As the base material B0a of the heat-resistant resin layer 2B, a biaxially stretched PET (polyterephthalic acid) film (manufactured by Toray Industries, Inc., product name: Lumirror S10) having a film thickness of 12 μm was used.

As the antistatic resin a, a PEDOT polythiophene-based resin (product name: MC-200, manufactured by Kasei Kogyo Co., Ltd.) was used to form a layer containing a polymer-based antistatic agent. More specifically, the antistatic resin a is applied and dried on one surface of the base material 2B0a of the heat-resistant resin layer 2B at a coating amount of 0.1 g/m ² to form a layer 2B1a containing a polymer-based antistatic agent.

The thermal dimensional change rate from 23 ° C to 120 ° C of the biaxially stretched PET film (heat resistant resin layer 2 Ba) to which the polymer antistatic agent-containing layer obtained as described above is applied is -0.1 in the longitudinal (MD) direction. %, the horizontal (TD) direction is 0.6%. Further, the biaxially stretched PET film had a melting point of 258 ° C and a heat of crystal fusion of 39.4 J/g.

As the release layers 2A and 2A', a 4-methyl-1-pentene copolymer resin film 2Aa (2A'a) having no extension was used. Specifically, a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. was used to form a film having a thickness of 15 μm without stretching. (Melting point: 229 ° C, heat of crystal melting: 21.7 J/g)

The non-extended 4-methyl-1-pentene copolymer resin film is obtained from the viewpoint of improving the adhesion of the adhesive when the water contact angle of one of the film surfaces is 30° or more according to JIS R3257. Apply corona treatment to make It becomes 30 or less.

The thermal dimensional change rate of the 4-methyl-1-pentene copolymer resin 2Aa film from 23 ° C to 120 ° C was 6.5% in the MD (MD) direction and 3.1% in the transverse (TD) direction.

(adhesive)

The following urethane-based adhesive a was used as the adhesive used for the dry lamination of each film.

[Polyurethane adhesive a]

Main agent: TAKELAC A-616 (manufactured by Mitsui Chemicals, Inc.). Hardener: TAKENATA A-65 (manufactured by Mitsui Chemicals, Inc.). The main agent and the hardener were mixed at a mass ratio (main agent: hardener) of 16:1, and as a diluent, ethyl acetate was used.

(Manufacture of release film)

On one side of the biaxially stretched PET (heat resistant resin layer 2Ba) to which the antistatic layer was applied, the urethane-based adhesive α was applied by 1.5 g/m ² by gravure coating, and the stretch-free 4- The corona-treated surface of the methyl-1-pentene copolymer resin film Aa is adhered by dry lamination, and then the polyurethane-based adhesive α is 1.5 g on the side of the biaxially stretched PET film of the laminated film. /m ² is applied, and the corona-treated surface of the 4-methyl-1-pentene copolymer resin film A'a which is not extended is laminated by dry lamination to obtain a 5-layer structure (release layer 2A/sticky) A release film for the process of the bonding layer/heat resistant resin layer 1B/adhesive layer/release layer 2A').

The dry lamination conditions were as follows: a substrate width of 900 mm, a conveying speed of 30 m/min, a drying temperature of 50 to 60 ° C, a laminating roll temperature of 50 ° C, and a roll pressure of 3.0 MPa.

The thermal dimensional change rate of the release film for this process from 23 ° C to 120 ° C was 1.0% in the longitudinal (MD) direction and 1.4% in the transverse (TD) direction.

The tensile modulus, the release property, the appearance of the molded article, the mold followability, the surface specific resistance value, and the evaluation results of the ash adhesion test are shown in Table 2-1. The release film naturally exhibits good release property of the release film while the metal mold is open, and any of the release film and the semiconductor package is completely free of wrinkles and burrs, that is, the wrinkles can be sufficiently controlled in the semiconductor package. The body exhibits good metal mold followability with no resin defects. In other words, the release film for the process of the embodiment 2-1 is a release film for a process which is excellent in release property, appearance of the molded article, and good followability of the metal mold. In addition, ash adhesion is not recognized.

[Example 2-2~2-9]

A release film for a process was produced in the same manner as in Example 2-1 except that the film structure shown in Table 2-1 was used, and the package was released and molded, and the properties were evaluated. The results are shown in Table 2-1.

In addition, the details of the polymer antistatic agents b to e described in Table 2-1 and the layers 2B1b to 2B1e included in the following are as follows.

As the antistatic resin b, a PEDOT polythiophene-based resin (product name: S-495, manufactured by Nakagisa Oils and Fats Co., Ltd.) was used to form a layer containing a polymer-based antistatic agent. More specifically, the antistatic resin b is applied and dried on one surface of the base material 2B0a of the heat resistant resin layer 2B at a coating amount of 0.3 g/m ² to form a layer 2B1b containing a polymer antistatic agent. The thermal dimensional change rate from 23 ° C to 120 ° C of the biaxially stretched PET film of the layer containing the polymer antistatic agent obtained above was the result shown in Table 2-1.

As the antistatic resin c, a PEDOT polythiophene-based resin (product name: P-530RL, manufactured by Nagase Corporation) was used to form a layer containing a polymer-based antistatic agent. More specifically, the antistatic resin c is applied and dried on one surface of the base material 2B0a of the heat resistant resin layer 2B at a coating amount of 0.1 g/m ² to form a layer 2B1c containing a polymer antistatic agent. The thermal dimensional change rate from 23 ° C to 120 ° C of the biaxially stretched PET film of the layer containing the polymer antistatic agent obtained above was the result shown in Table 2-1.

As the antistatic resin d, a quaternary ammonium salt-containing resin (manufactured by Daisei Fine Chemical Co., Ltd., product name: 1SX-1090) was used to form a layer containing a polymer-based antistatic agent. More specifically, the antistatic resin d is applied and dried on one surface of the base material 2B0a of the heat resistant resin layer 2B at a coating amount of 0.4 g/m ² to form a layer 2B1d containing a polymer antistatic agent. The thermal dimensional change rate from 23 ° C to 120 ° C of the biaxially stretched PET film of the layer containing the polymer antistatic agent obtained above was the result shown in Table 2-1.

As the antistatic resin e, an anion-based synthetic clay mineral is used, and a polyester-based resin (product name: ASA-2050, manufactured by Takamatsu Oil Co., Ltd.) is used to form a layer containing a polymer-based antistatic agent. More specifically, the antistatic resin e is applied and dried on one surface of the base material 2B0a of the heat resistant resin layer 2B at a coating amount of 0.4 g/m ² to form a layer 2B1e containing a polymer antistatic agent. The negative ion-based synthetic clay mineral contains a polyester resin (product name: ASA-2050, manufactured by Takamatsu Oil Co., Ltd.) to form a layer containing a polymer-based antistatic agent. More specifically, the antistatic resin e is applied and dried on one surface of the base material 2B0a of the heat resistant resin layer 2B at a coating amount of 0.4 g/m ² to form a layer 2B1e containing a polymer antistatic agent. Test items and evaluations of the thermal dimensional change rate and water contact angle from 23 ° C to 120 ° C of the biaxially stretched PET film of the polymer antistatic agent-containing layer obtained as described above are shown in Table 2-1. Shown.

Any of the examples is a release film for a process which is excellent in release property, appearance of a molded article, followability of a metal mold, and all test items of a ash adhesion test, and which is balanced in performance.

In addition, the details of each film described in Table 2-1 are as follows.

(2Aa) No extension 4MP-1 (TPX) film

A 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. was used to form a non-stretched film having a thickness of 15 μm. (Melting point: 229 ° C, heat of crystal melting: 21.7 J/g)

(2Ab) no extension 4MP-1 (TPX) film

Forming thickness using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals Co., Ltd. 50 μm unstretched film. (Melting point: 229 ° C, heat of crystal melting: 21.7 J/g)

(2B0a) 2-axis extended PET film

Biaxially stretched PET (polyterpene terephthalate) film having a film thickness of 12 μm (manufactured by Toray Industries, Inc., product name: Lumila S10) (melting point: 258 ° C, heat of crystal melting: 39.4 J/g)

(2B0b) 2-axis extended nylon film

Biaxially stretched nylon film having a film thickness of 15 μm (manufactured by KOHJIN Film & Chemicals Co., Ltd., product name: BONYL RX) (melting point: 212 ° C, heat of crystal melting: 53.1 J/g)

(B0c) 2-axis extended polypropylene film

Biaxially oriented polypropylene film with a film thickness of 20 μm (manufactured by Mitsui Chemicals, Ltd., product name: U-2) (melting point: 160 ° C, heat of crystal melting: 93.3 J/g)

(2B0d) no stretch nylon film

Non-stretch nylon film with a film thickness of 20 μm (manufactured by Mitsubishi Plastics Co., Ltd., product name: Dainamiron C) (melting point 220 ° C, heat of crystal melting: 39.4 J/g)

(2B0e) non-extended polyterephthalic acid film

A polyethylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used to form a non-stretch film having a thickness of 20 μm. (Melting point: 219 ° C, heat of crystal melting: 48.3 J/g)

(2B0f) non-extended polyterephthalic acid film

Using polyterephthalic acid tree made by Mitsubishi Engineering Plastics Co., Ltd. Fat (brand name: 5505S), forming a non-stretch film having a thickness of 50 μm. (Melting point: 219 ° C, heat of crystal melting: 48.3 J/g)

[Reference Example 2-1~2-3]

The properties of the release film for the process were evaluated in the same manner as in Example 2-1 except that the film composition shown in Table 2-1 was used.

The overall performance of any of the reference examples is not as good as the examples, especially the adhesion test results are not good. Further, the appearance did not give good results except for Reference Example 2-1.

[table 3]

[Example 2-10~2-17]

In the combination shown in Table 2-2, except that each of the films described in Table 2-2 was used as the release layers 2A and 2A' and the heat-resistant resin layer 2B, a release film for a process was produced in the same manner as in Example 2-1. Package, release, and evaluate features.

As shown in Fig. 3, the release film was placed between the upper mold and the lower mold with a tension of 20 N, and then vacuum-adsorbed to the parting surface of the upper mold. Next, after encapsulating the semiconductor wafer on the substrate, the semiconductor wafer fixed to the substrate is placed in the lower mold and the mold is closed. At this time, the temperature (forming temperature) of the molding die was 170 ° C, the molding pressure was 10 MPa, and the molding time was 100 seconds. Next, as shown in FIG. 3c, after the semiconductor wafer is encapsulated with a sealing resin, the resin-encapsulated semiconductor wafer (semiconductor package) is released from the release film. The results are shown in Table 2-2.

Although any of the examples were evaluated at a high temperature region of 170 ° C, all the test items of the release property, the appearance of the molded article, the mold followability, and the ash adhesion test were good, and the process was balanced in terms of performance. Type film. In particular, Examples 2-15 to 2-17 are release films for process release, mold appearance, mold followability, and ash adhesion test results.

[Reference Example 2-4~2-9]

Except for the film configuration shown in Table 2-2, and examples As in 2-10 to 2-17, a release film for the process was produced, packaged, released, and evaluated. The results are shown in Table 2-2.

The comprehensive performance of any of the reference examples was not as good as that of the respective examples, and in particular, both the appearance of the molded article and the ash adhesion test failed to give good results.

The details of the respective films described in Table 2-2 are the same as those described above for each film described in Table 2-1.

The details of the base materials 2B0g and 2B0h of the heat resistant resin layer described in Table 2-2 are as follows.

(2B0g) 2-axis extended nylon film

Biaxially stretched nylon film with a film thickness of 15 μm (manufactured by Shinko Co., Ltd., product name: UNILON S330) (melting point: 221 ° C, heat of crystal melting: 60.3 J/g)

(2B0h) 2-axis extended PET film

A 2-axis extended PET film (manufactured by Teijinfilmsolutions Co., Ltd., product name: FT3PE) having a film thickness of 25 μm (melting point: 214 ° C, heat of crystal melting: 40.3 J/g) was used.

[Table 4]

[Industry use possibility]

In the release film for process of the first aspect of the present invention, since the high-grade release property, wrinkle suppression, and metal mold followability which were not achieved by the prior art are used, the release film can be used to form the semiconductor. A molded article obtained by a resin package such as a wafer can be easily released, and a molded article having no appearance defects such as wrinkles or defects can be produced with high productivity, and a practically high-value technical effect can be obtained from the semiconductor. From the process industry to the various fields of the industry, there is a high possibility of utilization.

In addition, the release film for the process of the first aspect of the present invention can be used for forming a metal mold other than the semiconductor industry, because it is not limited to the semiconductor package, and can be used for forming various metal molds such as a fiber-reinforced plastic molding process and a plastic lens molding process. There are also high utilization possibilities in various fields of the industry.

In the release film for process of the second aspect of the present invention, since the high-level release property, wrinkle suppression, and metal mold followability which have not been achieved by the prior art are used, the release film can be used to form the semiconductor. A molded article obtained by a resin package such as a wafer can be easily released, and a molded article having no appearance defects such as wrinkles or defects can be produced with high productivity, and a practically high-value technical effect can be obtained from the semiconductor. From the process industry to the various fields of the industry, there is a high possibility of utilization.

In addition, the release film for the process of the second aspect of the invention can be molded into various metal molds such as a fiber-reinforced plastic molding process and a plastic lens molding process, and can be molded into a metal mold other than the semiconductor industry. There are also high utilization possibilities in various fields of the industry.

10‧‧‧ release film

12‧‧‧Heat Resin Layer 1B, 2B

14‧‧‧Adhesive layer

16‧‧‧ Release layer 1A, 2A

Claims (46)

A release film for a process comprising a release film of a release layer 1A and a heat resistant resin layer 1B, wherein a contact angle of the release layer 1A with respect to water is 90° to 130°; The tensile modulus at °C is from 75 MPa to 500 MPa. The release film for a process according to claim 1, wherein the thermal film dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 120 ° C is 3% or less. The release film for a process according to claim 1 or 2, wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 from the vertical (MD) direction. The sum of the thermal dimensional change rates from ° C to 120 ° C is 6% or less. A release film for a process comprising a release film of a release layer 1A and a heat resistant resin layer 1B, wherein a contact angle of the release layer 1A with respect to water is 90° to 130°; The tensile modulus at °C is from 75 MPa to 500 MPa. The release film for a process according to claim 4, wherein a thermal dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 170 ° C is 4% or less. The process release film according to claim 4, wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 from the vertical (MD) direction. °C to 170°C The sum of the thermal dimensional change rates up to 7% or less. The release film for a process according to any one of claims 1 to 6, wherein the heat-resistant resin layer 1B has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of 3% or less. The release film for a process according to claim 7, wherein the heat-resistant resin layer 1B has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 120 ° C is 6% or less. The process release film according to any one of claims 1 to 6, wherein the heat-resistant resin layer 1B has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction of 3% or less. The release film for a process according to claim 9, wherein the heat-resistant resin layer 1B has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 170 ° C is 5% or less. The release film for a process according to any one of claims 1 to 10, wherein the release layer 1A comprises: a fluororesin, a 4-methyl-1-pentene (co)polymer, and a polyphenylene A resin selected from the group consisting of ethylene resins. The process release film according to any one of claims 1 to 11, wherein the heat resistant resin layer 1B comprises a stretched film. The release film for a process according to claim 12, wherein the stretched film is selected from the group consisting of an extended polyester fiber film, a stretched polyamide film, and an extended polypropylene film. The release film for a process according to any one of claims 1 to 13, wherein the heat-resistant resin layer 1B is in the first temperature-increasing process measured by differential scanning calorimetry (DSC) based on JIS K7221 The heat of crystal melting is 20 J/g or more and 100 J/g or less. The release film for a process according to any one of claims 1 to 14, wherein the laminated film further has a release layer 1A', and the release layer 1A, the heat resistant resin layer 1B, and the foregoing The order of the type layer 1A' is contained; the contact angle of the release layer 1A' with respect to water is from 90 to 130. The release film for a process according to claim 15, wherein at least one of the release layer 1A and the release layer 1A' comprises: a fluororesin, a 4-methyl-1-pentene (total) A resin selected from the group consisting of a polymer and a polystyrene resin. The release film for a process according to any one of claims 1 to 16, which is used for a packaging process by a thermosetting resin. The release film for a process according to any one of claims 1 to 17, which is used for a semiconductor packaging process. The process release film according to any one of claims 1 to 17, which is used for a fiber reinforced plastic molding process or a plastic lens forming process. A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming an inner surface of the molding die as in any one of claims 1 to 16 The release film for a semiconductor package process is disposed such that the release layer 1A faces the semiconductor device; after the mold is molded, the semiconductor device and the semiconductor package process are separated Between the types of films, the encapsulation resin is injected into the forming process. A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming a semiconductor package process as described in claim 15 or 16 on the inner surface of the molding die a process of disposing the release layer 1A' opposite to the semiconductor device by using a release film; and after molding the mold, and between the semiconductor device and the release film for the semiconductor package process, The encapsulating resin is injected into the forming process. A release film for a process comprising a release film 2A and a heat resistant resin layer 2B, wherein the release layer 2A has a contact angle with respect to water of 90° to 130°; and the heat resistant resin layer 2B contains The layer 2B1 of the polymer antistatic agent; the tensile modulus of the laminated film at 120 ° C is 75 MPa to 500 MPa. The release film for a process according to claim 22, wherein a thermal dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 120 ° C is 3% or less. The process release film according to claim 22, wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 from the vertical (MD) direction. The sum of the thermal dimensional change rates from ° C to 120 ° C is 6% or less. A release film for a process comprising a release film 2A and a heat resistant resin layer 2B, wherein the release layer 2A has a contact angle with respect to water of 90° to 130°; and the heat resistant resin layer 2B contains The layer 2B1 of the polymer antistatic agent; and the tensile modulus of the laminated film at 170 ° C is 75 MPa to 500 MPa. The release film for a process according to claim 25, wherein a thermal dimensional change ratio of the laminated film in the transverse (TD) direction from 23 ° C to 170 ° C is 4% or less. The process release film according to claim 25, wherein the laminate film has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 from the vertical (MD) direction. The sum of the thermal dimensional change rates from ° C to 170 ° C is 7% or less. The process release film according to any one of the preceding claims, wherein the heat resistant resin layer 2B comprises a layer 2B1 containing a polymer antistatic agent and an adhesive layer 2B2 containing a binder. The release film for a process according to any one of the preceding claims, wherein the heat-resistant resin layer 2B comprises a polymer-based antistatic agent and an adhesive layer 2B3 containing a binder. The release film for a process according to any one of the preceding claims, wherein the heat-resistant resin layer 2B has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of 3% or less. The release film for a process according to claim 30, wherein the heat-resistant resin layer 2B has a thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 120 ° C is 6% or less. The release film for a process according to any one of the preceding claims, wherein the heat-resistant resin layer 2B has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction of 3% or less. The release film for a process according to claim 32, wherein the heat-resistant resin layer 2B has a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse (TD) direction and 23 ° C in the vertical (MD) direction. The sum of the thermal dimensional change rates up to 170 ° C is 5% or less. The release film for a process according to any one of claims 1 to 3, wherein the release layer 2A comprises: a fluororesin, a 4-methyl-1-pentene (co)polymer, and a polyphenylene A resin selected from the group consisting of ethylene resins. The process release film according to any one of the preceding claims, wherein the heat resistant resin layer 2B comprises a stretched film. The release film for a process according to claim 35, wherein the stretched film is selected from the group consisting of an extended polyester fiber film, a stretched polyamide film, and an extended polypropylene film. Process release type as described in any one of claims 22 to 36 In the film, the heat of crystal fusion in the first temperature rising process measured by differential scanning calorimetry (DSC) of the heat resistant resin layer 2B is JISK7221, and is 20 J/g or more and 100 J/g or less. The process release film according to any one of the preceding claims, wherein the release layer 2A has a surface specific resistance of 1 × 10 ¹³ Ω/□ or less. The release film for a process according to any one of the preceding claims, wherein the laminated film further has a release layer 2A', and the release layer 2A, the heat resistant resin layer 2B, and the foregoing The order of the type layer 2A' is contained; the contact angle of the release layer 2A' with respect to water is from 90 to 130. The release film for a process according to claim 39, wherein at least one of the release layer 2A and the release layer 2A' comprises: a fluororesin, a 4-methyl-1-pentene (total) A resin selected from the group consisting of a polymer and a polystyrene resin. The process release film according to claim 39 or 40, wherein the release layer 2A' has a surface specific resistance of 1 × 10 ¹³ Ω/□ or less. The release film for a process according to any one of claims 22 to 41, which is used for a packaging process by a thermosetting resin. The process release film according to any one of claims 22 to 42, which is used in a semiconductor packaging process. The release film for process according to any one of claims 22 to 42 is used for a fiber reinforced plastic molding process or a plastic lens molding process. Cheng. A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming an inner surface of the molding die as recited in any one of claims 22 to 43 a release film for a semiconductor package process, wherein the release layer 2A is disposed to face the semiconductor device; after the mold is molded, the semiconductor device and the semiconductor package process release film are used In between, the encapsulation resin is injected into the forming process. A method of manufacturing a resin-encapsulated semiconductor, comprising: arranging a resin-encapsulated semiconductor device at a predetermined position in a molding die; and forming an inner surface of the molding die as recited in any one of claims 39 to 41; a release film for a semiconductor package process, wherein the release layer 2A' is disposed to face the semiconductor device; after the mold is molded, the semiconductor device and the semiconductor package are removed. The encapsulation resin is injected into the forming process between the films.