KR20180072716A - Title: Release film for process, use thereof, and manufacturing method of resin sealing semiconductor using the same - Google Patents

Abstract

A releasing film for a process which can easily release a molded article after resin sealing without depending on the amount of a metal mold structure or a release agent and can obtain a molded article free from appearance defects such as creases and scratches (process release film).
The above problem is solved by a process for producing a release film for a process, which is a laminated film comprising a release layer A, a heat-resistant resin layer B and an optional release layer A ', wherein the contact angle of the release layer A (and the release layer A' Is 90 DEG to 130 DEG and the laminated film has a predetermined thermal dimensional change rate and / or a tensile modulus of elasticity, or a laminated film including the release layer A and the heat-resistant resin layer B and optionally the release layer A ' Wherein the contact angle of the release layer A (and the release layer A ', if present) of the laminated film with respect to water is 90 ° to 130 °, and the surface resistivity of the release layer A is 1 × 10 ¹³ Ω / □ or less, the heat-resistant resin layer B includes a layer B1 containing a polymeric antistatic agent, and the laminated film is resolved by the process release film having a predetermined thermal dimensional change rate and / or a tensile elastic modulus do.

Description

Title: Release film for process, use thereof, and manufacturing method of resin sealing semiconductor using the same

The first and second inventions relate to a process release film, preferably a release film for a semiconductor encapsulation process. In particular, a semiconductor chip or the like is disposed in a metal mold to perform injection molding The present invention relates to a release film for a process which is disposed between a semiconductor chip or the like and an inner surface of a metal mold, and a process for producing a resin seal semiconductor using the same.

The third and fourth aspects of the present invention relate to a release film for process which can effectively inhibit appearance defects, particularly appearance defects due to creases, of a molded article, preferably a release film for a semiconductor sealing process, The present invention relates to a release film for a process which is disposed between a semiconductor chip and the inner surface of a metal mold when a resin is injected and molded by disposing a semiconductor chip or the like.

2. Description of the Related Art In recent years, it has been studied to reduce the use amount of a sealing resin in accordance with the size and weight reduction of semiconductor packages and the like. It is also required to reduce the amount of release agent contained in the encapsulating resin in order to securely adhere the interface between the semiconductor chip and the resin even if the amount of the encapsulating resin used is reduced. Accordingly, a method of disposing a release film between the inner surface of a metal mold and a semiconductor chip or the like has been adopted as a method of obtaining releasability between a sealing resin and a metal mold after curing and molding.

As such release films, fluorine resin films excellent in releasability and heat resistance (for example, Patent Documents 1 and 2), poly 4-methyl-1-pentene resin films (for example, Patent Document 3) and the like are proposed. However, such a release film tends to generate a crease when it is mounted on the inner surface of the metal mold, and this wrinkle is transferred to the surface of the molded article, which causes a problem of defective appearance.

On the other hand, a laminated release film having a release layer and a heat-resistant layer has been proposed. This release film is intended to obtain releasability in the release layer and to suppress wrinkles and appearance defects in the heat resistant layer. Representative examples of such proposals are based on the relationship between the storage modulus of the release layer and the heat-resistant layer (see, for example, Patent Document 4-6). For example, Patent Document 4 discloses a laminated release film in which the storage modulus of the release layer is relatively low and the storage modulus of the heat resistant layer is relatively high, more specifically, the release layer has a storage elastic modulus E 'at 175 DEG C of 45 MPa or more And a storage elastic modulus E 'at a temperature of 175 deg. C of 100 MPa or more and 250 MPa or less.

Such a release film for a process can be used not only in a semiconductor sealing process but also in a process of forming a reflector for a light emitter such as a light emitting diode (see, for example, Patent Document 7).

Also, the electrification of the release film is also a cause of defective appearance of the molded article. Since the release film used in the semiconductor encapsulation process is a resin film as described above, charging is generally easy. For example, when the releasing film is wound and used, static electricity is generated when the releasing film is peeled off, so that foreign matter such as dust existing in the manufacturing environment adheres to the charged release film, It causes mold contamination. Particularly, a sealing resin of a semiconductor chip has been selected as a sealing resin, so that a shape abnormality or a metal mold contamination caused by adhesion of dust generated from a granular resin to a release film and an appearance defect caused thereby are negligible It is not.

In recent years, there has been an increase in the number of packages that flip-chip semiconductor chips to expose the backside of the chips in response to requests for thinning of packages and improvement of heat dissipation. This process is called a Molded Under Film (MUF) process. In the MUF process, the release film is sealed with the semiconductor chip in direct contact to protect and mask the semiconductor chip. At this time, the release film tends to be charged, and there is a fear that the semiconductor chip is destroyed by the charge-discharge when peeling off.

Therefore, various techniques for preventing the charging of the sealing film have been proposed. For example, in Patent Document 6, a first thermoplastic resin layer in contact with a curable resin, a second thermoplastic resin layer in contact with a metal mold, and an intermediate layer disposed between the first thermoplastic resin layer and the second thermoplastic resin layer are disposed And the intermediate layer comprises a layer containing a polymeric antistatic agent.

[Patent Document 1] Japanese Patent Laying-Open No. 2001-310336 [Patent Document 2] Japanese Unexamined Patent Publication No. 2002-110722 [Patent Document 3] Japanese Unexamined Patent Publication No. 2002-361643 [Patent Document 4] Japanese Unexamined Patent Publication No. 2010-208104 [Patent Document 5] International Publication No. 2015/133631 A1 pamphlet [Patent Document 6] International Publication No. 2015/133630 A1 pamphlet [Patent Document 7] JP-A-2014- 14928

However, with the development of the related art, the demand for release films for process such as release films for semiconductor encapsulation processes is increasing year by year, and there is a demand for release films for processes in which generation of wrinkles is suppressed even under the worse process conditions, Particularly, there is a strong demand for a release film for processes in which the moldability, the suppression of wrinkles and the trackability of the metal mold are balanced to a higher level.

In addition, there is a demand for a releasing film for a process in which the appearance defect of a molded product is suppressed even under more severe processing conditions. In particular, a releasing film for a process which is balanced at a very high level, Is strongly required.

The first invention of the present application has been made in view of the above circumstances, and it is an object of the present invention to provide a molded article which can easily release a molded article after resin sealing without depending on the amount of the metal mold structure or releasing agent and can obtain a molded article free from appearance defects such as wrinkles and scratches And a process for producing the same.

The second invention of the present application has been made in view of such circumstances, and it is an object of the present invention to provide a molded article which can be easily releasably molded, without depending on a metal mold structure or a releasing agent, and which is excellent in wrinkles, scratches, Which can obtain a molded article free from appearance defects such as burrs and adhesion of foreign substances caused by adhesion of the sealing resin of the sealing resin to the release film by static electricity or the like.

The third invention of the present application has been made in view of the above circumstances and it is an object of the present invention to provide a molded article which can easily release a molded article after resin sealing without depending on the amount of a metal mold structure or a releasing agent and is free from appearance defects such as wrinkles and scratches And a process for producing the same.

The fourth invention of the present application has been made in view of the above circumstances, and it is an object of the present invention to provide a molded article which can be easily released without being subjected to a resin molding or a metal mold structure or a mold releasing agent and is excellent in appearance defects such as wrinkles, scratches, Which is capable of obtaining a molded article which is free from the above-mentioned problems.

As a result of intensive investigations to solve the above problems, the present inventors have found that the thermal dimensional change rate at a specific temperature of the process release film, particularly the TD direction of the laminated film constituting the process release film It is important to appropriately control the rate of change in thermal dimensional change in the direction perpendicular to the longitudinal direction at the time of manufacture, hereinafter also referred to as "transverse direction ", is important for suppressing wrinkles when mounted on the inner surface of the metal mold, The present invention has been completed based on these findings.

As a result of intensive investigations to solve the above problems, the present inventors have found that the rate of change of thermal dimensional change at a specific temperature of the release film for process, particularly, the change rate of thermal dimensional change in the TD direction of the laminated film constituting the release film for processing, And that a layer containing a polymer-based charged agent is provided in the heat-resistant resin layer constituting the laminated film is important for suppressing appearance defects, and to complete the second aspect of the present invention It came.

The inventors of the present invention have made intensive investigations to solve the above problems. As a result, they have found that the thermal dimensional change rate at a specific temperature of the process release film, particularly, the TD direction of the laminated film constituting the process release film It is important to appropriately control the rate of change in thermal dimensional change in the direction perpendicular to the longitudinal direction at the time of film production, hereinafter referred to as "transverse direction" 3 inventions have been completed.

As a result of intensive investigations to solve the above problems, the inventors of the present invention have found that the tensile modulus at a specific temperature of a releasing film for a process can be suitably controlled, and that the heat resistant resin layer constituting the laminated film contains a polymeric charge- Layer is particularly important for suppressing appearance defects, and thus the present invention has been accomplished.

That is, the first invention of the present application and each mode thereof are as described in the following [1] to [19].

[One]

As a release film for a process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,

The contact angle of the release layer 1A with respect to water (hereinafter, the 'contact angle with respect to water' may be referred to as a 'water contact angle') is 90 ° to 130 °,

Wherein the thermal dimensional change ratio of the heat resistant resin layer 1B in the transverse direction (TD) direction from 23 ° C to 120 ° C is 3% or less.

[2]

Wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 120 占 폚 in the longitudinal (MD) direction is 6% or less. Release film.

[3]

As a release film for a process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,

The contact angle of the release layer 1A with respect to water is 90to 130,

Wherein the thermal dimensional change ratio of the heat-resistant resin layer 1B in the transverse direction (TD) direction from 23 ° C to 170 ° C is 4% or less.

[4]

Wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 170 占 폚 in the longitudinal (MD) direction is 7% or less. Release film.

[5]

The release film for a process according to any one of [1] to [4], wherein 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% or less.

[6]

Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 1B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 6% Process release film.

[7]

The release film for a process according to any one of [1] to [4], wherein the thermal dimensional change ratio in the transverse (TD) direction of the heat resistant resin layer 1B from 23 ° C to 170 ° C is 3% or less.

[8]

Wherein a sum of a thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 1B and a thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 4% or less. Process release film.

[9]

Wherein the release layer 1A comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene-based resin. To (8) above.

[10]

The release film for a process according to any one of [1] to [9], wherein the heat-resistant resin layer 1B comprises a stretch film.

[11]

The release film for a process according to [10], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film and a stretched polypropylene film.

[12]

Wherein the heat of crystal melting in the first heating step measured by differential scanning calorimetry (DSC) according to JIS K7221 of the heat-resistant resin layer 1B is 15 J / g or more and 60 J / g or less [1 To (11) above.

[13]

The laminated film further has a release layer 1A ', and further includes the release layer 1A, the heat-resistant resin layer 1B and the release layer 1A'

The release film for a process according to any one of [1] to [12], wherein the contact angle of the release layer 1A 'with respect to water is 90 ° to 130 °.

[14]

Wherein at least one of the release layer 1A and the release layer 1A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene resin. Release film.

[15]

The release film for a process according to any one of [1] to [14], which is used in a sealing step with a thermosetting resin.

[16]

The release film for a process according to any one of [1] to [15], which is used in a semiconductor encapsulation process.

[17]

The release film for a process according to any one of [1] to [15], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.

[18]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

A step of disposing a release film for semiconductor encapsulation process according to any one of [1] to [14] on the inner surface of the metal mold so that the release layer 1A faces the semiconductor device;

Molding the metal mold to form a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process;

And a step of forming the resin-sealed semiconductor.

[19]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;

A step of disposing a release film for semiconductor encapsulation process described in [13] or [14] on the inner surface of the metal mold such that the release layer 1A 'faces the semiconductor device;

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

And a step of forming the resin-sealed semiconductor.

The second invention of the present application and each mode thereof are as described in the following [20] to [40].

[20]

As a release film for a process which is a laminated film including a release layer 2A and a heat-resistant resin layer 2B,

The contact angle of the release layer 2A with respect to water in the laminated film is 90 to 130 and the surface resistivity is 1 x 10 < ¹³ >

The heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,

Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.

[21]

Wherein a sum of a thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the direction of the laminated film TD and a thermal dimensional change rate from 23 占 폚 to 120 占 폚 in the longitudinal direction (MD) is 6% or less. Release film.

[22]

As a release film for a process which is a laminated film including a release layer 2A and a heat-resistant resin layer 2B,

The contact angle of the release layer 2A with respect to water in the laminated film is 90 to 130 and the surface resistivity is 1 x 10 < ¹³ >

Wherein the heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,

Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.

[23]

Wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 170 占 폚 in the longitudinal (MD) direction is 7% or less.

[24]

The release film for processing according to any one of [20] to [23], wherein the heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent and an adhesive layer 2B2 including an adhesive.

[25]

The release film for a process according to any one of [20] to [24], wherein the thermal dimensional change ratio in the transverse direction (TD) direction of the heat-resistant resin layer 2B from 23 ° C to 120 ° C is 3% or less.

[26]

Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 6% or less. Process release film.

[27]

The release film for a process according to any one of [20] to [24], wherein a thermal dimensional change ratio in the transverse (TD) direction of the heat-resistant resin layer 2B from 23 ° C to 170 ° C is 3% or less.

[28]

Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 4% or less. Process release film.

[29]

The release layer 2A is a release film for process according to any one of [20] to [28], wherein the releasing layer 2A comprises a resin selected from the group consisting of a fluorine resin, a 4-methyl-1-pentene (co) polymer and a polystyrene- .

[30]

The release film for a process according to any one of [20] to [29], wherein the heat-resistant resin layer 2B comprises a stretched film.

[31]

The release film for a process according to [30], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film and a stretched polypropylene film.

[32]

[20] to [31], wherein the crystal heat of fusion of the heat-resistant resin layer 2B in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 is 15 J / g or more and 60 J / Wherein the releasing film is formed on the surface of the release film.

[33]

The laminated film further has a release layer 2A ', and further includes the release layer 2A, the heat-resisting resin layer 2B, and the release layer 2A'

The release film for a process according to any one of [20] to [32], wherein the contact angle of the release layer 2A 'with respect to water is 90 ° to 130 °.

[34]

The release film for a process according to [33], wherein the release layer 2A 'has a surface resistivity of 1 × 10 ¹³ Ω / □ or less.

[35]

[14] or [15], wherein at least one of the release layer 2A and the release layer 2A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene- And a release film for a process according to the present invention.

[36]

The release film for a process according to any one of [20] to [35], which is used in a sealing step with a thermosetting resin.

[37]

The release film for a process according to any one of [20] to [36], which is used in a semiconductor sealing process.

[38]

The release film for a process according to any one of [20] to [36], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.

[39]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

A step of disposing the release film for semiconductor encapsulation process according to any one of [20] to [35] on the inner surface of the metal mold so that the release layer 2A faces the semiconductor device;

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

And a step of forming the resin-sealed semiconductor.

[40]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

A step of disposing a release film for semiconductor encapsulation process according to any one of [33] to [35] on the inner surface of the metal mold so that the release layer 2A 'faces the semiconductor device;

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

And a step of forming the resin-sealed semiconductor.

The third invention of the present application and the respective aspects thereof are as described in the following [41] to [61].

[41]

As a release film for a process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,

The contact angle of the release layer 3A with respect to water is 90to 130,

Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.

[42]

The release film for a process according to [41], wherein a rate of change in thermal dimensional change from 23 ° C to 120 ° C in the transverse direction (TD) direction of the laminated film is 3% or less.

[43]

41] or [42], wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 120 占 폚 in the longitudinal (MD) And a release film for a process according to the present invention.

[44]

As a release film for a process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,

The contact angle of the release layer 3A with respect to water is 90to 130,

Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.

[45]

The release film for a process according to [44], wherein a rate of change in thermal dimensional change from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film is 4% or less.

[46]

[44] or [45], wherein a sum of a thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and a thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction is 7% And a release film for a process according to the present invention.

[47]

The release film for a process according to any one of [41] to [46], wherein the thermal dimensional change ratio of the heat-resistant resin layer 3B in the transverse (TD) direction from 23 ° C to 120 ° C is 3% or less.

[48]

Wherein a sum of a thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and a thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 6% or less. Process release film.

[49]

The release film for a process according to any one of [41] to [46], wherein the thermal dimensional change ratio in the transverse (TD) direction of the heat resistant resin layer 3B from 23 ° C to 170 ° C is 3% or less.

[50]

Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) direction is 5% or less. Process release film.

[51]

The release layer 3A is a release film for process according to any one of [41] to [50], which comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- .

[52]

The release film for a process according to any one of [41] to [51], wherein the heat-resistant resin layer 3B comprises a stretched film.

[53]

The release film for a process according to [52], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film and a stretched polypropylene film.

[54]

[41] to [53], wherein the heat of fusion of the heat-resistant resin layer 3B in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 is 20 J / g or more and 100 J / Wherein the releasing film is a film for a process.

[55]

The laminated film further has a release layer 3A 'and sequentially includes the release layer 3A, the heat-resistant resin layer 3B and the release layer 3A'

The release film for a process according to any one of [41] to [54], wherein the contact angle of the release layer 3A 'with respect to water is 90 ° to 130 °.

[56]

Wherein at least one of the release layer 3A and the release layer 3A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene resin. Release film.

[57]

The release film for process according to any one of [41] to [56], which is used in a sealing step with a thermosetting resin

[58]

The release film for a process according to any one of [41] to [57], which is used in a semiconductor encapsulation process.

[59]

The release film for a process according to any one of [41] to [57], which is used for a fiber-reinforced plastic molding process or a plastic lens molding process.

[60]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

A step of disposing the release film for semiconductor encapsulation process according to any one of [41] to [56] on the inner surface of the metal mold so that the release layer 3A faces the semiconductor device;

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

Wherein the step of forming the resin-sealed semiconductor comprises the steps of:

[61]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

The step of disposing the release film for semiconductor encapsulation process described in [55] or [56] so that the release layer 3A 'is opposed to the semiconductor device on the inner surface of the metal mold,

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

Wherein the step of forming the resin-sealed semiconductor comprises the steps of:

The fourth invention of the present application and the respective aspects thereof are as described in the following [62] to [86].

[62]

A releasing layer 4A and a heat-resisting resin layer 4B,

The contact angle of the release layer 4A with respect to water is 90to 130,

The heat-resistant resin layer 4B includes a layer 4B1 containing a polymeric antistatic agent,

Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.

[63]

The release film for a process according to [62], wherein a rate of change in thermal dimensional change from 23 ° C to 120 ° C in the transverse direction (TD) direction of the laminated film is 3% or less.

[64]

62] or [63], wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 120 占 폚 in the longitudinal (MD) And a release film for a process according to the present invention.

[65]

A releasing layer 4A and a heat-resisting resin layer 4B,

The contact angle of the release layer 4A with respect to water is 90to 130,

The heat-resistant resin layer 4B includes a layer 4B1 containing a polymeric antistatic agent,

Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.

[66]

The release film for a process according to [65], wherein a rate of change in thermal dimensional change from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film is 4% or less.

[67]

65] or [66], wherein the sum of the thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) And a release film for a process according to the present invention.

[68]

The heat-resistant resin layer 4B includes the layer 4B1 containing a polymeric antistatic agent and the adhesive layer 4B2 including an adhesive. The processable release film according to any one of [62] to [67]

[69]

The heat-resistant resin layer 4B is a release film for a process according to any one of [62] to [67], wherein the heat-resistant resin layer 4B comprises a layer 4B3 containing a polymeric antistatic agent and an adhesive.

[70]

The release film for a process according to any one of [62] to [69], wherein the thermal dimensional change ratio in the transverse (TD) direction of the heat-resistant resin layer 4B from 23 ° C to 120 ° C is 3% or less.

[71]

Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 6% or less. Process release film.

[72]

The release film for processing according to any one of [62] to [69], wherein the thermal dimensional change ratio in the transverse (TD) direction of the heat-resistant resin layer 4B from 23 ° C to 170 ° C is 3% or less.

[73]

Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) direction is 5% or less. Process release film.

[74]

The release layer 4A is a release film for process according to any one of [62] to [73], which comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- .

[75]

The release film for a process according to any one of [62] to [74], wherein the heat-resistant resin layer 4B comprises a stretched film.

[76]

The release film for a process according to [75], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film and a stretched polypropylene film.

[77]

[62] to [76], wherein the heat of crystal melting in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 of the heat-resistant resin layer 4B is 20 J / g or more and 100 J / Wherein the releasing film is a film for a process.

[78]

The release film for a process according to any one of [62] to [77], wherein the release layer 4A has a surface resistivity of 1 x 10 < ¹³ >

[79]

The laminated film further has a release layer 4A ', and further includes the release layer 4A, the heat-resistant resin layer 4B and the release layer 4A'

The release film for a process according to any one of [62] to [78], wherein the contact angle of the release layer 4A 'with respect to water is 90 ° to 130 °.

[80]

At least one of the release layer 4A and the release layer 4A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene resin. Release film.

[81]

The release film for a process according to [79] or [80], wherein the release layer 4A 'has a surface resistivity of 1 x 10 < ¹³ >

[82]

The release film for process according to any one of [62] to [81], which is used in the sealing step with a thermosetting resin

[83]

The release film for a process according to any one of [62] to [82], which is used in a semiconductor sealing process.

[84]

The release film for a process according to any one of [62] to [82], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.

[85]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

A step of disposing the release film for semiconductor encapsulation process described in any one of [62] to [83] on the inner surface of the metal mold so that the release layer 4A faces the semiconductor device;

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

Wherein the step of forming the resin-sealed semiconductor comprises the steps of:

[86]

A method for producing a resin-sealed semiconductor,

Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,

The step of disposing the release film for semiconductor encapsulation process according to any one of [79] to [81] so that the release layer 4A 'is opposed to the semiconductor device on the inner surface of the metal mold,

A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,

Wherein the step of forming the resin-sealed semiconductor comprises the steps of:

The term "semiconductor device" is also a concept including a semiconductor element (chip).

The release film for a process according to the first invention of the present application has a high level of releasability, suppression of wrinkles and followability of metal moldings which can not be realized in the prior art. Therefore, by using this, a molded article obtained by resin- And a molded product free from appearance defects such as wrinkles and scratches can be produced with high productivity.

The release film for a process according to the second invention of the present invention has a high level of releasability, suppression of defective appearance, and ability to follow a metal mold, which could not be realized in the prior art. Therefore, by using the release film, a molded product obtained by resin- And a molded article free from appearance defects such as wrinkles, scratches, and abnormal shapes (foreign matters adhered), etc. can be produced with high productivity. Even if the sealing resin is in the form of solid granules at room temperature, defective molding such as roughness due to adhesion of the sealing resin to the release film due to static electricity can be prevented in advance. The process release film of the second invention of the present application is particularly suitable for use in a sealing device employing a granular resin as a sealing resin.

The release film for a process according to the third invention of the present invention has a high level of releasability, suppression of wrinkles and followability of metal moldings which can not be realized in the prior art. Therefore, by using this, a molded article obtained by resin- And a molded article free from appearance defects such as wrinkles and scratches can be produced with high productivity.

The release film for a process according to the fourth invention of the present invention has a high level of releasability, suppression of appearance defects, and ability to follow a metal mold, which could not be realized in the prior art. Therefore, by using the release film, a molded product obtained by resin- And a molded article free from appearance defects such as wrinkles, scratches, and abnormal shapes (foreign matters adhered), etc. can be produced with high productivity. The process release film of the fourth invention of the present application is particularly suitable for use in a sealing device employing a granular resin as a sealing resin.

1 is a schematic view showing an example of a release film for processing of the present invention.
2 is a schematic view showing another example of the release film for processing of the present invention.
Fig. 3-1 is a schematic diagram showing an example of a method for producing a resin-sealed semiconductor using the release films for processing according to the first, third, and fourth inventions of the present application.
3-2 is a schematic diagram showing an example of a method for producing a resin-sealed semiconductor using the release film for processing according to the second invention of the present application.
4A is a schematic view showing an example of a method for producing a resin-sealed semiconductor using the release film for processing of the present invention.
4B is a schematic diagram showing an example of a method for producing a resin-sealed semiconductor using the release film for processing of the present invention.
Fig. 5 is a schematic view showing an example of a resin-sealing semiconductor obtained by the method of manufacturing the resin-sealed semiconductor of Figs. 4A and 4B.

Process release film

The process release film of the first invention of the present application includes the following four embodiments.

(Embodiment 1-1)

As a release film for a process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,

The contact angle of the release layer 1A with respect to water is 90to 130,

Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.

(Embodiment 1-2)

As a release film for a process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,

The contact angle of the release layer 1A with respect to water is 90to 130,

Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.

(Embodiments 1-3)

As a release film for a process, which is a laminated film comprising a release layer 1A, a heat-resistant resin layer 1B and a release layer 1A '

The contact angle of the release layer 1A and the release layer 1A 'with respect to water is 90 ° to 130 °,

Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.

(Embodiments 1-4)

As a release film for a process, which is a laminated film comprising a release layer 1A, a heat-resistant resin layer 1B and a release layer 1A '

The contact angle of the release layer 1A and the release layer 1A 'with respect to water is 90 ° to 130 °,

Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.

As is apparent from the respective embodiments, the release film for process according to the first aspect of the present invention (hereinafter, simply referred to as "release film") comprises a release layer 1A having releasability to a molded article and a metal mold, And a heat-resistant resin layer 1B for supporting the release layer.

The process release film of the first invention of the present application is disposed on the inner surface of the molded metal mold when the semiconductor element or the like is sealed in the molded metal mold. At this time, it is preferable to dispose the release layer 1A of the release film (which may be the release layer 1A 'if the release layer 1A' is present) on the resin-sealed semiconductor element or the like (molded product) side. By disposing the release film of the first invention of the present application, the resin-sealed semiconductor element or the like can be easily released from the metal mold.

The contact angle of the release layer 1A with respect to water is 90to 130. By having such a contact angle, the release layer 1A has low wettability and can easily release the molded article without adhering to the surface of the hardened sealing resin and the metal mold. can do.

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

As described above, since the release layer 1A (in some cases, the release layer 1A ') is disposed on the side of the molded article, the occurrence of wrinkles in the release layer 1A (and in some cases, the release layer 1A' desirable. There is a high possibility that the formed wrinkles are transferred to the molded article and the appearance of the molded article is defective.

The first invention of the present application provides a laminated film constituting a process release film for achieving the above object, which comprises a release layer 1A (and optionally a release layer 1A ') and a heat-resistant resin layer 1B for supporting the release layer A laminated film is used which is a laminated film and whose thermal dimensional change ratio in the transverse direction (TD) indicates a specific value.

That is, the laminated film including the releasing layer 1A (and optionally the releasing layer 1A ') and the heat-resistant resin layer 1B supporting the releasing layer has a thermal dimension in the TD direction (transverse direction) from 23 DEG C to 120 DEG C The change ratio is 3% or less, or the thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the TD direction (transverse direction) is 4% or less. The laminated film has a thermal dimensional change ratio of 3% or less from 23 ° C to 120 ° C in the TD direction (transverse direction) and a thermal dimensional change ratio of 23% to 170 ° C in the TD direction (transverse direction) of 4% Is more preferable.

The thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (transverse direction) of the laminated film is 3% or less, or the thermal dimensional change rate from 23 ° C to 170 ° C in the TD direction (transverse direction) is 4% It is possible to effectively suppress occurrence of wrinkles in the release layer in a resin sealing step or the like. Since the laminated film constituting the process release film has a thermal dimensional change ratio in the transverse (TD) direction as described above, the mechanism by which the generation of wrinkles in the release layer is suppressed is not necessarily clear, but the thermal expansion / It is presumed that the use of this small laminated film is related to suppression of thermal expansion / contraction of the release layer 1A (or release layer 1A ') due to heating / cooling in the process.

The laminated film constituting the process release film of the first invention of the present invention preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of from 23 ° C to 120 ° C of 2.5% or less, more preferably 2.0% or less, % Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 120 ° C.

The laminated film constituting the process release film of the first invention of the present invention preferably has a thermal dimensional change ratio in the TD direction (transverse direction) from 23 ° C to 170 ° C of 3.5% or less, more preferably 3.0% or less, % Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 170 ° C.

Since the resin layer in which the thermal dimensional change ratio in the transverse (TD) direction exhibits the above-mentioned specific value is used as the heat-resistant resin layer 1B, the mechanism by which the occurrence of wrinkles in the release layer is more effectively suppressed is not necessarily clear, but a relatively thermal expansion / It is presumed that the use of the small heat-resistant resin layer 1B is related to suppression of thermal expansion / contraction of the release layer 1A (or release layer 1A ') due to heating / cooling during processing.

The release film for a process according to the first invention of the present invention, which is a laminated film comprising a release layer 1A (and optionally a release layer 1A ') and a heat-resistant resin layer 1B for supporting the release layer, It is preferable that the sum of the dimensional change rate and the thermal dimensional change rate of the MD direction (longitudinal direction at the time of production of the film, hereinafter also referred to as " longitudinal direction ") is not more than a specific value.

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

The thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film including the release layer 1A (and optionally the release layer 1A ') and the heat resistant resin layer 1B, Is 6% or less, it is possible to more effectively suppress the occurrence of wrinkles when the metal mold is mounted in the metal mold.

The thermal dimensional change ratio in the transverse direction (TD) direction including the release layer 1A (and optionally the release layer 1A ') and the heat-resistant resin layer 1B from 23 ° C to 170 ° C and the longitudinal direction The laminated film preferably has a thermal dimensional change ratio from 23 DEG C to 170 DEG C in the TD direction (transverse direction) and a thermal dimensional change ratio in the longitudinal (MD) direction of 23 DEG C to 170 DEG C, Lt; 0 > C to 170 < 0 > C is preferably -5.0% or more.

The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction is 7% or less, It is possible to more effectively suppress the generation of wrinkles when the wrinkles are formed.

Heterogeneous layer  1A

The release layer 1A constituting the process release film of the first invention of the present application has a contact angle with respect to water of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115 °, Preferably from 100 [deg.] To 110 [deg.]. It is preferable to include a resin selected from the group consisting of a fluorine resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene-based resin from the viewpoints of excellent moldability of the molded article and ease of obtaining.

The fluororesin usable for the release layer 1A may be a resin containing a constituent unit derived from tetrafluoroethylene. It may be a tetrafluoroethylene homopolymer, but may be a copolymer with another olefin. Examples of other olefins include ethylene. A copolymer containing tetrafluoroethylene and ethylene as monomer constituent units is a preferred example. In such a copolymer, the proportion of the constituent unit derived from tetrafluoroethylene is 55 to 100% by mass, and the constituent unit derived from ethylene Is preferably 0 to 45% by mass.

The 4-methyl-1-pentene (co) polymer which can be used for the release layer 1A may be a homopolymer of 4-methyl-1-pentene, (Hereinafter referred to as an " olefin having 2 to 20 carbon atoms ").

In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, an olefin having 2 to 20 carbon atoms to be copolymerized with 4-methyl-1-pentene is added to 4-methyl- Flexibility can be given. Examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, hexadecene, 1-heptadecene, 1-octadecene, 1-eicosen, 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 proportion of the constituent unit derived from 4-methyl-1-pentene is 96 to 99 mass% And the proportion of the structural units derived from olefins of 2 to 20 is preferably 1 to 4% by mass. By decreasing the content of the constituent unit derived from olefin having 2 to 20 carbon atoms, the copolymer can be hardened, that is, the storage elastic modulus E 'can be made high, which is advantageous for suppressing occurrence of wrinkles such as sealing processes. On the other hand, by increasing the content of the olefin-derived structural unit having 2 to 20 carbon atoms, the copolymer can be softened, that is, the storage elastic modulus E 'can be lowered, which is advantageous for improving the followability of the metal mold.

The 4-methyl-1-pentene (co) polymer may be prepared by methods known to those skilled in the art. For example, a known catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst or the like. It is preferable that the 4-methyl-1-pentene (co) polymer is a (co) polymer having high crystallinity. As the crystalline copolymer, any of a copolymer having an isotactic structure and a copolymer having a syndiotactic structure may be used. In particular, a copolymer having an isotactic structure is preferable from the viewpoint of physical properties, It is also easy to obtain. Further, the 4-methyl-1-pentene (co) polymer can be formed into a film form, so that stereoregularity and molecular weight are not particularly limited as long as the 4-methyl-1-pentene (co) polymer has strength enough to withstand temperature or pressure at the time of metal die casting. The 4-methyl-1-pentene copolymer may be a commercially available copolymer such as, for example, TPX (registered trademark) of Mitsui Chemicals Co.,

The polystyrene type resin that can be used for the release layer 1A includes a homopolymer and a copolymer of styrene, and the structural unit derived from styrene contained in the polymer is preferably at least 60% by weight, more preferably at least 80% Or more.

The polystyrene type resin may be isotactic polystyrene or syndiotactic polystyrene, but isotactic polystyrene is preferable from the viewpoints of transparency, availability and the like, and syndiotactic polystyrene is preferable from the viewpoints of releasability, heat resistance and the like. One kind of polystyrene may be used alone, or two or more kinds of polystyrene may be used in combination.

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

In order to have crystallinity in the release layer 1A, for example, in the case of a fluororesin, it is preferable to include at least a structural unit derived from tetrafluoroethylene, and in the case of 4-methyl-1-pentene (co) It is preferable to include at least a constituent unit derived from 1-pentene, and in the polystyrene-based resin, it is preferable to include at least syndiotactic polystyrene. The resin constituting the release layer 1A contains a crystal component, which makes it difficult for wrinkles to be generated in the resin sealing step and the like, and is suitable for suppressing occurrence of appearance defect due to transfer of wrinkles to the molded article.

The resin containing the crystalline component constituting the release layer 1A preferably has a heat of crystal fusion of 15 J / g or more and 60 J / g or more in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221, g or less, more preferably 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, heat resistance and releasability that can withstand the hot press molding in the resin sealing step and the like can be more effectively expressed, and the rate of dimensional change can be suppressed, so that occurrence of wrinkles can be prevented. On the other hand, when the crystalline melting heat quantity is 60 J / g or less, the releasing layer 1A has appropriate hardness, so that sufficient followability to the metal mold of the film can be obtained in the resin sealing step and the like.

The release layer 1A may contain another resin besides a fluororesin, a 4-methyl-1-pentene copolymer, and / or a polystyrene-based resin. In this case, it is preferable that the hardness of the other resin is relatively high. Examples of other resins include polyamide-6, polyamide-66, polybutylene terephthalate, and polyethylene terephthalate. As described above, even when the release layer 1A contains, for example, a large amount of soft resin (for example, when a 4-methyl-1-pentene copolymer contains a large amount of olefins having 2 to 20 carbon atoms) By additionally including a high resin, the release layer 1A can be made hard, and it is advantageous in suppressing the generation of wrinkles in the sealing step and the like.

The content of such another resin is preferably 3 to 30 mass%, for example, with respect to the resin component constituting the release layer 1A. When the content of the other resin is 3 mass% or more, the effect of the addition can be made substantial, and when it is 30 mass% or less, releasability to metal moldings and molded articles can be maintained.

The release layer 1A may contain, in addition to the fluororesin, 4-methyl-1-pentene (co) polymer and / or polystyrene resin, a thermostable stabilizer, a weatherability stabilizer, Rusting inhibitors, copper harm-resistant stabilizers, antistatic agents, and the like, which are generally incorporated in film resins. The content of such an additive may be, for example, 0.0001 to 10 parts by weight based on 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 1A is not particularly limited as long as the releasability to the molded article is sufficient, but is usually 1 to 50 mu m, preferably 5 to 30 mu m.

The surface of the release layer 1A may have a concavo-convex shape if necessary, thereby improving the releasability. The method of imparting unevenness to the surface of the release layer 1A is not particularly limited, but general methods such as embossing can be employed.

Heterogeneous layer  1A '

The process release film of the first invention of the present application may have a release layer 1A 'in addition to the release layer 1A and the heat-resistant resin layer 1B. That is, the process release film of the first invention of the present application may be a release film for process which is a laminated film comprising a release layer 1A, a heat-resistant resin layer 1B and a release layer 1A 'sequentially.

The contact angle of the release layer 1A 'which can constitute the process release film of the first invention of the present invention with respect to water is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115 ° , More preferably from 100 [deg.] To 110 [deg.]. The preferable materials, constitution, physical properties, etc. of the release layer 1A 'are the same as those described above for the release layer 1A.

The release layer 1A and the release layer 1A 'in the case where the process release film is a laminated film sequentially including the release layer 1A, the heat-resistant resin layer 1B and the release layer 1A' may be layers having the same constitution, have.

From the viewpoints of preventing a curve and ease of handling by having the same releasability on all sides, the releasing layer 1A and the releasing layer 1A 'preferably have the same or substantially the same constitution, and the releasing layer 1A and the releasing layer 1A ', For example, the release layer 1A is made excellent in releasability from the metal mold, and the releasing layer 1A' is made excellent in releasability from the molded product, and the like It is preferable that the release layer 1A and the release layer 1A 'have different structures.

In the case where the release layer 1A and the release layer 1A 'have different structures, the release layer 1A and the release layer 1A' are made of the same material, but they can have different structures such as thickness and the like. .

Heat-resistant resin layer 1B

The heat-resistant resin layer 1B constituting the process release film of the first invention of the present invention supports the release layer 1A (and the release layer 1A 'as the case may be) and has a function of suppressing the generation of wrinkles due to the temperature of the metal mold .

In the release film for a process according to the first aspect of the present invention, the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 1B is 3% or less, or 23 DEG C It is preferable that the thermal dimensional change ratio up to 170 캜 is 3% or less. In the heat-resistant resin layer 1B, the thermal dimensional change ratio in the transverse direction (TD) from 23 DEG C to 120 DEG C is 3% or less, more preferably 3% or less in the transverse direction (TD) direction from 23 DEG C to 170 DEG C Do.

An optional resin layer including a non-oriented film can be used for the heat-resistant resin layer 1B, but it is particularly preferable to include a stretched film.

The stretched film tends to have a low thermal expansion coefficient or a negative thermal expansion due to the effect of stretching in the manufacturing process, and the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) is 3% or less, or the heat resistant resin layer 1B It is relatively easy to realize a characteristic that the rate of change in thermal dimensional change from 23 DEG C to 170 DEG C in the transverse direction (TD) is 3% or less. Therefore, 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 DEG C to 120 DEG C is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

The thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat-resistant resin layer 1B is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

The stretched film may be a uniaxially stretched film or a biaxially stretched film. In the case of a uniaxially stretched film, it may be any of longitudinal stretching and transverse stretching, but it is preferred that stretching proceeds at least in the transverse (TD) direction.

The method and apparatus for obtaining the stretched film are not particularly limited, and the stretching can be performed by a method known in the art. For example, it can be stretched by a heating roll and a tenter-type stretching machine.

As the stretched film, it is preferable to use a stretched film selected from the group consisting of stretched polyester film, stretched polyamide film and stretched polypropylene film. Such a stretched film is comparatively easy to lower the thermal expansion coefficient in the transverse (TD) direction due to stretching or to be negative, has mechanical properties suitable for the purposes of the first invention of the present invention, and is relatively easy to obtain at low cost, It is particularly suitable as a stretched film in layer 1B.

As the stretched polyester film, a stretched polyethylene terephthalate (PET) film and a stretched polybutylene terephthalate (PBT) film are preferable, and a biaxially stretched polyethylene terephthalate (PET) film is particularly preferable.

The polyamide constituting the oriented polyamide film is not particularly limited, but polyamide-6, polyamide-66 and the like can be preferably used.

As the stretched polypropylene film, a uniaxially stretched polypropylene film and a biaxially stretched polypropylene film can be preferably used.

The stretching magnification is not particularly limited and may appropriately be set appropriately in order to appropriately control the rate of change in thermal dimensional and to realize suitable mechanical properties. For example, in the case of stretched polyester film, And in the case of the stretched polyamide film, it is preferable that the stretching ratio is in the range of 2.7 to 5.0 times in both b, s, longitudinal and transverse directions. In the case of the stretched polypropylene film, in the case of the biaxially stretched polypropylene film , The longitudinal direction and the transverse direction are preferably in the range of 5.0 to 10.0 times, and in the case of the uniaxially stretched polypropylene film, the longitudinal direction is preferably in the range of 1.5 to 10.0 times.

The heat-resistant resin layer 1B preferably has heat resistance capable of withstanding the temperature of the metal mold (generally 120 to 180 DEG C) at the time of molding in view of controlling the strength of the film and the rate of change in thermal dimensional thereof to an appropriate range. From this viewpoint, the heat-resistant resin layer 1B preferably contains a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 125 DEG C or higher, more preferably 155 DEG C or higher and 300 DEG C or lower More preferably 185 or more and 210 占 폚 or less, and particularly preferably 185 or more and 205 占 폚 or less.

In the above-described embodiment, the heat-resistant resin layer 1B preferably includes a crystalline resin having a crystalline component. As the crystalline resin contained in the heat-resistant resin layer 1B, a part or all of a crystalline resin such as a polyester resin, a polyamide resin, and a polypropylene resin can be used. Concretely, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the above-mentioned crystalline resin in the heat-resistant resin layer 1B, wrinkles are less likely to occur in the resin sealing step and the like, and it is more advantageous to suppress wrinkles from being transferred to the molded article and causing appearance defects.

The resin constituting the heat-resistant resin layer 1B preferably has a crystal melting heat amount of not less than 20 J / g and not more than 100 J / g in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221, More preferably 25 J / g or more and 55 J / g or less, even more preferably 28 J / g or more and 50 J / g or less, more preferably 28 J / g or more and 40 J / g or less, and more preferably 28 J / g or more and 35 J / g or less. If it is 20 J / g or more, heat resistance and releasability that can withstand hot press forming such as a resin sealing process can be effectively exhibited, and also the rate of dimensional change can be suppressed to a small extent, so that occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal fusion is not more than 100 J / g, the heat-resistant resin layer 1B can be given appropriate hardness, so that it is possible to ensure sufficient followability to the metal mold in the resin sealing process or the like, There is no possibility of becoming easy. Further, in this embodiment, the crystal melting heat quantity is determined by the relationship between the heat quantity (J / g) of the longitudinal axis obtained in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 and the temperature Refers to a numerical value obtained by summing up peak areas having peaks at 120 占 폚 or higher in the chart shown.

The heat of crystal melting of the heat-resistant resin layer 1B can be adjusted by appropriately setting heating, cooling conditions and stretching conditions in the production of the film.

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

Other layers

The process release film of the first invention of the present application 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 is against the object of the first invention of the present application. For example, an adhesive layer may be provided between the release layer 1A (or release layer 1A ') and the heat-resistant resin layer 1B as required. The material used for the adhesive layer is not particularly limited as long as it can firmly adhere the release layer 1A and the heat-resistant resin layer 1B and does not peel off in the resin sealing step or the release step.

For example, when the releasing layer 1A (or the releasing layer 1A ') contains a 4-methyl-1-pentene copolymer, the adhesive layer may be a graft- An olefin-based adhesive resin composed of a copolymer resin, a 4-methyl-1-pentene copolymer and an -olefin copolymer, and the like. When the releasing layer 1A (or releasing layer 1A ') contains a fluorine resin, 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 can improve the adhesion of the release layer 1A (or release layer 1A ') and the heat-resistant resin layer 1B, and is, for example, 0.5 to 10 μm.

The total thickness of the release film for process according to the first aspect of the present invention is not particularly limited, but is preferably 10 to 300 占 퐉, more preferably 30 to 150 占 퐉. When the total thickness of the release film is within the above range, handling property when used as a roll is good, and the amount of film to be wasted is small, which is preferable.

Hereinafter, preferred embodiments of the release film for process according to the first aspect of the present invention will be described in more detail. 1 is a schematic view showing an example of a release film for a process having 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 side thereof with an adhesive layer 14 therebetween.

The release layer 16 is the release layer 1A described above, the heat-resistant resin layer 12 is the heat-resisting resin layer 1B described above, and the adhesive layer 14 is the adhesive layer described above. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing step; The heat-resistant resin layer 12 is desirably disposed on the side in contact with the inner surface of the metal mold in the sealing step.

2 is a schematic view showing an example of a release film for a process having a five-layer structure. Members having the same functions as those in Fig. 1 are denoted by the same reference numerals. As shown in Fig. 2, the release film 20 has a release layer 16A and a release layer 16B formed through the heat-resistant resin layer 12 and the adhesive layer 14 on both sides thereof. The release layer 16A is the release layer 1A described above and the heat-resistant resin layer 12 is the heat-resisting resin layer 1B described above. The release layer 16B is the release layer 1A 'described above, Adhesive layer.

The compositions of the release layers 16A and 16B may be the same or different from each other. The release layers 16A and 16B may have the same or different thicknesses. However, if the release layers 16A and 16B have the same composition and thickness as each other, they are symmetrical, which is preferable because warping of the release film itself is less likely to occur. In particular, it is preferable that the release film of the first invention of the present invention suppresses warpage because stress may be generated by heating in the sealing process. Thus, if the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12, it is preferable that good releasability can be obtained in both the molded article and the metal mold inner surface.

Process for producing release film for process

The process release film of the first invention of the present application can be produced by any method. For example, 1) a method (co-extrusion molding method) of producing a releasing film for processing by co-extrusion molding and laminating the releasing layer 1A and the heat-resistant resin layer 1B; 2) (Coating method) of applying and drying a molten resin of a resin to be an adhesive layer, or applying and drying a resin solution in which a release layer 1A and a resin as an adhesive layer are dissolved in a solvent, 3) a method in which a film to be a releasing layer 1A and a film to be a heat-resistant resin layer 1B are prepared in advance and a releasing film for a process is produced by laminating (laminating) the film (laminating method).

In the method of 3), various known lamination methods may be employed as the method of laminating the respective resin films, and examples thereof include extrusion lamination, dry lamination and thermal lamination.

In the dry lamination method, each resin film is laminated using an adhesive. As the adhesive, known adhesives for dry lamination can be used. For example, a polyvinyl acetate adhesive; (Methacrylate, acrylonitrile, styrene, etc.) or a homopolymer or copolymer of an acrylic acid ester (such as ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate) or an acrylic ester and other monomers Acrylic ester-based adhesives; Cyanoacrylate-based adhesives; An ethylene copolymer system adhesive comprising a copolymer of ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc.); Cellulosic adhesives; Polyester-based adhesives; Polyamide adhesives; Polyimide-based adhesives; An amino resin-based adhesive comprising a urea resin or a melamine resin; Phenolic resin adhesives; Epoxy adhesive; Polyurethane-based adhesives for crosslinking polyol (polyetherpolyol, polyester polyol, etc.) with isocyanate and / or isocyanurate; Reactive (meth) acrylic adhesives; Rubber adhesives composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber and the like; Silicone adhesives; An inorganic adhesive composed of an alkali metal silicate, a low melting point glass or the like; Etc. may be used. The resin film laminated by the method 3) may be a commercially available resin film or a resin film produced by a known manufacturing method. The resin film may be subjected to a surface treatment such as a corona treatment, an atmospheric pressure plasma treatment, a vacuum plasma treatment, or a primer coating treatment. The production method of the resin film is not particularly limited, and a known production method can be used.

1) The co-extrusion molding method is preferable because defects due to impurities or the like between the resin layer serving as the release layer 1A and the resin layer serving as the heat-resistant resin layer 1B and the warpage of the release film are less likely to occur. 3) The lamination method (lamination method) is a suitable method when a stretched film is used for the heat-resistant resin layer 1B. In this case, it is preferable to form an appropriate adhesive layer at the interface between the films as necessary. After the adhesiveness between the films is enhanced, surface treatment such as corona discharge treatment can be performed on the interface between the films as required.

The process release film may be uniaxially or biaxially stretched as required, thereby increasing the strength of the film film.

The coating means of the above 2) coating method is not particularly limited, but various coaters such as a roll coater, a die coater and a spray coater are used. The melt extrusion means is not particularly limited, but for example, a T-die or an extruder having an inflation die is used.

Manufacture process

The process release film of the first invention of the present invention can be used by disposing a semiconductor chip or the like in a metal mold and arranging it between the semiconductor chip and the inner surface of the metal mold when injection molding the resin. By using the release film for process according to the first invention of the present application, it is possible to effectively prevent defective release and occurrence of roughness from metal molds.

The resin used in the production process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the art, and epoxy-based thermosetting resins are particularly preferred.

In the above manufacturing process, the sealing of the semiconductor chip is the most typical, but the present invention is not limited to this, and the first invention can be applied to a fiber reinforced plastic molding process, a plastic lens molding process, and the like.

Fig. 3-1, Fig. 4A and Fig. 4B are schematic diagrams showing an example of a method for producing a resin-sealed semiconductor using the release film of the first invention of the present application.

As shown in Fig. 3-1a, the release film 1 of the first invention of the present application is fed into a molded metal mold 2 by rolls 1-2 and rolls 1-3 in a roll-like roll. Next, the release film 1 is placed on the inner surface of the upper mold (upper mold) The inner surface of the upper mold 2 can be vacuum-sucked to adhere the releasing film 1 to the inner surface of the upper mold 2 as required. A semiconductor chip 6 disposed on a substrate is disposed on a molding die lower mold 5 and a sealing resin is placed on the semiconductor die 6 or a liquid phase The sealing resin 4 is accommodated between the upper metal mold 2 and the lower metal mold 5 on which the release film 1 which is exhausted and sucked by injecting the sealing resin is arranged. Next, as shown in Fig. 3-1B, the upper metal mold 2 and the lower metal mold 5 are closed through the mold release film 1 of the first invention of the present invention to cure the sealing resin 4 .

3-1c, the sealing resin 4 is fluidized in the metal mold, the sealing resin 4 flows into the space and is filled so as to surround the side surface of the semiconductor chip 6, The molds of the upper mold 2 and the lower mold 5 are opened and taken out. After the mold is opened and the molded article is taken out, the mold release film 1 is repeatedly used or a new mold release film is supplied and subjected to the following resin molding molding.

The release film of the first invention of the present invention is brought into close contact with the upper metal mold to interpose between the metal mold and the sealing resin to prevent the resin from adhering to the metal mold by resin mold and to prevent the resin mold surface of the metal mold from being dirty The molded article can easily be released without being stretched.

Alternatively, the release film may be supplied newly for every single resin mold operation to be resin molded, or may be newly supplied and resin molded for each resin mold operation for a plurality of times.

The sealing resin may be a liquid resin or a solid-state resin at room temperature, but a sealing material such as a liquid-phase sealing material can be suitably employed. Specifically, epoxy resin (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolak type epoxy resin, etc.) is used as the sealing resin material, and a polyimide resin Based resin), a silicone resin (thermosetting addition type), and the like can be used. In addition, resin sealing condition which is varied in accordance with the sealing resin used, e.g., curing temperature 120 ℃ ~ 180 ℃, can be appropriately set in forming pressure 10 ~ 50 kg / cm ^2, curing times range from 1 to 60 minutes.

Before and after the step of disposing the release film 1 on the inner surface of the molded metal mold 8 and the step of disposing the semiconductor chip 6 in the molded metal mold 8 are not particularly limited and can be performed simultaneously The release film 1 can be disposed after the semiconductor chip 6 is disposed and the semiconductor chip 6 can be disposed after the release film 1 is disposed.

As described above, since the release film 1 has the release layer 1A having high releasability (and optionally the release layer 1A '), the semiconductor package 4-2 can be easily released. Further, since the release film 1 has an appropriate flexibility, it is excellent in the ability to follow the shape of the metal mold, and it is difficult for wrinkles to be generated by the heat of the molded metal mold 8. As a result, the sealed semiconductor package 4-2 having a good appearance without wrinkles being transferred to the resin sealing surface of the sealed semiconductor package 4-2 or a portion where no resin is filled (resin scratches) Can be obtained.

Further, the present invention is not limited to the compression molding method in which the solid encapsulating resin material 4 shown in Fig. 3-1 is pressurized and heated, and a transfer mold method in which a sealing resin material in a flowing state is injected as described later have.

4A and 4B are schematic diagrams showing a transfer molding method, which is an example of a method for producing a resin-sealed semiconductor using the release film of the first invention of the present application.

4A, the release film 22 of the first invention of the present invention is fed from a roll of rolls into a shaped metal mold 28 by a roll 24 and a roll 26 (step a). Then, the release film 22 is placed on the inner surface 30A of the upper mold 30 (step b). The mold inner surface 30A can be vacuum-sucked to adhere the mold release film 22 to the inner mold inner surface 30A as required. Subsequently, the semiconductor chip 34 (the semiconductor chip 34 fixed to the substrate 34A) to be resin-sealed is disposed in the molded metal mold 28, and the sealing resin material 36 is set (step c ), And the mold is closed (step d).

Subsequently, as shown in Fig. 4B, the encapsulating resin material 36 is injected into the molded metal mold 28 under predetermined heating and pressurizing conditions (step e). The temperature (molding temperature) of the molded metal mold 28 at this time is, for example, 165 to 185 占 폚, the molding pressure is, for example, 7 to 12 Mpa, and the molding time is, for example, about 90 seconds. Then, the upper mold 30 and the lower mold 32 are opened and the resin-sealed semiconductor package 40 and the release film 22 are simultaneously or sequentially released (step f).

Then, as shown in Fig. 5, the desired semiconductor package 44 can be obtained by removing the excess resin portion 42 of the semiconductor package 40 thus obtained. The release film 22 can be used for resin encapsulation of another semiconductor chip as it is. However, every time the molding is completed, the roll is operated to eject the film and newly supply the release film 22 to the molded metal mold 28 .

Before and after the step of disposing the release film 22 on the inner surface of the molded metal mold 28 and the step of disposing the semiconductor chip 34 in the molded metal mold 28 are not particularly limited, The release film 22 may be disposed after the semiconductor chip 34 is disposed and the semiconductor chip 34 may be disposed after the release film 22 is disposed.

As described above, since the release film 22 has the release layer 1A having a high releasability (and optionally the release layer 1A '), the semiconductor package 40 can be easily released. Also, since the release film 22 has moderate flexibility, it is excellent in followability to the shape of the metal mold, and it is difficult for wrinkles to be generated due to the heat of the molded metal mold 28. As a result, it is possible to obtain a semiconductor package 40 having a good appearance without causing wrinkles to be transferred to the resin sealing surface of the semiconductor package 40 or a portion where no resin is filled (resin scratches).

The release film of the first invention of the present application is not limited to the resin encapsulation process but may be a process for molding and releasing various kinds of molded products using a molded metal mold such as a fiber reinforced plastic molding and mold release process, And the like.

Process release film

The process release film of the second invention of the present application includes the following four embodiments.

(Embodiment 2-1)

As a release film for a process which is a laminated film including a release layer 2A and a heat-resistant resin layer 2B,

The contact angle of the release layer 2A with respect to water in the laminated film is 90 to 130 and the surface resistivity is 1 x 10 < ¹³ >

Wherein the heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,

Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.

(Embodiment 2-2)

As a release film for a process which is a laminated film including a release layer 2A and a heat-resistant resin layer 2B,

The contact angle of the release layer 2A with respect to water in the laminated film is 90 to 130 and the surface resistivity is 1 x 10 < ¹³ >

The heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,

Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.

(Embodiment 2-3)

A release film for processing which is a laminated film comprising a release layer 2A, a heat-resistant resin layer 2B and a release layer 2A '

The contact angle of the release layer 2A and the release layer 2A 'of the laminated film with respect to water is 90 ° to 130 °, the surface resistivity of the release layer 2A is 1 × 10 ¹³ Ω / □ or less,

The heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,

Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.

(Embodiment 2-4)

A release film for processing which is a laminated film comprising a release layer 2A, a heat-resistant resin layer 2B and a release layer 2A '

The contact angle of the release layer 2A and the release layer 2A 'of the laminated film with respect to water is 90 ° to 130 °, the surface resistivity of the release layer 2A is 1 × 10 ¹³ Ω / □ or less,

The heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,

Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.

As is apparent from the above embodiments, the process release film of the second invention (hereinafter also simply referred to as a release film) of the present invention comprises a release layer 2A having releasability to a molded product and a metal mold, and optionally a release layer 2A ' And a heat-resistant resin layer 2B for supporting the release layer, and the heat-resistant resin layer 2B includes a layer 2B1 containing a polymeric antistatic agent.

The process release film of the second invention of the present application is disposed on the inner surface of the metal mold when the semiconductor element or the like is sealed in the molded metal mold. At this time, it is preferable to dispose the release layer 2A of the release film (which may be the release layer 2A 'if the release layer 2A' is present) on the side of the resin-sealed semiconductor element or the like (molded article). By disposing the release film of the second invention of the present application, a resin-sealed semiconductor element or the like can be easily released from a metal mold.

The contact angle of the release layer 2A with respect to water is 90 DEG to 130 DEG. By having such a contact angle, the release layer 2A is low in wettability and can easily release the molded article without adhering to the surface of the cured encapsulating resin and metal mold .

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

Further, since the surface resistivity of the release layer 2A is not more than 1 x 10 < ¹³ > OMEGA / & squ &, it is possible to effectively prevent the adherence of foreign matters or sealing resin to the release film. The surface resistivity of the release layer 2A is preferably 5 x 10 ¹² ? /? Or less, more preferably 1 x 10 ¹² ? / ?, still more preferably 5 x 10 ¹¹ ? /? Or less.

As described above, since the release layer 2A (or the release layer 2A 'in some cases) is disposed on the side of the molded article, wrinkles in the release layer 2A (in some cases, the release layer 2A' . There is a high possibility that the formed wrinkles are transferred to the molded article and the appearance of the molded article is defective.

In order to achieve the above object, the second invention of the present application provides a laminated film constituting a release film for processing, which comprises a release layer 2A (and optionally a release layer 2A ') and a heat-resistant resin layer 2B for supporting the release layer A laminated film is used in which a laminated film exhibiting a specific value of the thermal dimensional change ratio in the transverse direction (TD) is used and the heat-resistant resin layer 2B includes a layer 2B1 containing a polymeric antistatic agent. Here, the laminated film including the releasing layer 2A (and optionally the releasing layer 2A ') and the heat-resistant resin layer 2B supporting the releasing layer has a thermal dimension in the TD direction (transverse direction) from 23 DEG C to 120 DEG C The change ratio is 3% or less, or the thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the TD direction (transverse direction) is 4% or less.

The mechanism by which the appearance defects of the molded article can be extremely effectively suppressed by bonding the heat-resistant resin layer including the laminated film having the specified value and the layer containing the high molecular weight antistatic agent to the thermal dimensional change ratio in the transverse direction (TD) However, the thermal dimensional change ratio in the TD direction of the laminated film suppresses the generation of wrinkles due to the specific value, suppresses static electricity caused by having a layer containing a polymeric antistatic agent, and suppresses foreign matter inclusion such as powder in the process, It is presumed that they are demonstrating some synergy effects. In other words, since foreign matter such as powder can be a starting point of wrinkles, it is possible to suppress the occurrence of wrinkles more effectively by suppressing the incorporation of foreign matter, while the wrinkles can become cohesion points of foreign matter, It is presumed that there is some relationship with the suppression of the appearance defect of the molded article at a high level which can not be anticipated in the prior art.

As described above, the laminated film including the releasing layer 2A (and optionally the releasing layer 2A ') and the heat-resistant resin layer 2B supporting the releasing layer has heat of 23 DEG C to 120 DEG C in the TD direction (transverse direction) The dimensional change rate is 3% or less, or the thermal dimensional change ratio from 23 ° C to 170 ° C in the TD direction (transverse direction) is 4% or less. The laminated film has a thermal dimensional change ratio of 3% or less from 23 ° C to 120 ° C in the TD direction (transverse direction), a thermal dimensional change ratio of 23 ° C to 170 ° C in the TD direction (transverse direction) Or less.

The thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (transverse direction) of the laminated film is 3% or less, or the thermal dimensional change ratio from 23 ° C to 170 ° C in the TD direction (transverse direction) is 4% , Generation of wrinkles in the release layer such as a resin sealing process can be effectively suppressed. The mechanism of suppressing the occurrence of wrinkles in the release layer is not necessarily clear from the viewpoint of the change in thermal dimensional change in the transverse direction (TD) in the laminated film constituting the release film for the process. It is presumed that the thermal expansion / contraction of the release layer 2A (or the release layer 2A ') due to heating / cooling during the process is suppressed by using a laminated film having a small shrinkage.

The laminated film constituting the process release film of the second invention of the present invention preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of from 23 to 120 캜 of 2.5% or less, more preferably 2.0% or less, % Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 120 ° C.

The laminated film constituting the process release film of the second invention of the present invention preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of 23 to 170 캜 of 3.5% or less, more preferably 3.0% or less, % Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 170 ° C.

The mechanism by which the generation of wrinkles in the release layer is more effectively suppressed by using the resin layer in which the thermal dimensional change ratio in the transverse direction (TD) shows the above-mentioned specific value is used as the heat-resistant resin layer 2B is not necessarily clear, but the thermal expansion / It is presumed that the use of the small heat-resistant resin layer 2B is related to suppression of thermal expansion / contraction of the release layer 2A (or release layer 2A ') due to heating / cooling during processing.

The release film for a process according to the second invention of the present invention, which is a laminated film including a release layer 2A (and optionally a release layer 2A ') and a heat-resistant resin layer 2B for supporting the release layer, has a thermal dimensional change rate And the rate of change in thermal dimensional change in the MD direction (longitudinal direction at the time of production of the film, hereinafter also referred to as "longitudinal direction") is not more than a specific value.

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

The thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film including the release layer 2A (and optionally the release layer 2A ') and the heat resistant resin layer 2B, Is 6% or less, it is possible to more effectively suppress the occurrence of wrinkles when mounted inside the metal mold.

The thermal dimensional change ratio in the direction of the width direction (TD) of the laminated film including the release layer 2A (and optionally the release layer 2A ') and the heat-resistant resin layer 2B from 23 DEG C to 170 DEG C, The laminated film preferably has a thermal dimensional change ratio from 23 DEG C to 170 DEG C in the TD direction (transverse direction) and a thermal dimensional change ratio in the longitudinal (MD) direction of 23 DEG C to 170 DEG C, Lt; 0 > C to 170 < 0 > C is preferably -5.0% or more.

The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction is 7% or less, The generation of wrinkles can be suppressed more efficiently.

Heterogeneous layer  2A

The release layer 2A constituting the release film for processing of the second invention of the present invention has a contact angle to water of 90 to 130 °, preferably 95 to 120 °, more preferably 98 to 115 °, Lt; RTI ID = 0.0 > 110 < / RTI > The surface resistivity of the release layer 2A is not more than 1 x 10 ¹³ ? / ?, preferably not more than 5 x 10 ¹² ? / ?, more preferably not more than 1 x 10 ¹² ? / ?, still more preferably not more than 5 × 10 ¹¹ Ω / □ or less.

A resin selected from the group consisting of a fluorine resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene-based resin is preferable in terms of excellent releasability and easy accessibility of a molded article.

The fluororesin usable for the release layer 2A is the same as that described for the release layer 1A.

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

The polystyrene type resin that can be used for the release layer 2A is 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 metal mold (generally 120 to 180 DEG C) at the time of molding. From this point of view, the release layer 2A preferably contains a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 190 DEG C or higher, more preferably 200 DEG C or higher and 300 DEG C or lower.

In order to have crystallinity in the release layer 2A, it is preferable that at least a constituent unit derived from tetrafluoroethylene is contained in the fluorine resin, and 4-methyl-1-pentene (co) polymer in the 4-methyl- It is preferable to include at least a constituent unit derived from 1-pentene, and in the polystyrene-based resin, it is preferable to include at least syndiotactic polystyrene. Since the resin constituting the release layer 2A contains a crystal component, wrinkles are less likely to occur in a resin sealing process or the like, and wrinkles are suitable for suppressing transfer of the wrinkles to a molded product to cause appearance failure.

The resin containing the crystalline component constituting the release layer 2A preferably has a crystal melting heat amount of 15 J / g or more and 60 J / g or more in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 And more preferably 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, the heat resistance and releasability that can withstand the hot press molding such as the resin sealing process can be more effectively expressed, and the rate of dimensional change can be suppressed, so that the occurrence of wrinkles can be prevented. On the other hand, when the crystalline melting heat quantity is 60 J / g or less, the release layer 2A has appropriate hardness, so that sufficient followability can be obtained in the metal mold of the film in the resin sealing step and the like.

The release layer 2A may contain, in addition to the fluororesin, the 4-methyl-1-pentene copolymer, and / or the polystyrene resin, another resin. In this case, the other resin and its content are the same as those described for the release layer 1A.

In addition to the fluorine resin, the 4-methyl-1-pentene (co) polymer and / or the polystyrene-based resin, the releasing layer 2A may contain heat stabilizers, weather stabilizers, antioxidants, Stabilizers, antistatic agents, and other known additives generally added to film resins. The content of such an additive may be, for example, 0.0001 to 10 parts by weight based on 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 2A is not particularly limited as long as the releasability to the molded article is sufficient, but is usually 1 to 50 mu m, preferably 5 to 30 mu m.

The surface of the release layer 2A may have a concavo-convex shape if necessary, thereby improving the releasability. A method of imparting unevenness to the surface of the release layer 2A is not particularly limited, but general methods such as embossing can be employed.

Heterogeneous layer  2A '

The process release film of the second invention of the present invention may further include a release layer 2A 'in addition to the release layer 2A and the heat-resisting resin layer 2B. That is, the process release film of the second invention of the present invention may be a release film for processing which is a laminated film comprising a release layer 2A, a heat-resistant resin layer 2B and a release layer 2A 'sequentially.

The contact angle of the release layer 2A ', which can constitute the process release film of the second invention of the present invention, with respect to water is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115 ° , More preferably from 100 [deg.] To 110 [deg.]. The preferable materials, constitution, physical properties, etc. of the release layer 2A 'are the same as those described above for the release layer 2A.

The surface resistivity of the release layer 2A 'is preferably 1 x 10 ¹³ ? /? Or less, more preferably 5 x 10 ¹² ? /? Or less, still more preferably 1 x 10 ¹² ? /? And particularly preferably not more than 5 x 10 < ¹¹ > Since the surface resistivity of the release layer 2A 'is in the above range, adherence of foreign matter during the process and the like can be suppressed more effectively.

The release layer 2A and the release layer 2A 'in the case where the process release film is a laminated film sequentially including the release layer 2A, the heat-resistant resin layer 2B and the release layer 2A' may be the same constituent layer, have.

From the viewpoints of prevention of bending and ease of handling by having the same releasability on all sides, the releasing layer 2A and the releasing layer 2A 'preferably have the same or substantially the same constitution, and the releasing layer 2A and the releasing layer 2A' From the viewpoints of optimizing the respective processes in relation to the process, for example, from the viewpoints that the release layer 2A is excellent in releasability from the metal mold and the release layer 2A 'is excellent in releasability from the molded product, It is preferable that the layer 2A and the release layer 2A 'have different structures.

When the releasing layer 2A and the releasing layer 2A 'are made to have different constitutions, the releasing layer 2A and the releasing layer 2A' can be made of the same material with different structures such as thickness, have.

Heat-resistant resin layer 2B

The heat-resistant resin layer 2B constituting the release film for processing according to the second invention of the present invention supports the release layer 2A (and, in some cases, the release layer 2A ') and has a function of suppressing the generation of wrinkles due to the metal mold temperature.

The heat-resistant resin layer 2B constituting the release film for processing according to the second invention of the present application comprises a layer 2B1 containing a polymeric antistatic agent. Here, the term "containing" the layer 2B1 containing a polymeric antistatic agent means that the whole of the heat-resistant resin layer 2B is composed of a layer 2B1 containing a polymeric antistatic agent, and that a part of the heat-resistant resin layer 2B is a high- And a layer 2B1 containing an inhibitor. Therefore, the heat-resistant resin layer 2B may or may not include another layer other than the layer 2B1 containing the polymeric antistatic agent.

The heat-resistant resin layer 2B constituting the process release film according to the second aspect of the present invention includes the layer 2B1 containing the high-molecular-weight antistatic agent, the surface resistivity value of the release layer 2A (and the release layer 2A ' It contributes to prevention of electrification.

The presence of the layer 2B1 containing a polymeric antistatic agent effectively prevents the antistatic property on the surface of the release film for process according to the second aspect of the present invention. Therefore, it is possible to effectively suppress the adhesion of foreign substances such as dusts due to static electricity, and at the same time, even when a part of the semiconductor element comes into direct contact with the process release film during production of the semiconductor package, The breakdown of the semiconductor element can be effectively suppressed.

The surface resistance value of the heat-resistant resin layer 2B is preferably as low as possible from the standpoint of preventing electrification, and the lower limit is not particularly limited. The surface resistance value of the heat-resistant resin layer 2B tends to be smaller as the electrically conductive performance of the polymeric antistatic agent is higher and the content of the polymeric antistatic agent is greater.

As the layer other than the layer 2B1 containing the polymeric antistatic agent, for example, an adhesive layer 2B2 including an adhesive can be preferably used. That is, the heat-resistant resin layer 2B may include a layer 2B1 containing a polymeric antistatic agent and an adhesive layer 2B2 including an adhesive.

In this case, the heat-resistant resin layer 2B may be composed only of the layer 2B1 containing the polymeric antistatic agent and the adhesive layer 2B2 including the adhesive, and the layer 2B1 containing the polymeric antistatic agent and the adhesive layer 2B2 including the adhesive For example, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas barrier layer, and the like.

In the release film for a process according to the second aspect of the present invention, the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is 3% Deg.] C is preferably 3% or less. Further, in the heat-resistant resin layer 2B, the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) is 3% or less, and furthermore, the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) Do.

An optional resin layer including a non-oriented film can be used for the heat-resistant resin layer 2B, but it is particularly preferable to include a stretched film.

The stretched film tends to have a low thermal expansion coefficient or a negative thermal expansion due to the effect of stretching during the production process, and the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse direction (TD) is 3% It is relatively easy to realize the characteristic that the rate of change in thermal dimensional change from 23 deg. C to 170 deg. C in the (TD) direction is 3% or less. Therefore, it can be suitably used as the heat resistant resin layer 2B.

The thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 2B is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

The thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 2B is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

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

The heat-resistant resin layer 2B preferably has heat resistance capable of withstanding the temperature of the metal mold (generally 120 to 180 DEG C) at the time of molding in view of controlling the strength of the film and the rate of change in thermal dimensional thereof to an appropriate range. In view of this, the heat-resistant resin layer 2B preferably contains a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 125 DEG C or higher, more preferably 155 DEG C or higher and 300 DEG C or lower, More preferably from 185 to 210 ° C, and particularly preferably from 185 to 205 ° C.

As described above, the heat-resistant resin layer 2B preferably includes a crystalline resin having a crystal component. As the crystalline resin to be contained in the heat-resistant resin layer 2B, a part or all of a crystalline resin such as a polyester resin, a polyamide resin, and a polypropylene resin can be used. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 and polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the above-mentioned crystalline resin in the heat-resistant resin layer 2B, wrinkles are less likely to occur in the resin sealing step and the like, and it is more advantageous to suppress wrinkles from being transferred to the molded article and causing defective appearance.

The resin constituting the heat-resistant resin layer 2B preferably has a crystal melting heat amount of not less than 20 J / g and not more than 100 J / g in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221, More preferably 25 J / g or more and 55 J / g or less, even more preferably 28 J / g or more and 50 J / g or less, more preferably 28 J / g or more and 40 J / g or less, and more preferably 28 J / g or more and 35 J / g or less. If it is 20 J / g or more, heat resistance and releasability that can withstand hot press forming such as a resin sealing process can be effectively exhibited, and also the rate of dimensional change can be suppressed to a small extent, so that occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal fusion is not more than 100 J / g, the heat-resistant resin layer 2B can be given an appropriate hardness, so that it is possible to ensure sufficient followability to the metal mold in the resin- There is no possibility of becoming easy. Further, in this embodiment, the crystal melting heat quantity is determined by the relationship between the heat quantity (J / g) of the longitudinal axis obtained in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 and the temperature Refers to a numerical value obtained by summing up peak areas having peaks at 120 ° C or higher in the chart shown.

The heat of fusion of the heat of the heat-resistant resin layer 2B can be adjusted by appropriately setting heating, cooling, and stretching conditions in the production of the film.

The thickness of the heat-resistant resin layer 2B is not particularly limited as long as the film strength can be ensured, but is usually 1 to 100 μm, preferably 5 to 50 μm.

A layer containing a polymeric antistatic agent 2B1

As the polymeric antistatic agent of the layer 2B1 containing a polymeric antistatic agent suitably used for the heat-resistant resin layer 2B constituting the laminate of the second invention of the present application, a polymer compound known to have an antistatic function can be used . For example, a cationic copolymer having a quaternary ammonium base in a lateral group, an anionic compound containing polystyrene sulfonic acid, a compound having a polyalkylene oxide chain (a polyethylene oxide chain and a polypropylene oxide chain are preferable Polyether ester amides, polyether amide imides, polyether esters, ethylene oxide-epichlorohydrin copolymers, and the like. oxide-epichlorohydrin) copolymer, and? -conjugated conductive polymer. These may be used singly or in combination of two or more kinds.

Quaternary ammonium bases among copolymers having quaternary ammonium bases in the side groups have the effect of imparting rapid dielectric polarization relaxation due to dielectric lectric polarization and conductivity.

The copolymer preferably has a carboxy group together with a quaternary ammonium base at the side group. When having a carboxy group, the copolymer has cross-linking property and can form the intermediate layer 4 alone. When used in combination with an adhesive such as a urethane-based adhesive, it can react with the adhesive to form a crosslinked structure, and greatly improve adhesiveness, durability, and other mechanical properties.

The copolymer may further contain a hydroxy group at the side group. The hydroxy group has an effect of reacting with a functional group in the adhesive, for example, an isocyanate group to increase the adhesiveness.

The copolymer can be obtained by copolymerizing the above-mentioned monomers having functional groups. Specific examples of the monomer having a quaternary ammonium base include quaternary dimethylamino ethyl acrylate quats (including anions such as chloride, sulfate, sulfonate, alkyl sulfonate, etc. as a counter ion) . Specific examples of the monomer having a carboxy group include (meth) acrylic acid, (meta) acroyloxyethyl succinic acid, phthalic acid, and hexahydrophthalic acid.

Other monomers other than these may be copolymerized. Other monomers include vinyl derivatives such as alkyl (meth) acrylate, styrene, vinyl acetate, vinyl halide and olefin.

The ratio of the copolymer units having the respective functional groups of the copolymer may be appropriately set. The proportion of the copolymer unit having a quaternary ammonium base is preferably from 15 to 40 mol% based on the total amount of the copolymer units. When the ratio is 15 mol% or more, the antistatic effect is excellent. If it exceeds 40 mol%, the hydrophilicity of the copolymer may be excessively high. The proportion of the unit having a carboxy group is preferably 3 to 13 mol% based on the total of all the units.

When the copolymer has a carboxy group at the side group, a crosslinking agent (curing agent) is added to the copolymer. Examples of the crosslinking agent include bifunctional epoxy compounds such as glycerin diglycidyl ether, trifunctional epoxy compounds such as trimethylolpropane triglycidyl ether, and trimethylolpropane triazidinyl ether. And polyfunctional compounds such as imine compounds.

Imidazole derivatives such as 2-methyl imidazole, 2-ethyl and 4-methyl imidazole and other amines are added to the copolymer as ring-opening reaction catalysts of the above bifunctional and trifunctional epoxy compounds .

The? -conjugated conductive polymer is a conductive polymer having a main chain in which a? -conjugate is developed. As the? -conjugated conductive polymer, known ones may be used, and examples thereof include polythiophene, polypyrrole, polyaniline and derivatives thereof.

As the polymeric antistatic agent, those prepared by known methods can be used, and commercially available products can be used. Examples of commercially available products of PEDOT polythiophene resins include "MC-200" manufactured by kakensangyo.

Preferred examples of the layer 2B1 containing a polymeric antistatic agent include the following layer (1) and layer (2).

Layer (1): A layer formed by the polymeric antistatic agent itself having film-forming ability, the polymeric antistatic agent dissolved or dissolved in a solvent or a solvent, and dried if necessary.

Layer (2): A layer formed by melt-coating the polymeric antistatic agent, wherein the polymeric antistatic agent itself is meltable with film forming ability.

The fact that the polymeric antistatic agent itself has film forming ability in the layer (1) means that the film is formed when the polymeric antistatic agent is soluble in a solvent such as an organic solvent and the solution is wet coated and dried.

The fact that the polymeric antistatic agent itself is meltable in the layer (2) means that it is melted by heating.

The polymeric antistatic agent of the layer (1) may be one having a crosslinking property or not having a crosslinking property. When the polymeric antistatic agent has a crosslinking property, a crosslinking agent may be used in combination.

Examples of polymeric antistatic agents having film formability and crosslinking properties include copolymers having quaternary ammonium bases and carboxy groups in the side groups.

Examples of the cross-linking agent include those described above.

The thickness of the layer (1) is preferably 0.01 to 1.0 mu m, particularly preferably 0.03 to 0.5 mu m. Since the thickness of the layer 1 is not less than 0.01 탆, sufficient antistatic effect can be easily obtained, and since the thickness is not more than 1.0 탆, sufficient adhesiveness can be easily obtained at the time of lamination.

Examples of the polymeric antistatic agent of the layer (2) include a surfactant and a polyolefin resin containing carbon black or the like. Commercially available products include PELECTRON HS (manufactured by Sanyo Chemical Industries) and the like. The preferred range of thickness of layer (2) is equal to the preferred range of thickness of layer (1).

The layer 2B1 containing the polymeric antistatic agent may be a single layer or two or more layers. For example, any one of the layers (1) to (2), and may have both the layer (1) and the layer (2).

As the layer 2B1 containing a polymeric antistatic agent, the layer (1) is preferable in view of easy production. The layer (1) and the layer (2) can be used together.

Adhesive layer 2B2

As the adhesive contained in the adhesive layer 2B2 suitably used for the heat-resistant resin layer 2B constituting the laminate of the second invention of the present application, conventionally known adhesives can be suitably used. From the viewpoint of the production efficiency of the laminate of the second invention of the present application, an adhesive for dry lamination can be preferably used. For example, polyvinyl acetate adhesive; (Methacrylate, acrylonitrile, styrene, etc.) copolymers of acrylic acid esters (such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like) or copolymers of acrylic acid esters and other monomers Acrylic ester-based adhesives; Cyanoacrylate-based adhesives; An ethylene copolymer system adhesive comprising a copolymer of ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc.); Cellulosic adhesives; Polyester-based adhesives; Polyamide adhesives; Polyimide-based adhesives; An amino resin-based adhesive comprising a urea resin or a melamine resin; Phenolic resin adhesives; Epoxy adhesive; Polyurethane-based adhesives for crosslinking polyol (polyether polyol, polyester polyol, etc.) with isocyanate and / or isocyanurate; Reactive (meth) acrylic adhesive; Rubber-based adhesives comprising chloroprene rubber, nitrile rubber, styrene-butadiene rubber and the like; Silicone adhesives; An inorganic adhesive comprising an alkali metal silicate, a low melting point glass and the like; Etc. may be used.

Other layers

The process release film of the second invention of the present invention may have a layer other than the release layer 2A, the heat-resisting resin layer 2B and the release layer 2A ', as long as it is against the object of the second invention of the present application. The details of these other layers are the same as those described in the first aspect of the present invention.

The total thickness of the process release film of the second invention of the present invention is not particularly limited, but is preferably 10 to 300 μm, more preferably 30 to 150 μm. When the total thickness of the release film is within the above range, handling property when used as a roll is good, and the amount of film to be wasted is small, which is preferable.

Hereinafter, preferred embodiments of the release film for processing of the second invention of the present application will be described in more detail. 1 is a schematic view showing an example of a three-layer structure process release film. As shown in Fig. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one side thereof with an adhesive layer 14 interposed therebetween.

The release layer 16 is the release layer 2A described above, the heat-resistant resin layer 12 is the heat-resisting resin layer 2B described above, and the adhesive layer 14 is the adhesive layer described above. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing step; The heat-resistant resin layer 12 is desirably disposed on the side in contact with the inner surface of the metal mold in the sealing step.

2 is a schematic view showing an example of a release film for a process having a five-layer structure. Members having the same functions as those in Fig. 1 are denoted by the same reference numerals. 2, the release film 20 has a release layer 16A and a release layer 16B formed on both sides of the heat-resistant resin layer 12 through the adhesive layer 14. [ The release layer 16A is the release layer 2A described above and the heat resistant resin layer 12 is the heat resistant resin layer 2B described above. The release layer 16B is the release layer 2A 'described above. Adhesive layer.

The compositions of the release layers 16A and 16B may be the same or different from each other. The thicknesses of the release layers 16A and 16B may be the same or different from each other. However, if the releasing layers 16A and 16B have the same composition and thickness, they are symmetrical, which is preferable because warpage of the releasing film itself is less likely to occur. In particular, it is preferable that the release film of the second invention of the present application suppresses warpage because stress may be generated by heating in the sealing process. Thus, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good releasability is obtained for both the molding and the inner surface of the metal mold.

Process for producing release film for process

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

Manufacture process

The process release film of the second invention of the present invention can be used by disposing a semiconductor chip or the like in a metal mold and arranging it between the semiconductor chip or the like and the inner surface of the metal mold when injection molding the resin. By using the release film for processing according to the second invention of the present application, it is possible to effectively prevent defective mold release and occurrence of roughness from the metal mold.

The resin used in the production process may be either a thermoplastic resin or a thermosetting resin. In the art, thermosetting resins are widely used, and epoxy-based thermosetting resins are particularly preferred.

Although sealing of a semiconductor chip is the most typical example of the manufacturing process, the present invention is not limited thereto, and the second invention can be applied to a fiber-reinforced plastic molding process, a plastic lens molding process, and the like.

Figs. 3, 4A and 4B are schematic views showing an example of a method for producing a resin-sealed semiconductor using the release film of the second invention of the present application.

As shown in Fig. 3A, the release film 1 of the second invention of the present invention is fed from the roll-like roll into the molded metal mold 2 by rolls 1-2 and rolls 1-3. Then, it is placed on the inner surface of the upper mold 2 of the release film 1. The inner surface of the upper mold 2 can be vacuum-sucked to adhere the releasing film 1 to the inner surface of the upper mold 2 as required. Molding Molding Device A semiconductor die 6 disposed on a substrate is disposed on a lower metal die 5 and a sealing resin 4 in the form of a granule is preferably placed on the semiconductor die 6 The upper metal mold 2 and the lower metal mold 5, in which the releasing film 1 sucked and adhered by injecting the liquid sealing resin so as to cover the semiconductor chip 6, The sealing resin is accommodated. 3 (b), the upper metal mold 2 and the lower metal mold 5 are then closed through the mold release film 1 of the second invention of the present invention, and then the mold is closed, preferably in the form of granules Of the sealing resin.

3C, the sealing resin 4 is fluidized in the metal mold, the sealing resin 4 flows into the space and is filled to surround the side surface of the semiconductor chip 6, The upper semiconductor die 2 and the lower metal die 5 are opened and taken out from the sealed semiconductor chip 6. After the mold is opened and the molded product is taken out, the mold release film 1 is repeatedly used or a new mold release film is supplied and subjected to the following resin molding molding.

The release film of the second invention of the present invention is brought into close contact with the upper metal mold and interposed between the metal mold and the sealing resin to mold the resin to prevent the resin from adhering to the metal mold and to easily mold the molded product without defiling the resin mold surface of the metal mold. .

In addition, the release film can be newly supplied for one resin mold operation to be resin molded, or can be newly supplied and resin molded for several resin mold operations.

The sealing resin may be a liquid resin or a solid material at room temperature, for example, a granular resin, but a sealing material such as a liquid phase resin may be suitably employed. Specifically, epoxy resin (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolak type epoxy resin, etc.) is used as the sealing resin material, and a polyimide resin Based resin), a silicone resin (thermosetting addition type), and the like can be used. In addition, resin sealing conditions are, depending on the sealing resin used, e.g., curing temperature 120 ℃ ~ 180 ℃, can be appropriately set in forming pressure 10 ~ 50 kg / cm ^2, curing times range from 1 to 60 minutes.

Before and after the step of disposing the release film 1 on the inner surface of the molded metal mold 8 and the step of disposing the semiconductor chip 6 in the molded metal mold 8 are not particularly limited, The release film 1 can be disposed after the semiconductor chip 6 is disposed and the semiconductor chip 6 can be disposed after the release film 1 is disposed.

As described above, since the release film 1 has the release layer 2A having high releasability (and optionally the release layer 2A '), the semiconductor package 4-2 can be easily released. Further, since the release film 1 has an appropriate flexibility, it is excellent in the ability to follow the shape of the metal mold, and it is difficult for wrinkles to be generated by the heat of the molded metal mold 8. Thus, a sealed semiconductor package 4-2 having wrinkles transferred to the resin sealing surface of the sealed semiconductor package 4-2 or having a good appearance without causing a portion (resin scratches) not filled with resin is obtained . In addition, since the release film 1 has a relatively small surface resistance, it is possible to effectively suppress appearance defects due to static adhesion or the like on the release film of the granular sealing resin.

As shown in Fig. 3, the present invention is not limited to the compression molding method in which the solid encapsulating resin material 4, which is in the form of granules, is heated under pressure, and a transfer mold method in which a sealing resin material in a flowing state is injected Can be adopted.

4A and 4B are schematic diagrams showing a transfer molding method, which is an example of a method for producing a resin-sealed semiconductor using the release film of the second invention of the present application.

4A, the release film 22 of the second invention of the present invention is fed from a roll of rolls into a shaped metal mold 28 by a roll 24 and a roll 26 (step a). Then, the release film 22 is placed on the inner surface 30A of the upper mold 30 (step b). The mold inner surface 30A may be vacuum-sucked to adhere the mold release film 22 to the inner surface 30A of the mold. Subsequently, the semiconductor chip 34 (the semiconductor chip 34 fixed to the substrate 34A) to be resin-sealed is disposed in the molded metal mold 28, and the sealing resin material 36 is set (step c ), And the mold is closed (step d).

Subsequently, as shown in Fig. 4B, the encapsulating resin material 36 is injected into the molded metal mold 28 under predetermined heating and pressurizing conditions (step e). The temperature (molding temperature) of the molded metal mold 28 at this time is, for example, 165 to 185 占 폚, the molding pressure is, for example, 7 to 12 Mpa, and the molding time is, for example, about 90 seconds. After the upper mold 30 and the lower mold 32 are opened for a predetermined period of time, the resin-sealed semiconductor package 40 and the release film 22 are simultaneously or sequentially released (step f).

Then, as shown in Fig. 5, the desired semiconductor package 44 can be obtained by removing the excess resin portion 42 of the semiconductor package 40 thus obtained. The release film 22 can be used for resin encapsulation of another semiconductor chip as it is. However, every time the molding is completed, the roll is operated to eject the film and newly supply the release film 22 to the molded metal mold 28 .

Before and after the step of disposing the release film 22 on the inner surface of the molded metal mold 28 and the step of disposing the semiconductor chip 34 in the metal mold 28 are not particularly limited and can be performed simultaneously, The release film 22 may be disposed after the chip 34 is disposed and the semiconductor chip 34 may be disposed after the release film 22 is disposed.

As described above, since the release film 22 has the release layer 2A having high releasability (and optionally the release layer 2A '), the semiconductor package 40 can be easily released. Also, since the release film 22 has moderate flexibility, it is excellent in followability to the shape of the metal mold, and it is difficult for wrinkles to be generated due to the heat of the molded metal mold 28. As a result, it is possible to obtain a semiconductor package 40 having a good appearance without causing wrinkles to be transferred to the resin sealing surface of the semiconductor package 40 or a portion where no resin is filled (resin scratches).

The release film of the second invention of the present application is not limited to the step of sealing a semiconductor element, but may be a step of molding and releasing various molded articles by using a molded metal mold, for example, a fiber reinforced plastic molding and mold release process, And can also be preferably used in a mold releasing process.

Process release film

The process release film of the third invention includes the following four embodiments.

(Embodiment 3-1)

As a release film for processing which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,

The contact angle of the release layer 3A with respect to water is 90to 130,

Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.

(Embodiment 3-2)

As a release film for processing which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,

The contact angle of the release layer 3A with respect to water is 90to 130,

Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.

(Embodiment 3-3)

A releasing film for processing which is a laminated film including a releasing layer 3A, a heat-resisting resin layer 3B and a releasing layer 3A '

The contact angle of the release layer 3A and the release layer 3A 'with respect to water is 90 ° to 130 °,

Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.

(Embodiment 3-4)

A releasing film for processing which is a laminated film including a releasing layer 3A, a heat-resisting resin layer 3B and a releasing layer 3A '

The contact angle of the release layer 3A and the release layer 3A 'with respect to water is 90 ° to 130 °,

Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.

As is apparent from each of the above embodiments, the process release film (hereinafter, also referred to as a release film) of the third invention of the present invention comprises a release layer 3A having releasability to a molded article and a metal mold, and optionally a release layer 3A ' And a heat-resistant resin layer 3B for supporting the release layer.

The process release film of the third invention is disposed on the inner surface of the molded metal mold when the semiconductor element or the like is sealed in the molded metal mold. At this time, it is preferable to dispose the release layer 3A of the release film (which may be the release layer 3A 'if the release layer 3A' is present) on the resin-sealed semiconductor element or the like (molded product) side. By disposing the release film of the third invention, the resin-sealed semiconductor element or the like can be easily released from the metal mold.

The contact angle of the release layer 3A with respect to water is 90to 130. By having such a contact angle, the release layer 3A has low wettability and can easily release the molded article without adhering to the surface of the hardened sealing resin and the metal mold, can do.

The contact angle of the release layer 3A with respect to water is preferably 95 to 120 DEG, more preferably 98 to 115 DEG, still more preferably 100 to 110 DEG.

As described above, since the release layer 3A (or the release layer 3A 'in some cases) is disposed on the side of the molded article, the occurrence of wrinkles in the release layer 3A (or in some cases, the release layer 3A' desirable. This is because the wrinkles generated when the release layer 3A (and in some cases, the release layer 3A ') are transferred to the molded article is likely to cause defective appearance of the molded article.

In order to achieve the above object, the third invention of the present invention is a laminated film comprising a releasing layer 3A (and optionally a releasing layer 3A ') and a heat-resistant resin layer 3B for supporting the releasing layer A laminated film is used which has a specific value of tensile modulus.

That is, the laminated film including the release layer 3A (and optionally the release layer 3A ') and the heat-resistant resin layer 3B supporting the release layer has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa, Lt; RTI ID = 0.0 > 500 MPa. ≪ / RTI > The laminated film preferably has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa and a tensile elastic modulus at 170 ° C of 75 MPa to 500 MPa.

Since the laminated film has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa or a tensile elastic modulus at 170 ° C of 75 MPa to 500 MPa, it is possible to effectively suppress the generation of wrinkles in the release layer in a resin sealing process or the like. The mechanism in which the tensile modulus at a specific temperature of the laminated film constituting the process release film shows the specific value and the generation of wrinkles in the release layer is suppressed is not necessarily clear, It is presumed that the tensile elastic modulus is related to the fact that the deformation resulting from the generation of wrinkles is suppressed and that the tensile modulus of elasticity is less than a certain value. If it exceeds 500 MPa, the metal mold following property is deteriorated, so that the sealing resin is difficult to fill at the end portion, and there is a high possibility that the appearance defects such as resin scratches are caused.

The laminated film constituting the process release film of the third invention of the present invention has a tensile modulus of elasticity at 120 ° C of

It is preferably 80 MPa to 400 MPa,

More preferably from 85 MPa to 350 MPa,

More preferably from 88 MPa to 300 MPa,

Particularly preferably from 90 MPa to 280 MPa.

The laminated film constituting the process release film of the third invention of the present invention has a tensile modulus at 170 ° C of

It is preferably 80 MPa to 400 MPa,

More preferably from 85 MPa to 350 MPa,

More preferably from 88 MPa to 300 MPa,

More preferably from 90 MPa to 280 MPa,

More preferably from 95 MPa to 200 MPa,

And particularly preferably from 105 MPa to 170 MPa.

Since the laminated film constituting the process release film of the third invention has the tensile elastic modulus at 120 ° C and the tensile elastic modulus at 170 ° C within the above preferable range, desirable.

Further, the laminated film including the release layer 3A (and optionally the release layer 3A ') and the heat-resistant resin layer 3B supporting the release layer has a thermal dimension in the TD direction (transverse direction) from 23 DEG C to 120 DEG C It is preferable that the rate of change is 3% or less, or the rate of change in thermal dimensional change from 23 DEG C to 170 DEG C in the TD direction (transverse direction) is 4% or less. The laminated film has a thermal dimensional change ratio of 3% or less from 23 ° C to 120 ° C in the TD direction (transverse direction) and a thermal dimensional change ratio of 23 ° C to 170 ° C in the TD direction (transverse direction) of 4% Is more preferable.

The thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (transverse direction) of the laminated film is 3% or less, or the thermal dimensional change ratio from 23 ° C to 170 ° C in the TD direction (transverse direction) is 4% It is possible to more effectively suppress the occurrence of wrinkles in the release layer such as the resin sealing process. In this embodiment, the mechanism by which the generation of wrinkles of the release layer is more effectively suppressed by using the laminated film constituting the process release film as the thermal dimensional change ratio in the transverse direction (TD) indicates the specific value is not necessarily clear Although it is presumed that the thermal expansion / contraction of the release layer 3A (or the release layer 3A ') due to heating / cooling during the process is suppressed by using a laminated film having a comparatively small thermal expansion / contraction.

The laminated film constituting the process release film of the present embodiment preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of from 23 to 120 캜 of 2.5% or less, more preferably 2.0% or less, more preferably 1.5% Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 120 ° C.

The laminated film constituting the process release film of the present embodiment preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of 23 to 170 캜 of 3.5% or less, more preferably 3.0% or less, and more preferably 2.0% Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 170 ° C.

The release film for processing according to the third invention, which is a laminated film comprising a release layer 3A (and optionally a release layer 3A ') and a heat-resistant resin layer 3B for supporting the release layer, It is preferable that the sum of the thermal dimensional change rate and the thermal dimensional change rate of the MD direction (longitudinal direction at the time of production of the film, hereinafter also referred to as " longitudinal direction ") is not more than a specific value.

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

The thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film including the release layer 3A (and optionally the release layer 3A ') and the heat resistant resin layer 3B, Is 6% or less, it is possible to more effectively suppress the occurrence of wrinkles when the metal mold is mounted in the metal mold.

The thermal dimensional change ratio in the direction of the width direction (TD) of the laminated film including the release layer 3A (and optionally the release layer 3A ') and the heat-resistant resin layer 3B from 23 ° C to 170 ° C, The laminated film preferably has a thermal dimensional change ratio from 23 DEG C to 170 DEG C in the TD direction (transverse direction) and a thermal dimensional change ratio in the longitudinal (MD) direction of 23 DEG C to 170 DEG C, Lt; 0 > C to 170 < 0 > C is preferably -5.0% or more.

The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction is 7% or less, It is possible to more effectively suppress the generation of wrinkles when the wrinkles are formed.

Heterogeneous layer  3A

The release layer 3A constituting the release film for processing according to the third aspect of the present invention has a contact angle with respect to water of 90 to 130 DEG, preferably 95 to 120 DEG, more preferably 98 to 115 DEG, More preferably from 100 DEG to 110 DEG. It is preferable to include a resin selected from the group consisting of a fluorine resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene-based resin from the viewpoints of excellent moldability of the molded article and ease of obtaining.

The fluororesin usable for the release layer 3A may be a resin containing a constituent unit derived from tetrafluoroethylene. But it may be a tetrafluoroethylene homopolymer or a copolymer with other olefins. Examples of other olefins include ethylene. A copolymer containing tetrafluoroethylene and ethylene as monomer constituent units is a preferred example. In such a copolymer, the proportion of the constituent unit derived from tetrafluoroethylene is 55 to 100% by mass, and the constituent unit derived from ethylene Is preferably 0 to 45% by mass.

The 4-methyl-1-pentene (co) polymer which can be used for the release layer 3A may be a homopolymer of 4-methyl-1-pentene, (Hereinafter referred to as an " olefin having 2 to 20 carbon atoms ").

In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, an olefin having 2 to 20 carbon atoms to be copolymerized with 4-methyl-1-pentene is added to 4-methyl- Flexibility can be given. Examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, hexadecene, 1-heptadecene, 1-octadecene, 1-eicosen, 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 proportion of the constituent unit derived from 4-methyl-1-pentene is 96 to 99 mass% And the proportion of the structural units derived from olefins of 2 to 20 is preferably 1 to 4% by mass. By decreasing the content of the constituent unit derived from olefin having 2 to 20 carbon atoms, the copolymer can be hardened, that is, the storage elastic modulus E 'can be made high, which is advantageous for suppressing occurrence of wrinkles such as sealing processes. On the other hand, by increasing the content of the olefin-derived structural unit having 2 to 20 carbon atoms, the copolymer can be softened, that is, the storage elastic modulus E 'can be lowered, which is advantageous for improving the followability of the metal mold.

The 4-methyl-1-pentene (co) polymer may be prepared by methods known to those skilled in the art. For example, a known catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst or the like. It is preferable that the 4-methyl-1-pentene (co) polymer is a (co) polymer having high crystallinity. As the crystalline copolymer, any of a copolymer having an isotactic structure and a copolymer having a syndiotactic structure may be used. In particular, a copolymer having an isotactic structure is preferable from the viewpoint of physical properties, It is also easy to obtain. Further, the 4-methyl-1-pentene (co) polymer can be formed into a film form, so that stereoregularity and molecular weight are not particularly limited as long as the 4-methyl-1-pentene (co) polymer has strength enough to withstand temperature or pressure at the time of metal die casting. The 4-methyl-1-pentene copolymer may be a commercially available copolymer such as, for example, TPX (registered trademark) of Mitsui Chemicals Co.,

The polystyrene type resin that can be used for the release layer 3A includes a homopolymer and a copolymer of styrene, and the structural unit derived from styrene contained in the polymer is preferably at least 60 wt%, more preferably at least 80 wt% Or more.

The polystyrene type resin may be isotactic polystyrene or syndiotactic polystyrene, but isotactic polystyrene is preferable from the viewpoints of transparency, availability and the like, and syndiotactic polystyrene is preferable from the viewpoints of releasability, heat resistance and the like. One kind of polystyrene may be used alone, or two or more kinds of polystyrene may be used in combination.

The release layer 3A preferably has heat resistance capable of withstanding the temperature of the metal mold (generally 120 to 180 DEG C) at the time of molding. From this point of view, the release layer 3A preferably contains a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 190 DEG C or higher, more preferably 200 DEG C or higher and 300 DEG C or lower.

In order to have crystallinity in the release layer 3A, for example, in a fluorine resin, at least a constituent unit derived from tetrafluoroethylene is preferably contained, and in the case of 4-methyl-1-pentene (co) It is preferable to include at least a constituent unit derived from 1-pentene, and in the polystyrene-based resin, it is preferable to include at least syndiotactic polystyrene. The resin constituting the release layer 3A contains a crystal component, so that wrinkles are less likely to occur in the resin sealing step and the like, and the wrinkles are suitable for suppressing transfer of the wrinkles to the molded article to cause appearance failure.

The resin containing the crystalline component constituting the release layer 3A preferably has a crystal melting heat amount of 15 J / g or more and 60 J / g or more in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221, g or less, more preferably 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, heat resistance and releasability that can withstand the hot press molding in the resin sealing step and the like can be more effectively expressed, and the rate of dimensional change can be suppressed, so that occurrence of wrinkles can be prevented. On the other hand, when the crystalline melting heat quantity is 60 J / g or less, the releasing layer 3A has appropriate hardness, so that sufficient followability to the metal mold of the film in the resin sealing step and the like can be obtained.

The release layer 3A may contain another resin besides the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin. In this case, it is preferable that the hardness of the other resin is relatively high. Examples of other resins include polyamide-6, polyamide-66, polybutylene terephthalate, and polyethylene terephthalate. As described above, even when the release layer 3A contains, for example, a large amount of soft resin (for example, when a 4-methyl-1-pentene copolymer contains a large amount of olefins having 2 to 20 carbon atoms) By additionally including a high resin, the releasing layer 3A can be made hard, and it is advantageous for suppressing the generation of wrinkles in a sealing process or the like.

The content of such another resin is preferably 3 to 30 mass%, for example, with respect to the resin component constituting the release layer 3A. When the content of the other resin is 3 mass% or more, the effect of the addition can be made substantial, and when it is 30 mass% or less, releasability to metal moldings and molded articles can be maintained.

The release layer 3A may contain, in addition to a fluororesin, a 4-methyl-1-pentene (co) polymer and / or a polystyrene resin, a thermostable stabilizer, a weatherability stabilizer , Rusting inhibitors, copper harm-resistant stabilizers, antistatic agents, and the like, which are generally incorporated in film resins. The content of such an additive may be, for example, 0.0001 to 10 parts by weight based on 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 3A is not particularly limited as long as the releasability to the molded article is sufficient, but is usually 1 to 50 mu m, preferably 5 to 30 mu m.

The surface of the release layer 3A can have a concavo-convex shape if necessary, thereby improving the releasability. The method of imparting irregularities to the surface of the release layer 3A is not particularly limited, but general methods such as embossing can be employed.

Heterogeneous layer  3A '

The process release film according to the third aspect of the present invention may additionally have a release layer 3A 'in addition to the release layer 3A and the heat-resistant resin layer 3B. That is, the process release film of the third invention of the present invention may be a release film for processing which is a laminated film sequentially including a release layer 3A, a heat-resistant resin layer 3B and a release layer 3A '.

The contact angle of the release layer 3A 'which can constitute the process release film of the third invention of the present invention with respect to water is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115 ° Deg.], More preferably from 100 [deg.] To 110 [deg.]. The preferred materials, constitution, physical properties, etc. of the release layer 3A 'are the same as those described above for the release layer 3A.

The release layer 3A and the release layer 3A 'in the case where the process release film is a laminated film sequentially including the release layer 3A, the heat-resistant resin layer 3B and the release layer 3A' may be the same configuration layer, have.

The release layer 3A and the release layer 3A 'are preferably the same or substantially the same in constitution from the viewpoints of prevention of bending and ease of handling due to having the same releasability on all sides, and the release layer 3A and the release layer 3A' From the viewpoint of optimizing each of them in relation to the process of forming the release layer 3A, for example, from the viewpoint that the release layer 3A is excellent in releasability from the metal mold and that the release layer 3A ' It is preferable that the release layer 3A and the release layer 3A 'have different structures.

In the case where the release layer 3A and the release layer 3A 'have different structures, the release layer 3A and the release layer 3A' are made of the same material but can have different structures such as thickness, .

Heat-resistant resin layer 3B

The heat-resistant resin layer 3B constituting the process release film of the third invention supports the release layer 3A (and the release layer 3A 'as the case may be), and also has a function of suppressing the generation of wrinkles due to the temperature of the metal mold .

In the release film for a process according to the third aspect of the present invention, the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction of the heat-resistant resin layer 3B is 3% or less, or 23 ° C To 170 < 0 > C is preferably 3% or less. The heat resistant resin layer 3B has a thermal dimensional change ratio of 3% or less in the transverse direction (TD) direction from 23 ° C to 120 ° C and a thermal dimensional change ratio of 3% or less in the transverse direction (TD) desirable.

The thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less, or the thermal dimensional change ratio from 23 deg. C to 170 deg. C in the transverse (TD) direction of the heat resistant resin layer 3B is 3% It is possible to more effectively suppress the occurrence of wrinkles when mounted on the inner surface of the metal mold.

The mechanism by which the generation of wrinkles of the release layer is more effectively suppressed by using the resin layer in which the thermal dimensional change ratio in the transverse direction (TD) shows the above-mentioned specific value is used as the heat-resistant resin layer 3B is not necessarily clear, but the thermal expansion / It is presumed that thermal expansion / contraction of the release layer 3A (or release layer 3A ') due to heating / cooling during processing is suppressed by using the heat-resistant resin layer 3B.

An optional resin layer including a non-oriented film can be used for the heat-resistant resin layer 3B, but it is particularly preferable to include a stretched film.

The stretched film tends to have a low thermal expansion coefficient or a negative thermal expansion due to the effect of stretching in the manufacturing process, and the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse direction (TD) is 3% It is relatively easy to realize a characteristic that the rate of change in thermal dimensional change from 23 DEG C to 170 DEG C in the transverse direction (TD) is 3% or less. Therefore, it can be suitably used as the heat resistant resin layer 3B.

The thermal dimensional change ratio in the transverse (TD) direction of the heat-resistant resin layer 3B from 23 ° C to 120 ° C is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

The thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat-resistant resin layer 3B is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

In the release film for a process according to the third aspect of the present invention, the thermal dimensional change rate in the transverse (TD) direction of 23 ° C to 120 ° C in the heat resistant resin layer 3B and the thermal dimensional change rate Or the sum of the thermal dimensional change rate from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) direction of 5% or less . The sum of the thermal dimensional change rate from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is 6% It is more preferable that the sum of the thermal dimensional change rate in the transverse direction (TD) direction from 23 ° C to 170 ° C and the thermal dimensional change rate in the longitudinal (MD) direction from 23 ° C to 170 ° C is 5% or less. Since the sum of the thermal dimensional change ratio in the transverse (TD) direction and the longitudinal (MD) direction of the heat-resistant resin layer 3B is in the above range, the occurrence of wrinkles can be suppressed more effectively when the metal mold is mounted on the inner surface have.

The sum of the thermal dimensional change rate from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is more preferably from -3.0% to 5.0% , More preferably not less than -2.0% and not more than 4.5%.

The sum of the thermal dimensional change rate from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) direction is more preferably -15.5% to 5.0% , More preferably not less than -10.0% and not more than 4.5%.

From the viewpoint that the sum of the thermal dimensional change ratio in the transverse (TD) direction and the longitudinal (MD) direction of the heat-resistant resin layer 3B falls within the above range, it is advantageous to use a stretched film, It is advantageous.

The stretched film may be a uniaxially stretched film or a biaxially stretched film. In the case of a uniaxially stretched film, it may be any of longitudinal stretching and transverse stretching, but it is preferred that stretching proceeds at least in the transverse (TD) direction.

The method and apparatus for obtaining the stretched film are not particularly limited, and the stretching can be performed by a method known in the art. For example, it can be stretched by a heating roll and a tenter-type stretching machine.

As the stretched film, it is preferable to use a stretched film selected from the group consisting of stretched polyester film, stretched polyamide film and stretched polypropylene film. Such a stretched film is comparatively easy to lower the thermal expansion coefficient in the transverse (TD) direction due to stretching or to make it negative, and the mechanical properties are suitable for the use of the third invention of the present invention, and since it is relatively easy to obtain at low cost, And is particularly suitable as a stretched film in the resin layer 3B.

As the stretched polyester film, a stretched polyethylene terephthalate (PET) film and a stretched polybutylene terephthalate (PBT) film are preferable, and a biaxially stretched polyethylene terephthalate (PET) film is particularly preferable.

The polyamide constituting the oriented polyamide film is not particularly limited, but polyamide-6, polyamide-66 and the like can be preferably used.

As the stretched polypropylene film, a uniaxially stretched polypropylene film and a biaxially stretched polypropylene film can be preferably used.

The stretching magnification is not particularly limited and may appropriately be set appropriately in order to appropriately control the rate of change in thermal dimensional and to realize suitable mechanical properties. For example, in the case of stretched polyester film, And in the case of a stretched polyamide film, it is preferably in the range of 2.7 to 5.0 times in both the longitudinal direction and the transverse direction, and in the case of the stretched polypropylene film, in the case of the biaxially stretched polypropylene film, Direction and the transverse direction are preferably in the range of 5.0 to 10.0 times, and in the case of the uniaxially stretched polypropylene film, the longitudinal direction is preferably in the range of 1.5 to 10.0 times.

The heat-resistant resin layer 3B preferably has heat resistance capable of withstanding the temperature of the metal mold (generally 120 to 180 DEG C) at the time of molding in view of controlling the strength of the film and the rate of change in thermal dimensional thereof to an appropriate range. From this point of view, the heat-resistant resin layer 3B preferably contains a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 DEG C or higher, more preferably 155 DEG C or higher and 300 DEG C or lower More preferably 185 or more and 210 占 폚 or less, and particularly preferably 185 or more and 205 占 폚 or less.

As described above, the heat-resistant resin layer 3B preferably includes a crystalline resin having a crystal component. As the crystalline resin contained in the heat-resistant resin layer 3B, for example, a part or all of a crystalline resin such as a polyester resin, a polyamide resin, and a polypropylene resin can be used. Concretely, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystal component of the above-mentioned crystalline resin in the heat-resistant resin layer 3B, wrinkles are less likely to occur in the resin sealing step and the like, and it is more advantageous to suppress wrinkles from being transferred to the molded article and causing defective appearance.

The resin constituting the heat-resistant resin layer 3B preferably has a crystal melting heat amount of not less than 20 J / g and not more than 100 J / g in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221, More preferably 25 J / g or more and 55 J / g or less, even more preferably 28 J / g or more and 50 J / g or less, more preferably 28 J / g or more and 40 J / g or less, and more preferably 28 J / g or more and 35 J / g or less. If it is 20 J / g or more, heat resistance and releasability that can withstand hot press forming such as a resin sealing process can be effectively exhibited, and also the rate of dimensional change can be suppressed to a small extent, so that occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal fusion is 100 J / g or less, the heat resistance resin layer 3B can be given appropriate hardness, so that it is possible to ensure sufficient followability to the metal mold in the resin sealing step or the like, There is no possibility of becoming easy. Further, in this embodiment, the crystal melting heat quantity is determined by the relationship between the heat quantity (J / g) of the longitudinal axis obtained in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 and the temperature Refers to a numerical value obtained by summing up peak areas having peaks at 120 占 폚 or higher in the chart shown.

The heat of crystal fusion of the heat-resistant resin layer 3B can be adjusted by appropriately setting heating, cooling, and stretching conditions in the production of the film.

The thickness of the heat-resistant resin layer 3B is not particularly limited as long as the film strength can be ensured, but is usually 1 to 100 μm, preferably 5 to 50 μm.

Other layers

The process release film of the third invention may have a layer other than the release layer 3A, the heat-resistant resin layer 3B and the release layer 3A ', as long as it is against the object of the third invention of the present invention. For example, an adhesive layer may be provided between the release layer 3A (or the release layer 3A ') and the heat-resistant resin layer 3B as required. The material used for the adhesive layer is not particularly limited as long as it can firmly adhere the release layer 3A and the heat-resistant resin layer 3B and can not be peeled off in the resin sealing step or the release step.

For example, when the releasing layer 3A (or the releasing layer 3A ') comprises a 4-methyl-1-pentene copolymer, the adhesive layer may be a graft-modified 4-methyl- An olefin-based adhesive resin composed of a copolymer resin, a 4-methyl-1-pentene copolymer and an -olefin copolymer, and the like. When the release layer 3A (or the release layer 3A ') 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 can improve the adhesion of the release layer 3A (or the release layer 3A ') and the heat-resistant resin layer 3B, and is, for example, 0.5 to 10 μm.

Although the total thickness of the process release film of the third invention is not particularly limited, for example, it is preferably 10 to 300 占 퐉, more preferably 30 to 150 占 퐉. When the total thickness of the release film is within the above range, handling property when used as a roll is good, and the amount of film to be wasted is small, which is preferable.

Hereinafter, preferred embodiments of the process release film of the third invention will be described in more detail. 1 is a schematic view showing an example of a release film for a process having 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 side thereof with an adhesive layer 14 therebetween.

The release layer 16 is the release layer 3A described above, the heat-resistant resin layer 12 is the heat-resisting resin layer 3B described above, and the adhesive layer 14 is the adhesive layer described above. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing step; The heat-resistant resin layer 12 is desirably disposed on the side in contact with the inner surface of the metal mold in the sealing step.

2 is a schematic view showing an example of a release film for a process having a five-layer structure. Members having the same functions as those in Fig. 1 are denoted by 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 formed on both sides of the heat-resistant resin layer 12 with an adhesive layer 14 therebetween. The release layer 16A is the release layer 3A described above and the heat resistant resin layer 12 is the heat resisting resin layer 3B described above. The release layer 16B is the release layer 3A 'described above, Adhesive layer.

The compositions of the release layers 16A and 16B may be the same or different from each other. The thicknesses of the release layers 16A and 16B may be the same or different from each other. However, if the release layers 16A and 16B have the same composition and thickness as each other, they are symmetrical, which is preferable because warping of the release film itself is less likely to occur. In particular, it is preferable that the release film of the third invention of the present invention suppresses warpage because stress may be generated by heating in the sealing process. Thus, if the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12, it is preferable that good releasability is obtained in both the molded article and the metal mold inner surface.

Process for producing release film for process

The process release film of the third invention can be produced by any method. For example, a method (co-extrusion molding method) of producing 1) a releasing film for processing by co-extruding and laminating a releasing layer 3A and a heat-resisting resin layer 3B, 2) (Coating method) of applying and drying a molten resin of a resin to be an adhesive layer, or applying and drying a resin solution in which a release layer 3A and a resin as an adhesive layer are dissolved in a solvent, 3) a method in which a film to be the releasing layer 3A and a film to be the heat-resisting resin layer 3B are prepared, and the film is laminated (laminated) to produce a releasing film for processing (lamination method).

In the method of 3), various known lamination methods may be employed as the method of laminating the respective resin films, and examples thereof include extrusion lamination, dry lamination and thermal lamination.

In the dry lamination method, each resin film is laminated using an adhesive. As the adhesive, known adhesives for dry lamination can be used. For example, a polyvinyl acetate adhesive; Acrylic acid ester and other monomers (such as methyl methacrylate, acrylonitrile, styrene, etc.) such as acrylic acid esters (such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate) Acrylic ester-based adhesives; Cyanoacrylate-based adhesives; An ethylene copolymer system adhesive comprising a copolymer of ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc.); Cellulosic adhesives; Polyester-based adhesives; Polyamide adhesives; Polyimide-based adhesives; An amino resin-based adhesive comprising a urea resin or a melamine resin; Phenolic resin adhesives; Epoxy adhesive; Polyurethane-based adhesives for crosslinking polyol (polyetherpolyol, polyester polyol, etc.) with isocyanate and / or isocyanurate; Reactive (meth) acrylic adhesive; Rubber adhesives composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber and the like; Silicone adhesives; An inorganic adhesive composed of an alkali metal silicate, a low melting point glass or the like; Etc. may be used. The resin film laminated by the method 3) may be a commercially available resin film or a resin film produced by a known manufacturing method. The resin film may be subjected to a surface treatment such as a corona treatment, an atmospheric pressure plasma treatment, a vacuum plasma treatment, or a primer coating treatment. The production method of the resin film is not particularly limited, and a known production method can be used.

1) The co-extrusion molding method is preferable because defects due to impurities or the like between the resin layer serving as the release layer 3A and the resin layer serving as the heat-resistant resin layer 3B and warpage of the release film are less likely to occur. 3) The lamination method (lamination method) is a method suitable for the case where a stretched film is used for the heat-resistant resin layer 3B. In this case, it is preferable to form an appropriate adhesive layer at the interface between the films as necessary. After the adhesiveness between the films is enhanced, surface treatment such as corona discharge treatment can be applied to the interface between the films as necessary.

The process release film may be uniaxially or biaxially stretched as required, thereby increasing the strength of the film film.

The coating means of the above 2) coating method is not particularly limited, but various coaters such as a roll coater, a die coater and a spray coater are used. The melt extrusion means is not particularly limited, but for example, a T-die or an extruder having an inflation die is used.

Manufacture process

The release film for processing according to the third aspect of the present invention can be used by disposing a semiconductor chip or the like in a metal mold and arranging it between the semiconductor chip and the inner surface of the metal mold when injection molding the resin. By using the release film for process according to the third invention of the present invention, it is possible to effectively prevent defective mold release and occurrence of flash from metal molds.

The resin used in the production process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the art, and epoxy-based thermosetting resins are particularly preferred.

In the above manufacturing process, the sealing of the semiconductor chip is the most typical, but the present invention is not limited thereto. The third invention can be applied to a fiber reinforced plastic molding process, a plastic lens molding process, and the like.

Figs. 3, 4A and 4B are schematic diagrams showing an example of a method for producing a resin-sealed semiconductor using a release film according to the third invention of the present invention.

As shown in Fig. 3A, the release film 1 of the third invention is fed into a molded metal mold 2 by rolls 1-2 and rolls 1-3 in a rolled roll. Then, the release film (1) is arranged on the inner surface of the upper die (2). The inner surface of the upper mold 2 can be vacuum-sucked to adhere the releasing film 1 to the inner surface of the upper mold 2 as required. Molding Molding Apparatus The lower metal mold 5 is provided with a semiconductor chip 6 disposed on a substrate and a sealing resin is placed on the semiconductor chip 6 or a liquid sealing resin The sealing resin 4 is accommodated between the upper metal mold 2 and the lower metal mold 5 on which the releasing film 1 adhered by exhausting is injected. Next, as shown in Fig. 3B, the upper metal mold 2 and the lower metal mold 5 are closed through the mold release film 1 of the third invention, and the sealing resin 4 is cured.

3C, the sealing resin 4 is fluidized in the metal mold, the sealing resin 4 flows into the space and is filled to surround the side surface of the semiconductor chip 6, and the sealed semiconductor 4 is filled with the sealing resin 4, The chip 6 is opened to take out the molds of the upper metal mold 2 and the lower metal mold 5. After the mold is opened and the molded article is taken out, the mold release film 1 is repeatedly used or a new mold release film is supplied and subjected to the following resin molding molding.

The release film of the third invention is adhered to the upper metal die to interpose it between the metal die and the sealing resin to prevent the resin from adhering to the metal die by resin molding and to prevent the mold surface of the metal die from being contaminated The molded article can be easily released.

Alternatively, the release film may be supplied newly for every single resin mold operation to be resin molded, or may be newly supplied and resin molded for each resin mold operation for a plurality of times.

The sealing resin may be a liquid resin or a solid-state resin at room temperature, but a sealing material such as a liquid-phase sealing material can be suitably employed. Specifically, epoxy resin (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolak type epoxy resin, etc.) is used as the sealing resin material, and a polyimide resin Based resin), a silicone resin (thermosetting addition type), and the like can be used. In addition, resin sealing condition which is varied in accordance with the sealing resin used, e.g., curing temperature 120 ℃ ~ 180 ℃, can be appropriately set in forming pressure 10 ~ 50 kg / cm ^2, curing times range from 1 to 60 minutes.

Before and after the step of disposing the release film 1 on the inner surface of the molded metal mold 8 and the step of disposing the semiconductor chip 6 in the molded metal mold 8 are not particularly limited and can be performed simultaneously The release film 1 can be disposed after the semiconductor chip 6 is disposed and the semiconductor chip 6 can be disposed after the release film 1 is disposed.

As described above, since the release film 1 has the release layer 3A having high releasability (and optionally the release layer 3A '), the semiconductor package 4-2 can be easily released. Further, since the release film 1 has an appropriate flexibility, it is excellent in the ability to follow the shape of the metal mold, and it is difficult for wrinkles to be generated by the heat of the molded metal mold 8. As a result, the sealed semiconductor package 4-2 having a good appearance without wrinkles being transferred to the resin sealing surface of the sealed semiconductor package 4-2 or a portion where no resin is filled (resin scratches) Can be obtained.

Further, the present invention is not limited to the compression molding method for pressurizing and heating the solid encapsulating resin material 4 as shown in Fig. 3, but the transfer molding method for injecting the encapsulating resin material in the fluidized state as described later can be adopted.

4A and 4B are schematic views showing a transfer molding method, which is an example of a method of manufacturing a resin-sealed semiconductor using a release film according to the third invention of the present invention.

4A, the release film 22 of the third invention is supplied from a roll of rolls into a molded metal mold 28 by a roll 24 and a roll 26 (step a) . Then, the release film 22 is placed on the inner surface 30A of the upper mold 30 (step b). The mold inner surface 30A can be vacuum-sucked to adhere the mold release film 22 to the inner mold inner surface 30A as required. Subsequently, the semiconductor chip 34 (the semiconductor chip 34 fixed to the substrate 34A) to be resin-sealed is disposed in the molded metal mold 28, and the sealing resin material 36 is set (step c ), And the mold is closed (step d).

Subsequently, as shown in Fig. 4B, the encapsulating resin material 36 is injected into the molded metal mold 28 under predetermined heating and pressurizing conditions (step e). The temperature (molding temperature) of the molded metal mold 28 at this time is, for example, 165 to 185 占 폚, the molding pressure is, for example, 7 to 12 Mpa, and the molding time is, for example, about 90 seconds. After the upper mold 30 and the lower mold 32 are opened for a predetermined period of time, the resin-sealed semiconductor package 40 and the release film 22 are simultaneously or sequentially released (step f).

Then, as shown in Fig. 5, the desired semiconductor package 44 can be obtained by removing the excess resin portion 42 of the semiconductor package 40 thus obtained. The release film 22 can be used for resin encapsulation of another semiconductor chip as it is. However, every time the molding is completed, the roll is operated to eject the film and newly supply the release film 22 to the molded metal mold 28 .

Before and after the step of disposing the release film 22 on the inner surface of the molded metal mold 28 and the step of disposing the semiconductor chip 34 in the molded metal mold 28 are not particularly limited, The release film 22 may be disposed after the semiconductor chip 34 is disposed and the semiconductor chip 34 may be disposed after the release film 22 is disposed.

As described above, the release film 22 can easily release the semiconductor package 40 because it has the release layer 3A having high releasability (and optionally, the release layer 3A '). Also, since the release film 22 has moderate flexibility, it is excellent in followability to the shape of the metal mold, and it is difficult for wrinkles to be generated due to the heat of the molded metal mold 28. As a result, it is possible to obtain a semiconductor package 40 having a good appearance without causing wrinkles to be transferred to the resin sealing surface of the semiconductor package 40 or a portion where no resin is filled (resin scratches).

The release film of the third invention is not limited to the resin encapsulation process but may be a process for molding and releasing various kinds of molded products using a molded metal mold such as fiber reinforced plastic molding and mold release process, And can also be preferably used in a mold releasing process.

Process release film

The process release film of the fourth invention includes the following four embodiments.

(Embodiment 4-1)

A release film for processing which is a laminated film including a release layer 4A and a heat-resistant resin layer 4B,

The contact angle of the release layer 4A with respect to water is 90to 130,

The heat-resistant resin layer 4B includes a layer 4B1 containing a polymeric antistatic agent,

Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.

(Embodiment 4-2)

A release film for processing which is a laminated film including a release layer 4A and a heat-resistant resin layer 4B,

The contact angle of the release layer 4A with respect to water is 90to 130,

The heat-resistant resin layer 4B comprises a layer 4B1 containing a polymeric antistatic agent,

Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.

(Embodiment 4-3)

A release film for processing which is a laminated film including a release layer 4A, a heat-resistant resin layer 4B and a release layer 4A '

The contact angle of the release layer 4A and the release layer 4A 'with respect to water is 90 ° to 130 °,

The heat-resistant resin layer 4B comprises a layer 4B1 containing a polymeric antistatic agent,

Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.

(Embodiment 4-4)

A release film for processing which is a laminated film including a release layer 4A, a heat-resistant resin layer 4B and a release layer 4A '

The contact angle of the release layer 4A and the release layer 4A 'with respect to water is 90 ° to 130 °,

The heat-resistant resin layer 4B comprises a layer 4B1 containing a polymeric antistatic agent,

Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.

As apparent from each of the above embodiments, the process release film (hereinafter, simply referred to as a release film) of the fourth invention of the present invention comprises a release layer 4A having releasability to a molded product and a metal mold, And a heat-resistant resin layer 4B for supporting the release layer, and the heat-resistant resin layer 4B includes a layer 4B1 containing a polymeric antistatic agent.

The process release film according to the fourth aspect of the present invention is disposed on the inner surface of the metal mold when the semiconductor element or the like is sealed in the molded metal mold. At this time, it is preferable to dispose the release layer 4A of the release film (or the release layer 4A 'if the release layer 4A' is present) on the resin-sealed semiconductor element or the like (molded product) side. By disposing the release film of the fourth invention, the resin-sealed semiconductor element or the like can be easily released from the metal mold.

The contact angle of the release layer 4A with respect to water is 90 DEG to 130 DEG. By having such a contact angle, the release layer 4A has low wettability and can easily release the molded article without adhering to the surface of the hardened sealing resin and metal mold .

The contact angle of the release layer 4A with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.

As described above, since the release layer 4A (or the release layer 4A 'in some cases) is disposed on the side of the molded article, the occurrence of wrinkles in the release layer 4A (the release layer 4A' . This is because the occurrence of wrinkles in the release layer 4A (or in some cases, the release layer 4A ') causes the occurrence of corrugation to be transferred to the molded article, resulting in a high possibility of appearance failure of the molded article.

In order to achieve the above object, the fourth invention of the present invention is a laminated film comprising a releasing film 4A (and optionally a releasing layer 4A ') and a heat-resistant resin layer 4B for supporting the releasing layer As the film, a laminated film having a specific tensile modulus of elasticity is used, and as the heat-resistant resin layer 4B, a layer 4B1 containing a polymeric antistatic agent is used. Here, the laminated film including the release layer 4A (and optionally the release layer 4A ') and the heat-resistant resin layer 4B supporting the release layer has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa, Has a tensile modulus of 75 MPa to 500 MPa.

The mechanism by which the appearance defect of the molded article is extremely effectively suppressed by bonding the heat-resistant resin layer including the laminated film having the tensile modulus of the specific value and the layer containing the polymeric antistatic agent is not necessarily clear, but the tensile modulus It is presumed that suppressing the occurrence of wrinkles by the above specific value, suppressing static electricity by having a layer containing a polymeric antistatic agent, and suppressing the inclusion of foreign matter such as powder in the process exert some synergistic effects. In other words, since foreign matter such as powder can be a starting point of wrinkles, it is possible to suppress the occurrence of wrinkles more effectively by suppressing the incorporation of foreign matter, while the wrinkles can become cohesion points of foreign matter, It is presumed that there is some relationship with the suppression of the appearance defect of the molded article at a high level which can not be anticipated in the prior art.

Further, the surface resistivity of the release layer 4A (and optionally the release layer 4A ') of the laminated film is preferably 1 x 10 < ¹³ > or less, more preferably 1 x 10 < ¹³ & Is not more than 5 x 10 ¹² ? /?, More preferably not more than 1 x 10 ¹² ? / ?, and most preferably not more than 5 x 10 ¹¹ ? /.

The surface resistivity value of the release layer 4A (and optionally the release layer 4A ') of the laminated film can be measured, for example, by the method described in the Examples herein.

As described above, the laminated film including the release layer 4A (and optionally the release layer 4A ') and the heat-resistant resin layer 4B supporting the release layer has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa, And a tensile elastic modulus at 170 DEG C of 75 MPa to 500 MPa. The laminated film preferably has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa and a tensile elastic modulus at 170 ° C of 75 MPa to 500 MPa.

Since the laminated film has a tensile elastic modulus at 120 ° C of 75 MPa to 500 MPa or a tensile elastic modulus at 170 ° C of 75 MPa to 500 MPa, it is possible to effectively suppress the generation of wrinkles in the release layer in a resin sealing process or the like. The mechanism by which the generation of wrinkles of the release layer is suppressed is not necessarily clear, but it is preferable that the mechanism that the tensile elastic modulus at a specific temperature of the laminated film constituting the process release film is in the above- It is presumed that deformation resulting from the generation of wrinkles is suppressed with the elastic modulus, and that the distortion is dispersed due to the tensile modulus being not more than a certain value. If it exceeds 500 MPa, the metal mold following property is deteriorated, so that the sealing resin is difficult to fill at the end portion, and there is a high possibility that the appearance defects such as resin scratches are caused.

In the laminated film constituting the process release film of the fourth invention, the tensile elastic modulus at 120 ° C

It is preferably 80 MPa to 400 MPa,

More preferably from 85 MPa to 350 MPa,

More preferably from 88 MPa to 300 MPa,

Particularly preferably from 90 MPa to 280 MPa.

In the laminated film constituting the process release film of the fourth invention of the present invention, the tensile modulus at 170 ° C

It is preferably 80 MPa to 400 MPa,

More preferably from 85 MPa to 350 MPa,

More preferably from 88 MPa to 300 MPa,

More preferably from 90 MPa to 280 MPa,

More preferably from 95 MPa to 200 MPa,

And particularly preferably from 105 MPa to 170 MPa.

The laminated film constituting the process release film of the fourth invention is particularly preferable because the tensile elastic modulus at 120 ° C and the tensile elastic modulus at 170 ° C together fall within the above-mentioned preferable range because of the degree of freedom and application in processing Do.

The laminated film including the release layer 4A (and optionally the release layer 4A ') and the heat-resistant resin layer 4B for supporting the release layer has a thermal dimensional change rate in the TD direction (transverse direction) from 23 ° C to 120 ° C 3% or less, or the thermal dimensional change ratio from 23 ° C to 170 ° C in the TD direction (transverse direction) is preferably 4% or less. The laminated film has a thermal dimensional change ratio of 3% or less from 23 ° C to 120 ° C in the TD direction (transverse direction), a thermal dimensional change ratio of 23 ° C to 170 ° C in the TD direction (transverse direction) Or less.

The thermal dimensional change ratio from 23 ° C to 120 ° C in the TD direction (transverse direction) of the laminated film is 3% or less, or the thermal dimensional change ratio from 23 ° C to 170 ° C in the TD direction (transverse direction) is 4% It is possible to more effectively suppress occurrence of wrinkles in the release layer such as a resin sealing process. In the present embodiment, the mechanism by which the occurrence of wrinkles of the release layer is more effectively suppressed by using the laminated film constituting the release film for processing in which the thermal dimensional change ratio in the transverse direction (TD) It is presumed that the use of a laminated film having relatively small thermal expansion / contraction is related to suppression of thermal expansion / contraction of the release layer 4A (or release layer 4A ') due to heating / cooling in the process.

The laminated film constituting the process release film of the present embodiment preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of from 23 to 120 캜 of 2.5% or less, more preferably 2.0% or less, more preferably 1.5% Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 120 ° C.

The laminated film constituting the process release film of the present embodiment preferably has a thermal dimensional change ratio in the TD direction (transverse direction) of 23 to 170 캜 of 3.5% or less, more preferably 3.0% or less, and more preferably 2.0% Or less. On the other hand, it is preferable that the laminated film has a thermal dimensional change ratio of -5.0% or more in the TD direction (transverse direction) from 23 ° C to 170 ° C.

The process release film of the fourth invention, which is a laminated film including a release layer 4A (and optionally a release layer 4A ') and a heat-resistant resin layer 4B for supporting the release layer, has a thermal dimension in the TD direction It is preferable that the sum of the rate of change and the dimensional change rate of the MD direction (longitudinal direction at the time of production of the film, hereinafter also referred to as " longitudinal (MD) direction ") is not more than a specific value.

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

The thermal dimensional change ratio from 23 DEG C to 120 DEG C in the laminated film transverse direction (TD) including the release layer 4A (and optionally the release layer 4A ') and the heat resistant resin layer 4B, Is 6% or less, it is possible to more effectively suppress the occurrence of wrinkles when mounted inside the metal mold.

The thermal dimensional change ratio from 23 DEG C to 170 DEG C in the laminated film transverse direction (TD) including the release layer 4A (and optionally the release layer 4A ') and the heat resistant resin layer 4B, The laminated film preferably has a thermal dimensional change ratio in the TD direction (transverse direction) from 23 to 170 DEG C and a thermal dimensional change rate in the longitudinal (MD) direction of 23 DEG C To 170 캜 is preferably -5.0% or more.

The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction is 7% or less, The generation of wrinkles can be suppressed more efficiently.

Heterogeneous layer  4A

The release layer 4A constituting the process release film of the fourth invention of the present invention has a contact angle to water of 90 to 130, preferably 95 to 120, more preferably 98 to 115, Preferably from 100 [deg.] To 110 [deg.]. A resin selected from the group consisting of a fluorine resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene-based resin is preferable in terms of excellent releasability and easy accessibility of a molded article.

The fluororesin usable for the release layer 4A is the same as that described for the release layer 1A.

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

The polystyrene type resin that can be used for the release layer 4A is the same as that described for the release layer 1A.

The release layer 4A preferably has heat resistance capable of withstanding the temperature of the metal mold (generally 120 to 180 DEG C) at the time of molding. In view of this, the release layer 4A preferably contains a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 190 DEG C or higher, more preferably 200 DEG C or higher and 300 DEG C or lower.

In order to have crystallinity in the release layer 4A, it is preferable that at least a constituent unit derived from tetrafluoroethylene is contained in, for example, a fluorine resin, and in a 4-methyl-1-pentene (co) It is preferable to include at least a constituent unit derived from 1-pentene, and in the polystyrene-based resin, it is preferable to include at least syndiotactic polystyrene. The resin constituting the release layer 4A contains a crystal component, so that wrinkles are less likely to occur in the resin sealing step and the like, and the wrinkles are transferred to the molded article, which is suitable for suppressing appearance failure.

The resin containing the crystalline component constituting the release layer 4A has a heat of crystal fusion of 15 J / g or more and 60 J / g or more in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 And more preferably 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, the heat resistance and releasability that can withstand the hot press molding such as the resin sealing process can be more effectively expressed, and the rate of dimensional change can be suppressed, so that the occurrence of wrinkles can be prevented. On the other hand, if the crystalline melting heat quantity is 60 J / g or less, the releasing layer 4A has appropriate hardness, so that sufficient followability can be obtained in the metal mold of the film in the resin sealing step or the like.

The release layer 4A may contain, in addition to the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin, another resin. In this case, the other resin and its content are the same as those described for the release layer 1A.

The release layer 4A may contain, in addition to the fluorine resin, the 4-methyl-1-pentene (co) polymer and / or the polystyrene resin, a heat stabilizer, a weather stabilizer, an antioxidant, Stabilizers, antistatic agents, and other known additives generally added to film resins. The content of such an additive may be, for example, 0.0001 to 10 parts by weight based on 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 4A is not particularly limited as long as the releasability to the molded article is sufficient, but is usually 1 to 50 mu m, preferably 5 to 30 mu m.

The surface of the release layer 4A may have a concavo-convex shape if necessary, thereby improving the releasability. The method of imparting unevenness to the surface of the release layer 4A is not particularly limited, but general methods such as embossing can be employed.

Heterogeneous layer  4A '

The process release film of the fourth invention may further include a release layer 4A 'in addition to the release layer 4A and the heat-resisting resin layer 4B. That is, the process release film of the fourth invention of the present invention may be a release film for a process which is a laminated film sequentially including a release layer 4A, a heat-resistant resin layer 4B and a release layer 4A '.

The contact angle of the release layer 4A 'capable of constituting the process release film of the fourth invention with respect to water is 90 to 130, preferably 95 to 120, more preferably 98 to 115 Deg.], More preferably from 100 [deg.] To 110 [deg.]. The preferable material, constitution, physical properties and the like of the release layer 4A 'are the same as those described above for the release layer 4A.

The release layer 4A and the release layer 4A 'in the case where the process release film is a laminated film sequentially including the release layer 4A, the heat-resistant resin layer 4B and the release layer 4A' may be the same constituent layer, have.

The release layer 4A and the release layer 4A 'preferably have the same or substantially the same constitution in view of prevention of deformation and ease of handling by having the same releasability in any of the surfaces, and it is preferable that the release layer 4A and the release layer 4A' From the viewpoint of optimizing the respective processes in relation to the process, for example, from the viewpoint that the release layer 4A is excellent in releasability from the metal mold and that the release layer 4A 'is excellent in releasability from the molding, It is preferable that the layer 4A and the release layer 4A 'have different structures.

In the case where the release layer 4A and the release layer 4A 'have different constitutions, the release layer 4A and the release layer 4A' can be made of the same material and different in the constitution such as the thickness, have.

Heat-resistant resin layer 4B

The heat-resistant resin layer 4B constituting the process release film of the fourth invention supports the release layer 4A (and, in some cases, the release layer 4A ') and has a function of suppressing the generation of wrinkles due to the metal mold temperature and the like.

The heat-resistant resin layer 4B constituting the process release film of the fourth invention includes the layer 4B1 containing a high molecular weight antistatic agent. Here, "including" the layer 4B1 containing the polymeric antistatic agent is a case where the whole of the heat-resistant resin layer 4B is composed of the layer 4B1 containing the polymeric antistatic agent and the case where a part of the heat- And a layer 4B1 containing an inhibitor. Therefore, the heat-resistant resin layer 4B may or may not include another layer other than the layer 4B1 containing the polymeric antistatic agent.

Since the heat-resistant resin layer 4B constituting the process release film of the fourth invention includes the layer 4B1 containing a high molecular weight antistatic agent, the surface resistivity value is low and contributes to prevention of electrification.

The surface resistivity value of the heat-resistant resin layer 4B is preferably 1010? /? Or less, and particularly preferably 109? /? Or less, from the viewpoint of preventing adhesion of dust or the like to the release layer 4A of the multilayer film of the fourth invention. If the value of the surface resistivity is 1010? /? Or less, antistatic properties are effectively exhibited even on the surface of the release film for processing of the present invention. Therefore, it is possible to effectively suppress the adhesion of foreign substances such as dusts due to static electricity, and at the same time, even when a part of the semiconductor element comes into direct contact with the process release film during production of the semiconductor package, The breakdown of the semiconductor element can be effectively suppressed.

The value of the surface resistivity of the heat-resistant resin layer 4B is preferably as low as possible from the viewpoint of preventing adhesion of dust or the like to the release layer 4A of the negative-working film of the fourth invention invention, and the lower limit is not particularly limited. The surface resistivity value of the heat-resistant resin layer 4B tends to be smaller as the electrically conductive performance of the polymeric antistatic agent is higher and the content of the polymeric antistatic agent is greater.

The surface resistivity value of the heat-resistant resin layer 4B can be measured, for example, by the method described in this embodiment example. However, the heat-resistant resin layer 4B before lamination is used as a sample.

As the layer other than the layer 4B1 containing the polymeric antistatic agent, for example, an adhesive layer 4B2 including an adhesive can be preferably used. That is, the heat-resistant resin layer 4B may include a layer 4B1 containing a polymeric antistatic agent and an adhesive layer 4B2 including an adhesive.

In this case, the heat-resistant resin layer 4B may be composed of only the layer 4B1 containing the polymeric antistatic agent and the adhesive layer 4B2 including the adhesive, and the layer 4B1 containing the polymeric antistatic agent and the adhesive layer 4B2 containing the adhesive For example, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas barrier layer, and the like.

The layer 4B1 containing the polymeric antistatic agent may also contain an adhesive. That is, the heat-resistant resin layer 4B may include a layer 4B3 containing a polymeric antistatic agent and an adhesive.

In this case, the heat-resistant resin layer 4B may be composed only of the layer 4B3 containing the polymeric antistatic agent and the adhesive, and may be formed by using a layer other than the layer 4B3 containing the polymeric antistatic agent and the adhesive such as a polymeric antistatic agent , An adhesive layer 4B2 containing an adhesive, a thermoplastic resin layer not containing an antistatic agent and an adhesive, and a gas barrier layer.

In the release film for a process according to the fourth aspect of the present invention, the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse (TD) direction of the heat resistant resin layer 4B is 3% or less, or 23 DEG C It is preferable that the thermal dimensional change ratio up to 170 캜 is 3% or less. Further, the heat-resistant resin layer 4B preferably has a thermal dimensional change ratio of 3% or less in the transverse direction (TD) direction from 23 ° C to 120 ° C and a thermal dimensional change rate of 3% or less in the transverse direction (TD) Do.

The thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 4B is 3% or less, or the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 4B is 3% It is possible to more effectively suppress the occurrence of wrinkles when the metal mold is mounted inside the metal mold.

The mechanism by which the generation of wrinkles of the release layer is more effectively suppressed by using the resin layer in which the thermal dimensional change ratio in the transverse direction (TD) shows the above-mentioned specific value is used as the heat-resistant resin layer 4B is not necessarily clear, but a relatively small thermal expansion / contraction It is presumed that the thermal expansion / contraction of the release layer 4A (or release layer 4A ') by heating / cooling during the process is suppressed by using the heat-resistant resin layer 4B.

An optional resin layer including a non-oriented film can be used for the heat-resistant resin layer 4B, but it is particularly preferable to include a stretched film.

The stretched film tends to have a low thermal expansion coefficient or a negative thermal expansion due to the effect of stretching in the manufacturing process, and the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse direction (TD) is 3% It is relatively easy to realize a characteristic that the rate of change in thermal dimensional change from 23 deg. C to 170 deg. C in the (TD) direction is 3% or less. Therefore, it can be suitably used as the heat resistant resin layer 4B.

The thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat-resistant resin layer 4B is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

The thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat-resistant resin layer 4B is preferably 2% or less, more preferably 1.5% or less, further preferably 1% or less, desirable.

In the release film for a process according to the fourth aspect of the present invention, the thermal dimensional change ratio in the width direction (TD) direction of the heat resistant resin layer 4B from 23 ° C to 120 ° C and the thermal dimensional change rate Or 6% or the sum of the thermal dimensional change rate in the transverse direction (TD) direction from 23 ° C to 170 ° C in the direction of the thermal resistance resin layer 4B and the thermal dimensional change rate in the longitudinal direction (MD) direction from 23 ° C to 170 ° C is 5% desirable. Heat Resistant Layer 4B The sum of the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse (TD) direction and the thermal dimensional change from 23 ° C to 120 ° C in the longitudinal (MD) direction is 6% It is more preferable that the sum of the thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the longitudinal direction (TD) and the thermal dimensional change rate from 23 占 폚 to 170 占 폚 in the longitudinal (MD) direction is 5% or less. Since the sum of the thermal dimensional change ratio in the transverse (TD) direction and the longitudinal (MD) direction of the heat-resistant resin layer 4B is in the above range, it is possible to more effectively suppress the occurrence of wrinkles when mounted on the inner surface of the metal mold .

The sum of the thermal dimensional change rate from 23 DEG C to 120 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) direction is more preferably from -3.0% to 5.0% , More preferably not less than -2.0% and not more than 4.5%.

The sum of the thermal dimensional change rate from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) direction is more preferably -15.5% , More preferably not less than -10.0% and not more than 4.5%.

It is advantageous to use a stretched film in view of keeping the sum of the thermal dimensional change ratio in the transverse (TD) direction and the longitudinal (MD) direction of the heat-resistant resin layer 4B within the above range, Do.

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

The heat-resistant resin layer 4B preferably has heat resistance capable of withstanding the temperature of the metal mold (generally 120 to 180 DEG C) at the time of molding in view of controlling the strength of the film and the rate of change in thermal dimensional thereof to an appropriate range. In view of this, the heat-resistant resin layer 4B preferably contains a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 DEG C or higher, more preferably 155 DEG C or higher and 300 DEG C or lower, More preferably from 185 to 210 ° C, and particularly preferably from 185 to 205 ° C.

As described above, the heat-resistant resin layer 4B preferably includes a crystalline resin having a crystal component. As the crystalline resin to be contained in the heat-resistant resin layer 4B, a part or all of a crystalline resin such as a polyester resin, a polyamide resin, and a polypropylene resin can be used. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 and polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the above-mentioned crystalline resin in the heat-resistant resin layer 4B, wrinkles are less likely to occur in the resin sealing step and the like, and it is more advantageous to suppress wrinkles from being transferred to the molded article and causing defective appearance.

The resin constituting the heat-resistant resin layer 4B preferably has a crystal melting heat amount of not less than 20 J / g and not more than 100 J / g in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221, More preferably 25 J / g or more and 55 J / g or less, even more preferably 28 J / g or more and 50 J / g or less, more preferably 28 J / g or more and 40 J / g or less, and more preferably 28 J / g or more and 35 J / g or less. If it is 20 J / g or more, heat resistance and releasability that can withstand hot press forming such as a resin sealing process can be effectively exhibited, and also the rate of dimensional change can be suppressed to a small extent, so that occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal melting is not more than 100 J / g, the heat-resistant resin layer 4B can be provided with appropriate hardness, so that it is possible to ensure sufficient followability to the metal mold in the resin sealing process or the like, There is no possibility of becoming easy. Further, in this embodiment, the crystal melting heat quantity is determined by the relationship between the heat quantity (J / g) of the longitudinal axis obtained in the first heating step measured by a differential scanning calorimeter (DSC) according to JIS K7221 and the temperature Refers to a numerical value obtained by summing up peak areas having peaks at 120 ° C or higher in the chart shown.

The heat of crystal fusion of the heat-resistant resin layer 4B can be controlled by appropriately setting heating, cooling, and stretching conditions during the production of the film.

The thickness of the heat-resistant resin layer 4B is not particularly limited as long as the film strength can be secured, but is usually 1 to 100 μm, preferably 5 to 50 μm.

A layer containing a polymeric antistatic agent 4B1

As a polymeric antistatic agent for the layer 4B1 containing a polymeric antistatic agent suitably used for the heat-resistant resin layer 4B constituting the laminate of the fourth invention, a polymer compound known to have antistatic function can be used have. For example, a cationic copolymer having a quaternary ammonium base in a lateral group, an anionic compound containing polystyrene sulfonic acid, a compound having a polyalkylene oxide chain (a polyethylene oxide chain and a polypropylene oxide chain are preferable Polyether ester amides, polyether amide imides, polyether esters, ethylene oxide-epichlorohydrin copolymers, and the like. oxide-epichlorohydrin) copolymer, and? -conjugated conductive polymer. These may be used singly or in combination of two or more kinds.

Quaternary ammonium bases among copolymers having quaternary ammonium bases in the side groups have the effect of imparting rapid dielectric polarization relaxation by dielectric polarization and conductivity.

The copolymer preferably has a carboxy group together with a quaternary ammonium base at the side group. When having a carboxy group, the copolymer has crosslinkability and can form the layer 4B1 alone. When used in combination with an adhesive such as a urethane-based adhesive, it can react with the adhesive to form a crosslinked structure, and greatly improve adhesiveness, durability, and other mechanical properties.

The copolymer may further contain a hydroxy group at the side group. The hydroxy group has an effect of reacting with a functional group in the adhesive, for example, an isocyanate group to increase the adhesiveness.

The copolymer can be obtained by copolymerizing the above-mentioned monomers having functional groups. Specific examples of the monomer having a quaternary ammonium base include quaternary dimethylamino ethyl acrylate quats (including anions such as chloride, sulfate, sulfonate, alkyl sulfonate, etc. as a counter ion) . Specific examples of the monomer having a carboxy group include (meth) acrylic acid, (meta) acroyloxyethyl succinic acid, phthalic acid, and hexahydrophthalic acid.

Other monomers other than these may be copolymerized. Other monomers include vinyl derivatives such as alkyl (meth) acrylate, styrene, vinyl acetate, vinyl halide and olefin.

The ratio of the copolymer units having the respective functional groups of the copolymer may be appropriately set. The proportion of the copolymer unit having a quaternary ammonium base is preferably from 15 to 40 mol% based on the total amount of the copolymer units. When the ratio is 15 mol% or more, the antistatic effect is excellent. If it exceeds 40 mol%, the hydrophilicity of the copolymer may be excessively high. The proportion of the unit having a carboxy group is preferably 3 to 13 mol% based on the total of all the units.

When the copolymer has a carboxy group at the side group, a crosslinking agent (curing agent) is added to the copolymer. Examples of the crosslinking agent include bifunctional epoxy compounds such as glycerin diglycidyl ether, trifunctional epoxy compounds such as trimethylolpropane triglycidyl ether, and trimethylolpropane triazidinyl ether. And polyfunctional compounds such as imine compounds.

Imidazole derivatives such as 2-methyl imidazole, 2-ethyl and 4-methyl imidazole and other amines are added to the copolymer as ring-opening reaction catalysts of the above bifunctional and trifunctional epoxy compounds .

The? -conjugated conductive polymer is a conductive polymer having a main chain in which a? -conjugate is developed. As the? -conjugated conductive polymer, known ones may be used, and examples thereof include polythiophene, polypyrrole, polyaniline and derivatives thereof.

The polymeric antistatic agent may be a product prepared by a known method, or a commercially available product may be used. For example, a commercial product of a copolymer having a quaternary ammonium base and a carboxy group in its side group, and "BONDEIP (trade name) -PA100 main preparation" manufactured by KONISHI.

Preferred examples of the layer 4B1 containing a polymeric antistatic agent include the following layers (1) to (4) and the like.

Layer (1): A layer formed by the polymeric antistatic agent itself having film-forming ability, the polymeric antistatic agent dissolved or dissolved in a solvent or a solvent, and dried if necessary.

Layer (2): A layer formed by melt-coating the polymeric antistatic agent, wherein the polymeric antistatic agent itself is meltable with film forming ability.

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

Layer (4): The layer formed by the binder having film-forming ability, the composition containing the binder and the polymeric antistatic agent dissolved or dissolved in a solvent or a solvent, and dried if necessary. However, it is assumed that the layer (1) does not correspond to the layer (4).

The fact that the polymeric antistatic agent itself has film forming ability in the layer (1) means that the film is formed when the polymeric antistatic agent is soluble in a solvent such as an organic solvent and the solution is wet coated and dried.

The fact that the polymeric antistatic agent itself is meltable in the layer (2) means that it is melted by heating. The term " having film-forming ability ", " meltable ", for the binder of layer (3) (4) has the same meaning.

The polymeric antistatic agent of the layer (1) may be one having a crosslinking property or not having a crosslinking property. When the polymeric antistatic agent has a crosslinking property, a crosslinking agent may be used in combination.

Examples of polymeric antistatic agents having film formability and crosslinking properties include copolymers having quaternary ammonium bases and carboxy groups in the side groups.

Examples of the cross-linking agent include those described above.

The thickness of the layer (1) is preferably 0.01 to 1.0 mu m, particularly preferably 0.03 to 0.5 mu m. Since the thickness of the layer 1 is not less than 0.01 탆, sufficient antistatic effect can be easily obtained, and since the thickness is not more than 1.0 탆, sufficient adhesiveness can be easily obtained at the time of lamination.

Examples of the polymeric antistatic agent of the layer (2) include a surfactant and a polyolefin resin containing carbon black or the like. Commercially available products include PELECTRON HS (manufactured by Sanyo Chemical Industries) and the like. The preferred range of thickness of layer (2) is equal to the preferred range of thickness of layer (1).

As the binder for the layer 3, a general-purpose thermoplastic resin can be mentioned. The thermoplastic resin is preferably a resin having a functional group which contributes to adhesion so as to be bonded at the time of melt molding. Examples of the functional group include a carbonyl group and the like.

The content of the polymeric antistatic agent in the layer (3) is preferably from 10 to 40 parts by mass, more preferably from 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 a composition for forming layer 4 is an adhesive. The adhesive means a product containing a main agent and a curing agent and cured by heating or the like to exhibit an adhesive force.

At this time, the layer 4B1 containing the high molecular weight antistatic agent also corresponds to the layer 4B3 containing the high molecular weight antistatic agent and the adhesive.

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

Examples of the adhesive for forming the layer 4 (hereinafter, also referred to as an adhesive for forming the layer 4) include those obtained by adding a polymeric antistatic agent to an adhesive containing no high molecular weight antistatic agent, and the like have.

The polymeric antistatic agent to be added to the adhesive may have a film-forming ability and may be an element having no film-forming ability (for example, a? -Conjugated conductive polymer).

As the adhesive containing no polymeric antistatic agent, known adhesives for dry lamination can be used. For example, a polyvinyl acetate adhesive; Or a copolymer of an acrylic acid ester and other monomers (such as methyl methacrylate, acrylonitrile, styrene, etc.) with an acrylic acid ester (such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate) Polyacrylate ester adhesives; Cyanoacrylate-based adhesives; An ethylene copolymer system adhesive comprising a copolymer of ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc.); Cellulosic adhesives; Polyester-based adhesives; Polyamide adhesives; Polyimide-based adhesives; An amino resin-based adhesive composed of a urea resin or a melamine resin; Phenolic resin adhesives; Epoxy adhesive; Polyurethane-based adhesives for crosslinking polyol (polyether polyol, polyester polyol, etc.) with isocyanate and / or isocyanurate; Reactive (meth) acrylic adhesive; Rubber-based adhesives comprising chloroprene rubber, nitrile rubber, styrene-butadiene rubber and the like; Silicone adhesives; An inorganic adhesive comprising an alkali metal silicate, a low melting point glass and the like; Etc. may be used.

The content of the polymeric antistatic agent in the adhesive for forming the layer (4) is preferably such an amount that the surface resistivity of the layer (4) is 10 10? /? Or less, and particularly preferably 10 6? /? Or less.

From the viewpoint of preventing electrification, it is preferable that the content of the high molecular weight antistatic agent in the adhesive for forming the layer (4) is as large as possible. However, when the high molecular weight antistatic agent is a? -Conjugated conductive polymer, Based conductive antistatic agent is used as an adhesive for forming the layer 4 to form the layer 4B1, the adhesiveness of the layer 4 is lowered when the content of the high molecular weight antistatic agent is increased, and the adhesiveness of the first thermoplastic resin layer The adhesion between the first thermoplastic resin layer 2 and the second thermoplastic resin layer 3 may be insufficient. Therefore, in this case, the content of the polymeric antistatic agent in the adhesive for forming the layer 4 is preferably 40 mass% or less, more preferably 30 mass% or less, based on the solid content of the binder resin. The lower limit is preferably 1% by mass, and particularly preferably 5% by mass.

The thickness of the layer 4 is preferably 0.2 to 5 mu m, particularly preferably 0.5 to 2 mu m. When the thickness of the layer 4 is not less than the lower limit of the above range, the first thermoplastic resin layer and the second thermoplastic resin layer are excellent in adhesion and also excellent in antistatic property. When the upper limit of the above range is reached, the productivity is excellent.

The polymeric antistatic layer of layer 4B1 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 layers may be used.

As the polymeric antistatic layer, layer (1) is preferable in view of easiness of production. It may be used in combination with at least one of the layers (1) and (2) to (4).

Adhesive layer 4B2

As the adhesive contained in the adhesive layer 4B2 suitably used for the heat-resistant resin layer 4B constituting the laminate of the fourth invention, conventionally known adhesives can be suitably used. From the standpoint of the production of the layered product of the fourth invention, an adhesive for dry lamination can be preferably used. For example, a polyvinyl acetate adhesive; Or a copolymer of an acrylic acid ester and other monomers (such as methyl methacrylate, acrylonitrile, styrene, etc.) with an acrylic acid ester (such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate) Polyacrylate ester adhesives; Cyanoacrylate-based adhesives; An ethylene copolymer system adhesive comprising a copolymer of ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc.); Cellulosic adhesives; Polyester-based adhesives; Polyamide adhesives; Polyimide-based adhesives; An amino resin-based adhesive comprising a urea resin or a melamine resin; Phenolic resin adhesives; Epoxy adhesive; Polyurethane-based adhesives for crosslinking polyol (polyether polyol, polyester polyol, etc.) with isocyanate and / or isocyanurate; Reactive (meth) acrylic adhesive; Rubber-based adhesives comprising chloroprene rubber, nitrile rubber, styrene-butadiene rubber and the like; Silicone adhesives; An inorganic adhesive comprising an alkali metal silicate, a low melting point glass and the like; Etc. may be used.

A layer containing a high molecular weight antistatic agent and an adhesive 4B3

As the polymeric antistatic agent contained in the layer 4B3 containing the polymeric antistatic agent and the adhesive suitably used for the heat-resistant resin layer 4B constituting the laminate of the fourth invention, a layer containing a polymeric antistatic agent 4B1 can be suitably used. As the adhesive, an adhesive similar to that described above for the adhesive layer 4B2 including an adhesive can be suitably used.

In the layer 4 described above, when the composition for forming the layer 4 is an adhesive, it is a particularly preferable example as the layer 4B3 containing the polymeric antistatic agent and the adhesive.

Other layers

The process release film of the fourth invention may have a layer other than the release layer 4A, the heat-resisting resin layer 4B and the release layer 4A ', as long as it is against the object of the fourth invention of the present invention. The details of these other layers are the same as those described in the third invention of the present specification.

Although the total thickness of the process release film of the fourth invention is not particularly limited, for example, it is preferably 10 to 300 占 퐉, and more preferably 30 to 150 占 퐉. When the total thickness of the release film is within the above range, handling property when used as a roll is good, and the amount of film to be wasted is small, which is preferable.

Hereinafter, preferred embodiments of the process release film of the fourth invention will be described in more detail. 1 is a schematic view showing an example of a three-layer structure process release film. As shown in Fig. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one side thereof with an adhesive layer 14 interposed therebetween.

The releasing layer 16 is the release layer 4A described above, the heat-resistant resin layer 12 is the heat-resisting resin layer 4B described above, and the adhesive layer 14 is the adhesive layer described above. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing step; The heat-resistant resin layer 12 is desirably disposed on the side in contact with the inner surface of the metal mold in the sealing step.

2 is a schematic view showing an example of a release film for a process having a five-layer structure. Members having the same functions as those in Fig. 1 are denoted by the same reference numerals. 2, the release film 20 has a release layer 16A and a release layer 16B formed on both sides of the heat-resistant resin layer 12 through the adhesive layer 14. [ The release layer 16A is the release layer 4A described above and the heat resistant resin layer 12 is the heat resistant resin layer 4B described above, the release layer 16B is the release layer 4A 'described above, Adhesive layer.

The compositions of the release layers 16A and 16B may be the same or different from each other. The thicknesses of the release layers 16A and 16B may be the same or different from each other. However, if the releasing layers 16A and 16B have the same composition and thickness, they are symmetrical, which is preferable because deformation of the releasing film itself is less likely to occur. Particularly, in the release film of the fourth invention of the present invention, stress may be generated by heating in the sealing step, so that it is desirable to suppress deformation. Thus, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good releasability is obtained for both the molding and the inner surface of the metal mold.

Process for producing release film for process

The release film for process according to the fourth invention of the present invention can be produced by any method, but its preferred production method is the same as that described for the third invention of the present specification.

Manufacture process

The release film for a process according to the fourth invention of the present invention can be used by disposing a semiconductor chip or the like in a metal mold and arranging it between the semiconductor chip and the inner surface of the metal mold when injection molding the resin. By using the release film for processing according to the fourth invention of the present invention, it is possible to effectively prevent defective mold release and occurrence of flash from metal molds.

The resin used in the production process may be either a thermoplastic resin or a thermosetting resin. In the art, thermosetting resins are widely used, and epoxy-based thermosetting resins are particularly preferred.

Although the sealing of the semiconductor chip is the most typical example of the manufacturing process, the invention is not limited thereto. The fourth invention can be applied to a fiber-reinforced plastic molding process, a plastic lens molding process, and the like.

The details of the manufacturing process using the process release film of the fourth invention are the same as those described in the third invention of the present specification.

The release film of the fourth invention is not limited to the step of sealing a semiconductor element, but may be a step of molding and releasing various molded articles using a molded metal mold, for example, a fiber reinforced plastic molding and mold release process, And a releasing process.

[Example]

Hereinafter, the first to fourth inventions of the present application will be described in more detail by way of examples, but the first and second inventions of the present application are not limited thereto.

In the following Examples / Reference Examples, properties / properties were evaluated in the following manner.

(Thermal dimensional change rate)

The film sample was cut into a length of 20 mm and a width of 4 mm respectively in the MD and TD directions of the film and the distance between the chucks was measured using a TA Instrument TMA (thermomechanical analyzer, product name: Q400) The load was maintained at 23 DEG C for 5 minutes under a load of 8 mm to 0.005 N, and then the temperature was elevated from 23 DEG C to 120 DEG C at a rate of 10 DEG C / min to measure the dimensional change in each direction. The dimensional change rate was calculated.

Thermal dimensional change ratio (%) (23? 120 占 폚) = {[(L ₂ -L ₁ ) / L ₁ ] × 100}

L ₁ : Sample length (mm) at 23 ° C

L ₂ : Sample length at 120 ° C (mm)

Similarly, the dimensional change rate in each direction was measured by raising the temperature from 23 占 폚 to 170 占 폚 at a heating rate of 10 占 폚 / min, and the dimensional change rate was calculated according to the following equation (2).

Thermal dimensional change rate (%) (23 - 170 캜) = {[(L ₃ -L ₁ ) / L ₁ ] × 100}

L ₁ : Sample length (mm) at 23 ° C

L ₃ : Sample length at 170 ° C (mm)

Contact angle for water (water contact angle)

The contact angle of water on the surface of the release layer A and the like was measured using a contact angle meter (FACECA-W, manufactured by Kyowa Interfac Science) according to JIS R 3 2 5 7.

(Tensile modulus)

Method of measuring tensile modulus

The tensile modulus at 23 ° C, 120 ° C and 170 ° C was determined in accordance with JIS K7127.

Measurement conditions: Tensile mode

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

(Surface resistivity value)

The test piece of 10 x 10 cm cut out from the obtained release film was stored at a temperature of 23 DEG C and a humidity of 50% RH for 24 hours. Thereafter, an applied voltage was measured at 0.10 V, a temperature of 23 DEG C, and a humidity of 50% RH using a digital ultra-high resistance / microammeter (8340A) and a resistivity chamber (R12704) manufactured by Advantest.

(Reattachment test of ashes)

The antistatic property of the release film was evaluated by rubbing the release film 10 times with a cloth of polyester fiber under the conditions of 20 캜 and 50% RH,

No attachment: ○

Significant adhesion: x

Respectively.

(Melting point (Tm), crystal melting heat amount)

About 5 mg of a polymer sample was precise weighed using a Q100 of TA Instruments by differential scanning calorimetry (DSC), and the sample was precisely weighed at 25 ° C under a nitrogen gas inflow rate of 50 ml / min in accordance with JIS K7121 at a heating rate of 10 ° C / min to 280 deg. C to measure the heat fusion curve, and the melting point (Tm) and the crystal melting heat amount of the sample were obtained from the obtained heat melting curve.

(Dissimilarity)

As shown in Figs. 3-1 and 3-2, a release film for a process manufactured in each Example / Reference Example was subjected to a tensile force of 10 N between an upper metal mold (upper mold) and a lower metal mold And then vacuum adsorbed on the parting surface of the upper mold. Subsequently, the sealing resin was filled on the substrate so as to cover the semiconductor chip, and the semiconductor chip fixed on the substrate was placed on the lower mold and mold-closed. At this time, the temperature (molding temperature) of the molded metal mold was set at 120 DEG C, the molding pressure was set at 10 Mpa, and the molding time was set at 400 seconds. Then, as shown in Figs. 3-1C and 3-2C, the semiconductor chip was sealed with a sealing resin, and then the resin-sealed semiconductor chip (semiconductor package) was released from the release film.

The releasability of the release film was evaluated according to the following criteria.

◎: The release film peels off naturally at the same time the metal mold is opened

○: The releasing film is not peeled off naturally, but peeling easily when pulled by hand (applying tension)

X: The release film is in close contact with the resin sealing surface of the semiconductor package and is not peeled off by hand

(wrinkle)

After the release in the above process, the wrinkle state of the resin sealing surface of the release film and the semiconductor package was evaluated by the following criteria.

?: No wrinkles at all in the release film and the semiconductor package

?: The release film slightly wrinkled, but no wrinkle transfer to the semiconductor package

X: There are many wrinkles in the semiconductor package as well as in the release film

(Appearance of molded article)

After releasing in the above-mentioned process, the shape of the resin-sealed surface of the release film and the semiconductor package was evaluated according to the following criteria.

⊚: No wrinkles were found in any of the release film and the semiconductor package, and the outer periphery of the semiconductor package had no roughness at all

?: No wrinkles or slight wrinkles in the release film and the semiconductor package, and slight contusion in the outer periphery of the semiconductor package

X: There are many wrinkles in the semiconductor package as well as the release film, or there is a lot of roughness in the outer periphery of the semiconductor package

(Metal mold followability)

The followability of the metal mold of the release film when the release was performed in the above process was evaluated according to the following criteria.

◎: There is no resin scratch (part where resin is not charged) in semiconductor package

○: There is little resin scratch on the semiconductor package edge (but not scratches caused by wrinkles)

X: There is a lot of resin scratches on the end of semiconductor package (except scratches caused by wrinkles)

[Example 1-1]

As the heat-resistant resin layer 1B, biaxial stretching PET (polyethylene terephthalate) film (trade name: Lumirror F865 manufactured by Toray Co., Ltd.) having a thickness of 16 μm was used. The thermal dimensional change ratio of the biaxially stretched PET film from 23 ° C to 120 ° C was -1.6% in the longitudinal (MD) direction and -1.2% in the transverse (TD) direction. The melting point of the biaxially stretched PET film was 187 캜, and the heat of crystal fusion was 30.6 J / g.

As the release layers 1A and 1A ', an unoriented 4-methyl-1-pentene copolymer resin film was used. Specifically, a slit width of a T-die was adjusted by melt-extruding a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals Co., A film was used.

The unoriented 4-methyl-1-pentene copolymer resin film was subjected to corona treatment from the viewpoint of improvement in adhesiveness by an adhesive so that the surface of one film had a water contact angle of 30 ° or more according to JIS R3257 of 30 ° or more.

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

(glue)

The following urethane-based adhesive A was used as an adhesive used in a dry laminate process in which each film was stitched.

[Urethane-based adhesive A]

Main formulation: TAKELAC A-616 (manufactured by Mitsui Chemicals). Curing agent: TAKENATE A-65 (manufactured by Mitsui Chemicals). The main formulation and the curing agent were mixed so that the mass ratio (main agent: curing agent) was 16: 1 and ethyl acetate was used as a diluent.

(Production of release film)

On one side of a biaxially stretched PET (polyethylene terephthalate) film, a urethane-based adhesive A was coated with a gravure coat of 1.5 g / m ² , and the corona-treated side of the unstretched 4-methyl-1-pentene copolymer resin film was bonded by dry lamination Subsequently, the urethane-based adhesive A was coated at 1.5 g / m ² on the biaxially oriented PET (polyethylene terephthalate) film side of the laminated film and the corona-treated side of the unstretched 4-methyl-1-pentene copolymer resin film was bonded by dry lamination To obtain a release film for the process of a five-layer structure (release layer 1A / adhesive layer / heat-resistant resin layer 1B / adhesive layer / release layer 1A ').

Dry lamination conditions were 900 mm width of substrate, 30 m / min of conveying speed, 50-60 캜 of drying temperature, 50 캜 of laminate roll, and 3.0 MPa of roll pressure.

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

The results of evaluation of denticity, wrinkle and metal formability are shown in Table 1-1. The release film showed good releasability at the same time as the metal die was opened, and no wrinkles were found in either the release film or the semiconductor package, that is, the wrinkles were sufficiently suppressed, and the semiconductor package showed good metal moldability without any resin scratches gave. That is, the release film for process according to Example 1-1 was a release film for a process having good releasability, suppression of wrinkles, and good followability to a metal mold.

[Examples 1-2 to 1-12]

A release film for processing was produced in the same manner as in Example 1-1 except that each of the films shown in Table 1-1 was used as the release layers 1A and 1A 'and the heat-resistant resin layer 1B in the combination shown in Table 1-1 Sealing, releasing, and properties were evaluated. The results are shown in Table 1-1.

In some of them, the suppression of wrinkles or the followability of metal moldings did not reach Example 1-1. However, in all of the examples, good releasing films for processing were well balanced at a high level of releasability, suppression of wrinkles, and metal moldability.

The details of each film described in Table 1-1 are as follows.

(1A1) Pb-free 4MP-1 (TPX) film

A film of a lead-free film having a thickness of 15 μm formed by using a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(1A2) Pb-free 4MP-1 (TPX) film

A film of a lead-free film having a thickness of 15 μm formed using a 4-methyl-1-pentene copolymer resin (trade name: TPX, brand name: DX818) manufactured by Mitsui Chemicals Co., (Melting point: 235 DEG C, crystal melting heat amount: 28.1 J / g)

(1A3) Pb-free 4MP-1 (TPX) film

A film of a non-oriented film having a thickness of 50 μm formed by using a 4-methyl-1-pentene copolymer resin (trade name: TPX, brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(1A4) Pb-free 4MP-1 (TPX) film

A film of a non-oriented film having a thickness of 50 μm formed by using a 4-methyl-1-pentene copolymer resin (trade name: TPX, brand name: DX818) manufactured by Mitsui Chemicals Co., (Melting point: 235 DEG C, crystal melting heat amount: 28.1 J / g)

(1A5) Fluorine resin film

(Melting point: 256 占 폚, crystal melting heat amount: 33.7 J / g) made of ETFE (ethylene-tetrafluoroethylene) film (manufactured by Asahi Glass Co.,

(1A6) Polystyrene-based resin film

(Melting point: 253 deg. C, crystal melting heat amount: 19.2 J / g) made of a polystyrene type film having a thickness of 50 mu m (product name: Oidys CA-F,

(1B1) Biaxially oriented PET film

(Melting point: 187 占 폚, crystal melting heat amount: 30.6 J / g) made of biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror F865,

(1B2) Biaxially oriented PET film

(Melting point: 258 占 폚, crystal melting heat amount: 39.4 J / g) made of biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror S10,

(1B3) Biaxially oriented nylon film

A biaxially oriented nylon film (trade name: bonyl RX, manufactured by KOHJIN FILM & CHEMICALS CO., LTD. (Melting point: 212 DEG C, crystal melting heat amount: 53.1 J / g)

(1B4) Biaxially oriented nylon film

(Unilon S330 manufactured by Idemitsu Unitech Co., Ltd., melting point: 221 占 폚, crystal melting heat amount: 60.3 J / g)

(1B5) Biaxially oriented polypropylene film

(Melting point: 160 占 폚, crystal melting heat amount: 93.3 J / g, manufactured by Mitsui Chemicals Tohcello Co., Ltd., product name: U-2)

(1B6) Lead-free nylon film

(Melting point: 220 占 폚, crystal melting heat amount: 39.4 J / g) (Mitsubishi Plastics Co., Ltd., product name: DYNAMILON C)

(1B7) Biaxially oriented PET film

(Teijin dupont films Co., Ltd., product name: FT3PE) (melting point: 214 占 폚, crystal melting heat amount: 40.3 J / g)

(1B8) Lead-free polybutylene terephthalate film

A film of a non-oriented film of 20 μm in thickness formed by using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 223 DEG C, crystal melting heat amount: 49.8 J / g)

(1B9) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 20 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

(1B10) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 50 μm formed by using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 223 DEG C, crystal melting heat amount: 49.8 J / g)

(1B11) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 50 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

[Reference Examples 1-1 to 1-4]

The films 1A3, 1A4, 1B10, and 1B11 shown in Table 1-1 were individually used as release films for processing, and sealing and releasing were performed in the same manner as in Example 1-1, and the properties of the release films for the process were evaluated did.

In any of the reference examples, the performance remained comprehensively inferior to the examples, and in particular, the occurrence of wrinkles could not be suppressed.

[Examples 13 to 20]

In the combination shown in Table 1-2, a release film made of each of the films described in Table 1-2 as release layers 1A and 1A 'and a heat-resistant resin layer 1B was used in the same manner as in Example 1-1, Sealing, releasing, and evaluation of properties.

As shown in Fig. 4, the release film was placed between the upper mold and the lower mold in a state of applying tensile force of 20 N, and vacuum adsorbed onto the upper mold surface. Subsequently, the sealing resin was filled on the substrate so as to cover the semiconductor chip, and the semiconductor chip fixed on the substrate was placed on the lower mold and closed. At this time, the temperature (molding temperature) of the metal mold was set at 170 DEG C, the molding pressure was set at 10 Mpa, and the molding time was set at 100 seconds. Then, as shown in Fig. 3-1C, the semiconductor chip was sealed with a sealing resin, and then the resin-sealed semiconductor chip (semiconductor package) was released from the release film. The results are shown in Table 1-2.

In some of them, the metal formability was not satisfactory in Example 1-1. However, any of the Examples is a good releasing film for processes with good balance of releasability, suppression of wrinkles, and high followability of metal moldings. Examples 1-13 to 1-15 were release films for processes with good releasability, suppression of wrinkles, and good followability of metal moldings.

[Reference Examples 1-5 to 1-7]

In the same manner as in Examples 1-11 to 1-16 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 in the combination shown in Table 1-2, A releasing film was prepared, sealing and releasing were carried out, and the characteristics were evaluated. The results are shown in Table 1-2.

The mold releasability and metal mold conformability were as good as in the examples, but the occurrence of wrinkles could not be suppressed.

[Reference Examples 1-8 to 1-11]

The films 1A1, 1A2, 1B10 and 1B11 shown in Table 1-2 were individually used as release films for the process, and sealing and releasing were performed in the same manner as in Examples 1-11 to 1-16. The properties were evaluated.

In any of the reference examples, the performance remained in general not satisfying the respective examples, and in particular, the generation of wrinkles could not be suppressed.

[Example 2-1]

A biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror F865, manufactured by Toray Co., Ltd.) having a thickness of 16 μm was used as the substrate 2B0a of the heat-resistant resin layer 2B.

As the antistatic resin a, a layer containing a polymeric antistatic agent was formed using a PEDOT polythiophene resin (product name: MC-200, manufactured by kakensangyo). More specifically, the antistatic resin a was coated on one side of the substrate 2B0a of the heat-resistant resin layer 2B at a coverage of 0.1 g / m < ² > and dried to form a layer 2B1a containing a polymeric antistatic agent.

The thermal dimensional change ratio of the biaxially stretched PET film (heat-resistant resin layer 2Ba) obtained from the above obtained layer containing the polymeric antistatic agent to 23 ° C to 120 ° C was -1.8% in the longitudinal (MD) direction, To -1.4%. The melting point of the biaxially stretched PET film was 187 캜, and the heat of crystal fusion was 30.6 J / g.

As the release layers 2A and 2A ', a non-oriented 4-methyl-1-pentene copolymer resin film 2Aa (2A'a) was used. Specifically, a slit width of a T-die was adjusted by melt-extruding a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., I used the tabernacle.

The unoriented 4-methyl-1-pentene copolymer resin film was subjected to corona treatment from the viewpoint of improvement in adhesiveness by an adhesive so that the surface of one film had a water contact angle of 30 or more in accordance with JIS R3257 of 30 ° or more.

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

(glue)

As the adhesive used in the dry lamination process of attaching each film, the following urethane adhesive agent? Was used.

[Urethane-based adhesive a]

Main formulation: TAKELAC A-616 (manufactured by Mitsui Chemicals). Curing agent: TAKENATE A-65 (manufactured by Mitsui Chemicals). The main formulation and the curing agent were mixed so that the mass ratio (main agent: curing agent) was 16: 1 and ethyl acetate was used as a diluent.

(Production of release film)

On one side of the biaxially stretched PET film (heat-resistant resin layer 2Ba) provided with the antistatic layer, a urethane-based adhesive agent? Was coated with 1.5 g / m ² by a gravure coat and subjected to a corona treatment of the non-oriented 4-methyl-1-pentene copolymer resin film 2Aa The surface of the biaxially stretched PET film of the laminate film was coated with 1.5 g / m ² of urethane-based adhesive agent, and a 4-methyl-1-pentene copolymer resin film 2A'a of corona Treated surfaces were bonded to each other with a dry laminate to obtain a release film for a five-layer structure (release layer 2A / adhesive layer / heat-resistant resin layer 2B / adhesive layer / release layer 2A ').

Dry lamination conditions were 900 mm width of substrate, 30 m / min of conveying speed, 50 to 60 캜 of drying temperature, 50 캜 of laminate roll, and 3.0 MPa of roll pressure.

The thermal dimensional change ratio of the process release film from 23 ° C to 120 ° C was 2.2% in the longitudinal (MD) direction and 1.4% in the transverse (TD) direction.

The moldability, appearance of the molded part and evaluation results of metal moldability are shown in Table 2-1. The release film showed good releasability at the same time as the metal mold was opened, and the release film and the semiconductor package had no wrinkles or irregularities, that is, the wrinkles were sufficiently suppressed, so that a good metal mold And showed followership. That is, the release film for the process of Example 2-1 was a release film for a process having good releasability, appearance of a molded article, and good followability to a metal mold.

[Examples 2-2 to 2-8]

A release film for processing was produced in the same manner as in Example 2-1 except that the film composition shown in Table 2-1 was used, and sealing and releasing were performed and the characteristics were evaluated. The results are shown in Table 2-1.

The details of the polymeric antistatic agents 2b to 2e and the layers 2B1b to 2B1e described in Table 2-1 are as follows.

As the antistatic resin 2b, a layer containing a polymeric antistatic agent was formed using a PEDOT polythiophene resin (product name: S-495, manufactured by CHUKYO YUSHI CO., LTD.). More specifically, the antistatic resin 2b was coated on one side of the substrate 2B0a or the like of the heat-resistant resin layer 2B at a coating amount of 0.3 g / m < ² > and dried to form a layer 2B1b containing a polymeric antistatic agent. The thermal dimensional change ratio of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above from 23 占 폚 to 120 占 폚 is the result shown in Table 2-1.

As the antistatic resin 2c, a layer containing a polymeric antistatic agent was formed using a PEDOT polythiophene resin (product name: P-530RL, manufactured by NAGASE INDUSTRIES, LTD.). More specifically, the antistatic resin 2c was coated on one side of the substrate 2B0a or the like of the heat-resistant resin layer 2B with a coating amount of 0.1 g / m < ² > and dried to form a layer 2B1c containing a polymeric antistatic agent. The thermal dimensional change ratio of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above from 23 占 폚 to 120 占 폚 is the result shown in Table 2-1.

As the antistatic resin 2d, a layer containing a polymeric antistatic agent was formed using a quaternary ammonium salt-containing resin (manufactured by Taisei Fine Chemical Co., Ltd., product name: 1SX-1090). More specifically, the antistatic resin 2d was coated on one side of the substrate 2B0a or the like of the heat-resistant resin layer 2B with a coating amount of 0.4 g / m < ² > and dried to form the layer 2B1d containing the polymeric antistatic agent. The thermal dimensional change ratio of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above from 23 占 폚 to 120 占 폚 is the result shown in Table 2-1.

As the antistatic resin 2e, a layer containing a polymeric antistatic agent was formed by using an anionic-based synthetic clay mineral-containing polyester resin (product name: ASA-2050, manufactured by TAKAMATSU Oil & Fat Co., Ltd.). Specifically, by coating an antistatic resin 2e in coating amount of 0.4 g / m ² on one surface of a base material such as a heat-resistant resin layer 2B 2B0a and dried to form a layer 2B1e containing high-molecular antistatic agent. The test items and evaluation results of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above, such as the rate of change of thermal dimensional change from 23 ° C to 120 ° C and the water contact angle, were as shown in Table 2-1.

All embodiments were good in all test items of mold release, molded article appearance, metal mold follow-up and reattachment test, and were a balanced process release film in terms of performance.

The details of each film described in the table are as follows.

(2Aa) Pb-free 4MP-1 (TPX) film

A film made of a lead-free film having a thickness of 15 μm using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(2Ab) Pb-free 4MP-1 (TPX) film

A film of a non-oriented film having a thickness of 50 μm formed by using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(2Ac) fluororesin film

(Melting point: 256 占 폚, crystal melting heat amount: 33.7 J / g) made of ETFE (ethylene-tetrafluoroethylene) film (manufactured by Asahi Glass Co.,

(2B0a) Biaxially oriented PET film

(Melting point: 187 占 폚, crystal melting heat amount: 30.6 J / g) made of biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror F865,

(2B0b) Biaxially oriented polypropylene film

(Melting point: 160 占 폚, crystal melting heat amount: 93.3 J / g, manufactured by Mitsui Chemicals Tohcello Co., Ltd., product name: U-2)

(2B0c) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 20 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

(2B0d) Biaxially oriented nylon film

(Unilon S330 manufactured by Idemitsu Unitech Co., Ltd., melting point: 221 占 폚, crystal melting heat amount: 60.3 J / g)

(2B0e) Lead-free nylon film

(Melting point: 220 占 폚, crystal melting heat amount: 39.4 J / g, manufactured by Mitsubishi Plastics Co., Ltd., product name: DYNAMILON C)

(2B0f) Biaxially oriented PET film

(Melting point: 214 占 폚, crystal melting heat amount: 40.3 J / g, manufactured by Teijin DuPont Films Co., Ltd., product name: FT3PE)

(2B0g) Lead-free polybutylene terephthalate film

A film of a non-oriented film of 20 μm in thickness formed by using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 223 DEG C, crystal melting heat amount: 49.8 J / g)

(2B0h) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 50 μm formed by using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 223 DEG C, crystal melting heat amount: 49.8 J / g)

[Reference Examples 2-1 to 2-4]

The sealing and releasing were carried out in the same manner as in Example 2-1 except that the film composition shown in Table 2-1 was used, and the characteristics of the release film for the process were evaluated.

In any reference example, the overall performance remained unexpected, and the appearance of the molded article was inferior in particular. In addition, good results were not obtained except in Reference Example 2-2 in reattachment test.

[Examples 2-9 to 2-16]

A release film for processing was produced in the same manner as in Example 2-1 except that each of the films shown in Table 2-2 was changed to the release layers 2A and 2A 'and the heat-resistant resin layer 2B in the combination of Table 2-2, , The release was performed and the properties were evaluated.

As shown in FIG. 3A, the release film was placed between the upper mold and the lower mold in a state of applying tensile force of 20 N, and then vacuum adsorbed onto the upper molding surface. Subsequently, the sealing resin was filled on the substrate so as to cover the semiconductor chip, and the semiconductor chip fixed on the substrate was placed on the lower mold and closed. At this time, the temperature (molding temperature) of the molded metal mold was set to 170 ° C, the molding pressure was set to 10 Mpa, and the molding time was set to 100 seconds. Then, as shown in Fig. 3C, the semiconductor chip is sealed with a sealing resin, and then the resin-sealed semiconductor chip (semiconductor package) is released from the release film. The results are shown in Table 2-2.

Despite the evaluation of the high temperature range of 170 ° C in either embodiment, it was good in all test items of releasability, appearance of the molded article, metal formability and reattachment test, and it was a balanced release film for the process in terms of performance. In particular, Example 2-11 and Examples 2-13 to 2-15 were release films for processes with good releasability, appearance of the molded article and good followability to the metal mold.

[Reference Examples 2-5 to 2-7]

A release film for processing was produced in the same manner as in Examples 2-11 to 2-16 except that the film composition shown in Table 2-2 was used, and sealing and releasing were carried out and properties were evaluated. The results are shown in Table 2-2.

The releasability was as good as in the examples, but the appearance of wrinkles could not be suppressed and the appearance of the molded article was inferior. In addition, no good results were obtained except in Reference Example 2-6.

[Reference Examples 2-8 to 2-10]

Sealing and releasing were carried out in the same manner as in Example 2-9 except that the film composition shown in Table 2-2 was used, and the characteristics of the release film for the process were evaluated. The results are shown in Table 2-2.

All of the reference examples were comprehensively inferior in performance to each of the examples, in particular, the generation of wrinkles could not be suppressed, and the appearance of the molded article was inferior.

Hereinafter, the third and fourth inventions of the present application will be described in more detail by way of examples, but the third and fourth inventions of the present application are not limited thereto.

In the following Examples / Reference Examples, properties / properties were evaluated in the following manner.

(Thermal dimensional change rate)

The film sample was cut into a length of 20 mm and a width of 4 mm in the longitudinal (MD) and transverse (TD) directions of the film, respectively. Using a TA Instrument TMA (thermomechanical analyzer, product name: Q400) After maintaining a load of 0.005 N under a dry state at 23 캜 for 5 minutes, the temperature was raised from 23 캜 to 120 캜 at a rate of temperature increase of 10 캜 / min to measure the dimensional change in each direction. Respectively.

Thermal dimensional change ratio (%) (23? 120 占 폚) = {[(L ₂ -L ₁ ) / L ₁ ] × 100}

L ₁ : Sample length (mm) at 23 ° C

L ₂ : Sample length at 120 ° C (mm)

In the same manner, the temperature was raised from 23 占 폚 to 170 占 폚 at a heating rate of 10 占 폚 / min to measure the dimensional change in each direction, and the dimensional change rate was calculated according to the following formula (2).

Thermal dimensional change rate (%) (23 - 170 캜) = {[(L ₃ -L ₁ ) / L ₁ ] × 100}

L ₁ : Sample length (mm) at 23 ° C

L ₃ : Sample length at 170 ° C (mm)

Contact angle for water (water contact angle)

The contact angle of water on the surface of the release layer A and the like was measured using a contact angle meter (FACECA-W, manufactured by Kyowa Interfac Science) according to JIS R3257.

(Tensile modulus)

Method of measuring tensile modulus

The tensile modulus at 23 ° C, 120 ° C and 170 ° C was determined in accordance with JIS K7127.

Measurement conditions: Tensile mode

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

(Surface resistivity value)

The test piece of 10 10 cm cut out from the obtained release film was stored at a temperature of 23 캜 and a humidity of 50% RH for 24 hours. Thereafter, an applied voltage was measured at a voltage of 0.10 V, a temperature of 23 DEG C, and a humidity of 50% RH by using a digital ultra-high resistance / microammeter (8340A) and a resistivity chamber (R12704) manufactured by Advantest.

(Reattachment test of ashes)

The antistatic property of the release film was evaluated by rubbing the release film 10 times with a cloth of polyester fiber under the conditions of 20 占 폚 and 50% RH,

No attachment: ○

Significant adhesion: x

Respectively.

(Melting point (Tm), crystal melting heat amount)

About 5 mg of the polymer sample was precisely analyzed using a differential scanning calorimeter (DSC) of Q100 from TA Instrument, and the temperature was changed from 25 ° C at a nitrogen gas inflow rate of 50 ml / min to 280 ° C at a heating rate of 10 ° C / min according to JIS K7121 To measure the heat melting curve, and the melting point (Tm) and the crystal melting heat amount of the sample were obtained from the obtained heat melting curve.

(Dissimilarity)

As shown in Fig. 3, the release films for process made in each Example and Reference Example were placed in a state in which a tensile force of 10 N was applied between the upper mold and the lower mold, and then vacuum adsorbed onto the upper mold surface. Subsequently, the sealing resin was filled on the substrate so as to cover the semiconductor chip, and the semiconductor chip fixed on the substrate was placed on the lower mold and closed. At this time, the temperature (molding temperature) of the molded metal mold was set at 120 DEG C, the molding pressure was set at 10 Mpa, and the molding time was set at 400 seconds. Then, as shown in Fig. 3C, the semiconductor chip is sealed with a sealing resin, and then the resin-sealed semiconductor chip (semiconductor package) is released from the release film.

The releasability of the release film was evaluated according to the following criteria.

◎: The release film peels off naturally at the same time the metal mold is opened

○: The release film is not peeled off naturally, but is easily peeled off when it is pulled by hand (by applying tension).

X: The release film is in close contact with the resin sealing surface of the semiconductor package and is not peeled off by hand

(wrinkle)

After the release in the above process, the wrinkle state of the resin sealing surface of the release film and the semiconductor package was evaluated by the following criteria.

?: No wrinkles at all in the release film and the semiconductor package

?: The release film slightly wrinkled, but no wrinkle transfer to the semiconductor package

X: There are many wrinkles in the semiconductor package as well as in the release film

(Appearance of molded article)

After releasing in the above-mentioned process, the shape of the resin-sealed surface of the release film and the semiconductor package was evaluated according to the following criteria.

⊚: No wrinkles were found in any of the release film and the semiconductor package, and the outer periphery of the semiconductor package had no roughness at all

?: No wrinkles or slight wrinkles in the release film and the semiconductor package, and slight contusion in the outer periphery of the semiconductor package

X: There are many wrinkles in the semiconductor package as well as the release film, or there is a lot of roughness in the outer periphery of the semiconductor package

(Metal mold followability)

The followability of the metal mold of the release film when the release was performed in the above process was evaluated according to the following criteria.

◎: There is no resin scratch (part where resin is not charged) in semiconductor package

○: There is little resin scratch on the semiconductor package edge (but not scratches caused by wrinkles)

X: There is a lot of resin scratches on the end of semiconductor package (except scratches caused by wrinkles)

[Example 3-1]

As the heat-resistant resin layer 3B, a biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror S10 manufactured by Toray Co., Ltd.) having a thickness of 12 μm was used. The thermal dimensional change ratio 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. The melting point of the biaxially stretched PET film was 258 占 폚, and the heat of crystal melting was 39.4 J / g.

As the release layers 3A and 3A ', a non-oriented 4-methyl-1-pentene copolymer resin film was used. Specifically, a slit width of a T-die was adjusted by melt extruding the 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., I used the tabernacle.

The unoriented 4-methyl-1-pentene copolymer resin film was subjected to corona treatment from the viewpoint of improvement in adhesiveness by an adhesive so that the film surface of one of the films was 30 or less when the water contact angle according to JIS R3257 was 30 or more.

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

(glue)

The following urethane-based adhesive A was used as the adhesive used in the dry lamination process in which the respective films were pasted together.

[Urethane-based adhesive A]

Main formulation: TAKELAC A-616 (manufactured by Mitsui Chemicals). Curing agent: TAKENATE A-65 (manufactured by Mitsui Chemicals). The mass ratio of the main agent and the curing agent (main agent: curing agent) was adjusted to 16: 1 and ethyl acetate was used as a diluent.

(Production of release film)

On one side of a biaxially stretched PET (polyethylene terephthalate) film, a urethane-based adhesive A was coated with a gravure coat of 1.5 g / m ² , and the corona-treated side of the unstretched 4-methyl-1-pentene copolymer resin film was bonded by dry lamination , Followed by coating a urethane-based adhesive A at 1.5 g / m ² on the side of the biaxially stretched PET (polyethylene terephthalate) film side of the laminated film and drying the corona-treated side of the unstretched 4-methyl-1-pentene copolymer resin film by dry lamination (Release layer 3A / adhesive layer / heat-resistant resin layer 3B / adhesive layer / release layer 3A ').

Dry lamination conditions were 900 mm width of substrate, 30 m / min of conveying speed, 50 to 60 캜 of drying temperature, 50 캜 of laminate roll, and 3.0 MPa of roll pressure.

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

Table 3-1 shows the evaluation results of denticity, wrinkle and metal formability. The release film showed good releasability at the same time as the metal mold was opened, and no wrinkles were found in either the release film or the semiconductor package, that is, the wrinkles were sufficiently suppressed, so that a good metal mold follow- . That is, the release film for the process of Example 3-1 was a releasing film for a process having good releasability, suppression of wrinkles, and excellent followability to the metal mold.

[Examples 3-2 to 3-9]

A release film for processing was produced in the same manner as in Example 3-1, except that each of the films shown in Table 3-1 shown in Table 3-1 was used as the release layers 3A and 3A 'and the heat-resistant resin layer 3B , Sealing, releasing, and evaluation of properties. The results are shown in Table 3-1.

In some cases, the wrinkle suppression or metal moldability followability did not reach Example 3-1. However, all of the examples were good release films for processing, which were balanced at a high level of releasability, suppression of wrinkles and metal moldability.

The details of each film described in the table are as follows.

(3A1) Pb-free 4MP-1 (TPX) film

A film made of a lead-free film having a thickness of 15 μm using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(3A2) Pb-free 4MP-1 (TPX) film

A film of a lead-free film having a thickness of 15 μm formed by using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: DX818) manufactured by Mitsui Chemicals Co., (Melting point: 235 DEG C, crystal melting heat amount: 28.1 J / g)

(3A3) Pb-free 4MP-1 (TPX) film

A film of a non-oriented film having a thickness of 50 μm formed by using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(3B1) Biaxially oriented PET film

(Melting point: 258 占 폚, crystal melting heat amount: 39.4 J / g) made of biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror S10,

(3B2) Biaxially oriented nylon film

A biaxially oriented nylon film (trade name: bonyl RX, manufactured by KOHJIN FILM & CHEMICALS CO., LTD. (Melting point: 212 DEG C, crystal melting heat amount: 53.1 J / g)

(3B3) Biaxially oriented nylon film

(Unilon S330 manufactured by Idemitsu Unitech Co., Ltd., melting point: 221 占 폚, crystal melting heat amount: 60.3 J / g)

(3B4) Biaxially oriented polypropylene film

(Melting point: 160 占 폚, crystal melting heat amount: 93.3 J / g, manufactured by Mitsui Chemicals Tohcello Co., Ltd., product name: U-2)

(3B5) Lead-free nylon film

(Melting point: 220 占 폚, crystal melting heat amount: 39.4 J / g, manufactured by Mitsubishi Plastics Co., Ltd., product name: DYNAMILON C)

(3B6) Biaxially oriented PET film

(Melting point: 214 占 폚, crystal melting heat amount: 40.3 J / g, manufactured by Teijin DuPont Films Co., Ltd., product name: FT3PE)

(3B7) Lead-free polybutylene terephthalate film

A film of a non-oriented film of 20 μm in thickness formed by using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 223 DEG C, crystal melting heat amount: 49.8 J / g)

(3B8) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 20 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

(3B9) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 50 μm formed by using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 223 DEG C, crystal melting heat amount: 49.8 J / g)

(3B10) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 50 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

[Reference Examples 3-1 to 3-3]

The films 3A3, 3B9 and 3B10 shown in Table 3-1 were individually used as release films for the process, and sealing and releasing were performed in the same manner as in Example 3-1, and the characteristics of the release films for the process were evaluated.

In any reference example, the performance remained comprehensively inferior to the examples, and in particular, the occurrence of wrinkles could not be suppressed.

[Examples 3-10 to 3-14]

Using a release film made of the respective films shown in Table 3-2 as the release layers 3A and 3A 'and the heat-resistant resin layer 3B in the combination shown in Table 3-2, a process release film was obtained in the same manner as in Example 3-1 Sealing, releasing, and evaluation of properties.

As shown in Fig. 4, the release film was placed between the upper mold and the lower mold in a state of applying tensile force of 20 N, and vacuum adsorbed onto the upper mold surface. Subsequently, the sealing resin was filled on the substrate so as to cover the semiconductor chip, and the semiconductor chip fixed on the substrate was placed on the lower mold and closed. At this time, the temperature (molding temperature) of the metal mold was set at 170 占 폚, the molding pressure was set at 10 Mpa, and the molding time was set at 100 seconds. Then, as shown in Fig. 3C, the semiconductor chip is sealed with a sealing resin, and then the resin-sealed semiconductor chip (semiconductor package) is released from the release film. The results are shown in Table 3-2.

In some cases, the metal moldability was not satisfactory to Example 3-1. However, any of the Examples is a good releasing film for processing with good balance of releasability, suppression of wrinkles and high followability of metal moldings, -13 was a releasing film for process with good releasability, suppression of wrinkles and good followability of metal mold.

[Reference Examples 3-4 to 3-6]

In the same manner as in Examples 3-10 to 3-14 except that each of the films shown in Table 3-2 was used as the release layers 3A and 3A 'and the heat-resistant resin layer 3B in the combinations shown in Table 3-2, A release film was prepared, subjected to sealing and releasing, and the properties were evaluated. The results are shown in Table 3-2.

The mold releasability and metal mold conformability were as good as in the examples, but the occurrence of wrinkles could not be suppressed.

[Reference Examples 3-7 to 3-10]

The films 3A1, 3A2, 3B9 and 3B10 shown in Table 3-2 were individually used as release films for the process, and sealing and releasing were carried out in the same manner as in Examples 3-10 to 3-14, The properties were evaluated.

Any of the reference examples has remained in a performance which does not comprehensively satisfy the respective embodiments, and in particular, the occurrence of wrinkles can not be suppressed.

[Example 4-1]

As the substrate 4B0a of the heat-resistant resin layer 4B, a biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror S10 manufactured by Toray Co., Ltd.) having a thickness of 12 μm was used.

As the antistatic resin 4a, a layer containing a polymeric antistatic agent was formed using a PEDOT polythiophene resin (product name: MC-200, manufactured by kakensangyo). More specifically, the antistatic resin 4a was coated on one side of the substrate 4B0a of the heat-resistant resin layer 4B with a coverage of 0.1 g / m < ² > and dried to form a layer 4B1a containing a polymeric antistatic agent.

The thermal dimensional change ratio of the biaxially stretched PET film (heat-resistant resin layer 4Ba) obtained from the above obtained layer containing the polymeric antistatic agent to 23 ° C to 120 ° C was -0.1% in the longitudinal (MD) direction, Respectively. The melting point of the biaxially stretched PET film was 258 占 폚, and the heat of crystal melting was 39.4 J / g.

As the release layers 4A and 4A ', a non-oriented 4-methyl-1-pentene copolymer resin film 4Aa (4A'a) was used. Specifically, a non-oriented film having a thickness of 15 占 퐉 was formed by using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Corporation. (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

The unoriented 4-methyl-1-pentene copolymer resin film was subjected to corona treatment from the viewpoint of improvement in adhesiveness by an adhesive so that the surface of one film had a water contact angle of 30 or more in accordance with JIS R3257 of 30 ° or more.

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

(glue)

As the adhesive used in the dry lamination process of attaching each film, the following urethane adhesive agent? Was used.

[Urethane-based adhesive a]

Main formulation: TAKELAC A-616 (manufactured by Mitsui Chemicals). Curing agent: TAKENATE A-65 (manufactured by Mitsui Chemicals). The main formulation and the curing agent were mixed so that the mass ratio (main agent: curing agent) was 16: 1 and ethyl acetate was used as a diluent.

(Production of release film)

On one side of the biaxially stretched PET film (heat-resistant resin layer 4Ba) provided with the antistatic layer, a urethane-based adhesive agent? Was coated with 1.5 g / m ² by a gravure coat and subjected to corona treatment of a 4-methyl-1-pentene copolymer resin film 4Aa After the surface of the biaxially stretched PET film of the laminate film was coated with 1.5 g / m ² of urethane adhesive, a 4-methyl-1-pentene copolymer resin film 4A'a of corona The treated surfaces were bonded by dry lamination to obtain a release film for a five-layer structure (release layer 4A / adhesive layer / heat-resistant resin layer 4B / adhesive layer / release layer 4A ').

Dry lamination conditions were 900 mm width of substrate, 30 m / min of conveying speed, 50 to 60 캜 of drying temperature, 50 캜 of laminate roll, and 3.0 MPa of roll pressure.

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

Tensile Modulus, Dissimilarity, Appearance of Molded Products Table 4-1 shows the evaluation results of the metal mold-following surface resistivity and reattachment test. The mold release film showed good releasability at the same time as the metal mold was opened, and the mold release film and the semiconductor package had no wrinkles or irregularities, that is, the wrinkles were sufficiently suppressed, And showed followership. That is, the release film for a process of Example 4-1 was a release film for a process having good releasability, appearance of a molded article, and good followability to a metal mold. Also, adhesion of ashes was not recognized.

[Examples 4-2 to 4-9]

A release film for processing was produced in the same manner as in Example 4-1 except that the film composition shown in Table 4-1 was used, and sealing and releasing were performed and the characteristics were evaluated. The results are shown in Table 4-1.

The details of the polymeric antistatic agents 4b to 4e and the layers 4B1b to 4B1e containing the polymeric antistatic agents 4b1 to 4e1 described in Table 4-1 are as follows.

As the antistatic resin 4b, a layer containing a polymeric antistatic agent was formed using a PEDOT polythiophene resin (product name: S-495, manufactured by CHUKYO YUSHI CO., LTD.). More specifically, the antistatic resin 4b was coated on one side of the substrate 4B0a or the like of the heat-resistant resin layer 4B at a coating amount of 0.3 g / m < ² > and dried to form a layer 4B1b containing a polymeric antistatic agent. The thermal dimensional change ratio of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above from 23 ° C to 120 ° C is the results shown in Table 4-1.

As the antistatic resin 4c, a layer containing a polymeric antistatic agent was formed using a PEDOT polythiophene resin (product name: P-530RL, manufactured by NAGASE INDUSTRIES, LTD.). More specifically, the antistatic resin 4c was coated on one side of the substrate 4B0a or the like of the heat-resistant resin layer 4B with a coverage of 0.1 g / m < ² > and dried to form a layer 4B1c containing a polymeric antistatic agent. The thermal dimensional change ratio of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above from 23 ° C to 120 ° C is the results shown in Table 4-1.

As the antistatic resin 4d, a layer containing a polymeric antistatic agent was formed by using a quaternary ammonium salt-containing resin (product of Taisei Fine Chemical, product name: 1SX-1090). More specifically, the antistatic resin 4d was coated on one side of the substrate 4B0a or the like of the heat-resistant resin layer 4B with a coverage of 0.4 g / m < ² > and dried to form a layer 4B1d containing a polymeric antistatic agent. The thermal dimensional change ratio of the biaxially stretched PET film provided with the layer containing the polymeric antistatic agent obtained above from 23 ° C to 120 ° C is the results shown in Table 4-1.

As the antistatic resin 4e, a layer containing a polymeric antistatic agent was formed by using an anionic synthetic clay mineral-containing polyester resin (product name: ASA-2050 manufactured by TAKAMATSU Oil & Fat Co., Ltd.). Specifically, the antistatic resin 4e was coated on one side of the substrate 4B0a or the like of the heat-resistant resin layer 4B with a coating amount of 0.4 g / m < ² > and dried to form a layer 4B1e containing a polymeric antistatic agent.

A layer containing a polymeric antistatic agent was formed by using a polyester resin (TAKAMATSU Oil & Fat, product name: ASA-2050) containing an anionic synthetic clay mineral. Specifically, the antistatic resin 4e was coated on one side of the substrate 4B0a or the like of the heat-resistant resin layer 4B with a coating amount of 0.4 g / m < ² > and dried to form a layer 4B1e containing a polymeric antistatic agent. The test items and evaluation results of the biaxially stretched PET film obtained by the layer containing the polymeric antistatic agent obtained above, such as the rate of change of thermal dimensional change from 23 ° C to 120 ° C and the water contact angle, were as shown in Table 4-1.

All of the embodiments were good in all test items of mold release, molded article appearance, metal mold conformability and reattachment test, and it was a balanced release film for the process in terms of performance.

The details of each film described in Table 4-1 are as follows.

(4Aa) Pb-free 4MP-1 (TPX) film

A film made of a lead-free film having a thickness of 15 μm using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(4Ab) Lead-free 4MP-1 (TPX) film

A film of a non-oriented film having a thickness of 50 μm formed by using a 4-methyl-1-pentene copolymer resin (product name: TPX brand name: MX022) manufactured by Mitsui Chemicals Co., (Melting point: 229 캜, crystal melting heat amount: 21.7 J / g)

(4B0a) Biaxially oriented PET film

(Melting point: 258 占 폚, crystal melting heat amount: 39.4 J / g) made of biaxially stretched PET (polyethylene terephthalate) film (trade name: Lumirror S10,

(4B0b) Biaxially oriented nylon film

A biaxially oriented nylon film (trade name: bonyl RX, manufactured by KOHJIN FILM & CHEMICALS CO., LTD. (Melting point: 212 DEG C, crystal melting heat amount: 53.1 J / g)

(B0c) Biaxially oriented polypropylene film

(Melting point: 160 占 폚, crystal melting heat amount: 93.3 J / g, manufactured by Mitsui Chemicals Tohcello Co., Ltd., product name: U-2)

(4B0d) Lead-free nylon film

(Melting point: 220 占 폚, crystal melting heat amount: 39.4 J / g, manufactured by Mitsubishi Plastics Co., Ltd., product name: DYNAMILON C)

(4B0e) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 20 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

(4B0f) Lead-free polybutylene terephthalate film

A film of a non-oriented film having a thickness of 50 μm formed by using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering-Plastics Co., (Melting point: 219 DEG C, crystal melting heat amount: 48.3 J / g)

[Reference Examples 4-1 to 4-3]

Sealing and releasing were carried out in the same manner as in Example 4-1 except that the film composition shown in Table 4-1 was used, and the characteristics of the release film for the process were evaluated.

In any reference example, the performance was not comprehensively evaluated in Examples, and in particular, the results of reattachment tests were inferior. In addition, the appearance was not good except for Reference Example 4-1.

[Examples 4-10 to 4-17]

A release film for processing was produced in the same manner as in Example 4-1 except that each of the films shown in Table 4-2 was used in the form of the release layers 4A and 4A 'and the heat-resisting resin layer 4B in the combination shown in Table 4-2 And the characteristics were evaluated by performing sealing and releasing.

As shown in FIG. 3A, the release film was placed between the upper mold and the lower mold in a state of applying tensile force of 20 N, and then vacuum adsorbed onto the upper molding surface. Subsequently, the sealing resin was filled on the substrate so as to cover the semiconductor chip, and the semiconductor chip fixed on the substrate was placed on the lower mold and closed. At this time, the temperature (molding temperature) of the molded metal mold was set to 170 ° C, the molding pressure was set to 10 Mpa, and the molding time was set to 100 seconds. Then, as shown in Fig. 3C, the semiconductor chip is sealed with a sealing resin, and then the resin-sealed semiconductor chip (semiconductor package) is released from the release film. The results are shown in Table 4-2.

Despite the evaluation of the high temperature range of 170 占 폚, all of the examples were satisfactory in all the test items of releasability, appearance of the molded article, metal mold conformability and reattachment test, and it was a performance releasing film balanced in terms of performance. In particular, Examples 4-15 to 4-17 were good releasing films for the process, showing good releasability, appearance of the molded article, conformability of the metal mold, and adhesion test of ashes.

[Reference Examples 4-4 to 4-9]

A release film for processing was produced in the same manner as in Examples 4-10 to 4-17 except that the film composition shown in Table 4-2 was used, and sealing and releasing were performed to evaluate the characteristics. The results are shown in Table 4-2.

In any reference example, the performance remained in general not satisfying the respective embodiments, and in particular, the appearance and the reattachment test of the molded article did not yield good results.

The details of each film shown in Table 4-2 are the same as those described above for each of the films described in Table 4-1.

Details of 4B0g and 4B0h of heat-resistant resin layer listed only in Table 4-2 are as follows.

(4B0g) Biaxially oriented nylon film

(Unilon S330 manufactured by Idemitsu Unitech Co., Ltd., melting point: 221 占 폚, crystal melting heat amount: 60.3 J / g)

(4B0h) biaxially oriented PET film

(Melting point: 214 占 폚, crystal melting heat amount: 40.3 J / g, manufactured by Teijin DuPont Films Co., Ltd., product name: FT3PE)

Since the process release film of the first invention of the present invention has a high level of releasability, suppression of wrinkles and followability of metal moldings that can not be realized in the prior art, it is used so that a molded product obtained by resin- And it is possible to produce a molded product having no defective appearance such as wrinkles and scratches with high productivity and have high practical value and can be highly utilized in various fields of industries including the semiconductor processing industry.

In addition, since the process release film of the first invention of the present invention can be used not only for a semiconductor package but also for forming various metal molds such as a fiber reinforced plastic molding process and a plastic lens molding process, There is a possibility of high utilization in the field.

The release film for a process according to the second invention of the present invention has a high level of releasability, suppression of appearance defects and followability of a metal mold, which can not be realized in the prior art, so that a molded product obtained by resin- And it is possible to produce a molded product having no defective appearance such as wrinkles, scratches, and abnormal shapes (scum, foreign matters, etc.) with high productivity. There is a high possibility of use in each of the fields.

In addition, since the process release film of the second invention of the present invention can be used not only for a semiconductor package but also for forming various metal molds such as a fiber reinforced plastic molding process and a plastic lens molding process, There is a possibility of high utilization in the field.

The release film for a process according to the third invention of the present application has a high level of releasability, suppression of wrinkles and followability of metal moldings which can not be realized in the prior art. Therefore, by using this, a molded article obtained by resin- And it is possible to produce a molded product having no defective appearance such as wrinkles and scratches with high productivity, and has a high practical value and a high availability in various fields of industries including the semiconductor processing industry.

In addition, since the process release film of the third invention of the present invention can be used not only for a semiconductor package but also for forming various metal molds such as a fiber reinforced plastic molding process and a plastic lens molding process, There is a possibility of high utilization in the field.

The release film for a process according to the fourth invention of the present invention has a high level of releasability, suppression of wrinkles and followability of metal moldings which can not be realized in the prior art, and therefore it is possible to easily release a molded article obtained by resin- And it is possible to produce a molded product having no defective appearance such as wrinkles and scratches with high productivity, and has a high practical value and a high availability in various fields of industries including the semiconductor processing industry.

In addition, since the process release film of the fourth invention of the present invention can be used not only for a semiconductor package but also for forming various metal molds such as a fiber reinforced plastic molding process and a plastic lens molding process, There is a possibility of high utilization in the field.

1,1-2,1-3: release film
2: Upper metal die
3: Sucking population
4: Sealing resin
4-2: Semiconductor package
5: Lower metal mold
6: Semiconductor chip
7: substrate
8: Molded metal mold
10, 20, 22: release film
12: Heat-resistant resin layer 1B, 2B, 3B, 4B
14: Adhesive layer
16, 16A: release layers 1A, 2A, 3A, 4A
16B: release layer 1A'2A'3A'4A '
24, 26: roll
28: Molded metal mold
30: upper die
32: Lower mold
34: Semiconductor chip
34A: substrate
36: Sealing resin
40, 44: semiconductor package

Claims (86)

As a release film for a process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90to 130,
Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.
The method according to claim 1, wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 120 占 폚 in the longitudinal (MD) Release film.
As a release film for a process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90to 130,
Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.
The method according to claim 3, wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 占 폚 to 170 占 폚 in the longitudinal (MD) Release film.
The release film for a process according to any one of claims 1 to 4, wherein a thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less.
The thermosetting resin composition according to claim 5, wherein the thermal dimensional change ratio in the transverse direction (TD) direction of the heat-resistant resin layer 1B from 23 DEG C to 120 DEG C and the thermal dimensional change rate in the longitudinal (MD) direction from 23 DEG C to 120 DEG C is 6% , Release film for process.
The release film for a process according to any one of claims 1 to 4, wherein a thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less.
The thermosetting resin composition according to claim 7, wherein the thermal dimensional change ratio in the transverse direction (TD) direction of the heat resistant resin layer 1B from 23 DEG C to 170 DEG C and the thermal dimensional change rate in the longitudinal (MD) direction from 23 DEG C to 120 DEG C is 4% , Release film for process.
9. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the release layer 1A is selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- A resin, and a resin.
10. The release film according to any one of claims 1 to 9, wherein the heat-resistant resin layer 1B comprises a stretch film.
11. The release film according to claim 10, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
The method according to any one of claims 1 to 11, wherein the heat of crystallization of the heat-resistant resin layer 1B in the first heating step measured by differential scanning calorimetry (DSC) according to JIS K7221 15 J / g or more, and 60 J / g or less.
13. The laminated film according to any one of claims 1 to 12, wherein the laminated film further comprises a release layer 1A ', and further comprises the release layer 1A, the heat-resistant resin layer 1B and the release layer 1A'
And the contact angle of the release layer 1A 'with respect to water is 90 ° to 130 °.
14. The method according to claim 13, wherein at least one of the release layer 1A and the release layer 1A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- Release film.
15. The release film for a process according to any one of claims 1 to 14, which is used in a sealing step with a thermosetting resin.
16. A release film for a process according to any one of claims 1 to 15 for use in a semiconductor encapsulation process.
16. A release film according to any one of claims 1 to 15 for use in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 1 to 14 on the inner surface of the molded metal mold so that the release layer 1A faces the semiconductor device;
Molding the molded metal mold to form a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process;
And a step of forming the resin-sealed semiconductor.
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a metal mold,
A step of disposing the release film for semiconductor encapsulation process according to claim 13 or 14 on the inner surface of the metal mold such that the release layer 1A 'faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the metal mold,
And a step of forming the resin-sealed semiconductor.
As a release film for a process which is a laminated film including a release layer 2A and a heat-resistant resin layer 2B,
The contact angle of the release layer 2A with respect to water in the laminated film is 90 to 130 and the surface resistivity is 1 x 10 < ¹³ >
The heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,
Wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.
The method according to claim 20, wherein the sum of the thermal dimensional change ratio from 23 ° C to 120 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction is 6% Release film.
As a release film for a process which is a laminated film including a release layer 2A and a heat-resistant resin layer 2B,
The contact angle of the release layer 2A with respect to water in the laminated film is 90 to 130 and the surface resistivity is 1 x 10 < ¹³ >
Wherein the heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent,
Wherein a rate of change in thermal dimensional change from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction of the laminated film is 4% or less.
The method according to claim 22, wherein the sum of the thermal dimensional change ratio from 23 ° C to 170 ° C in the transverse direction (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction is 7% Release film.
24. The release film for a process according to any one of claims 20 to 23, wherein the heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent and an adhesive layer 2B2 comprising an adhesive.
The release film for a process according to any one of claims 20 to 24, wherein the thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse (TD) direction of the heat-resistant resin layer 2B is 3% or less.
26. The thermoplastic resin composition according to claim 25, wherein the sum of the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) , Release film for process.
The release film for a process according to any one of claims 20 to 24, wherein a thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse (TD) direction of the heat-resistant resin layer 2B is 3% or less.
The thermosetting resin composition according to claim 27, wherein the sum of the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse (TD) direction of the heat resistant resin layer 2B and the thermal dimensional change from 23 DEG C to 120 DEG C in the longitudinal (MD) , Release film for process.
29. The method according to any one of claims 20 to 28, wherein the release layer 2A comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- Release film.
30. The release film according to any one of claims 20 to 29, wherein the heat-resistant resin layer 2B comprises a stretched film.
31. The release film according to claim 30, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
32. The method according to any one of claims 20 to 31, wherein the heat of fusion of crystal in the first heating-up step of the heat-resistant resin layer 2B measured by a differential scanning calorimeter (DSC) according to JIS K7221 is not less than 15 J / g , And not more than 60 J / g.
32. The laminated film according to any one of claims 20 to 32, wherein the laminated film further has a release layer 2A 'and sequentially includes the release layer 2A, the heat-resistant resin layer 2B and the release layer 2A'
And the contact angle of the release layer 2A 'with respect to water is 90 ° to 130 °.
34. The release film for a process according to claim 33, wherein the release layer 2A 'has a surface resistivity of 1 x 10 < ¹³ >
16. The method according to claim 14 or 15, wherein at least one of the release layer 2A and the release layer 2A 'is a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- ≪ / RTI >
36. The release film for a process according to any one of claims 20 to 35, which is used in a sealing step with a thermosetting resin.
37. The release film for a process according to any one of claims 20 to 36, which is used in a semiconductor encapsulation process.
37. The release film according to any one of claims 20 to 36, for use in a fiber-reinforced plastic forming process or a plastic lens forming process.
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 20 to 35 on the inner surface of the molded metal mold so that the release layer 2A faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the mold metal mold,
And a step of forming the resin-sealed semiconductor.
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 33 to 35 on the inner surface of the molded metal mold such that the release layer 2A 'faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the mold metal mold,
And a step of forming the resin-sealed semiconductor.
As a release film for a process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90to 130,
Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.
42. The release film for process according to claim 41, wherein the rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.
The laminate film according to claim 41 or 42, wherein a sum of a thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse direction (TD) direction and a thermal dimensional change rate from 23 deg. C to 120 deg. % Or less.
As a release film for a process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90to 130,
Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.
45. The release film for a process according to claim 44, wherein a thermal dimensional change ratio in the transverse direction (TD) direction from 23 deg. C to 170 deg. C is 4% or less.
The laminated film according to claim 44 or 45, wherein a sum of a thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse direction (TD) direction and a thermal dimensional change rate from 23 占 폚 to 170 占 폚 in the longitudinal (MD) % Or less.
46. The release film for a process according to any one of claims 41 to 46, wherein the thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less.
The thermosetting resin composition according to claim 47, wherein the sum of the thermal dimensional change ratio from 23 占 폚 to 120 占 폚 in the transverse (TD) direction of the heat-resistant resin layer 3B and the thermal dimensional change rate from 23 占 폚 to 120 占 폚 in the longitudinal (MD) , Release film for process.
The process for producing a release film for a process according to any one of claims 41 to 46, wherein a thermal dimensional change ratio from 23 占 폚 to 170 占 폚 in the transverse (TD) direction of the heat-resistant resin layer 3B is 3% or less.
Wherein the sum of the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse direction (TD) direction of the heat resistant resin layer 3B and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) direction is 5% , Release film for process.
50. The method according to any one of claims 41 to 50, wherein the release layer 3A comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- Release film.
The process for producing a release film according to any one of claims 41 to 51, wherein the heat-resistant resin layer 3B comprises a stretched film.
53. The release film of claim 52, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
The method according to any one of claims 41 to 53, wherein the heat of crystal fusion in the first heating-up step of the heat-resistant resin layer 3B measured by a differential scanning calorimeter (DSC) according to JIS K7221 is 20 J / g Or more and 100 J / g or less.
The method of manufacturing a semiconductor device according to any one of claims 41 to 54, wherein the laminated film further has a release layer 3A 'and sequentially includes the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A'
And the contact angle of the release layer 3A 'with respect to water is 90 ° to 130 °.
56. The method of claim 55, wherein at least one of the release layer 3A and the release layer 3A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene- Release film.
57. The process for producing a thermoplastic resin film according to any one of claims 41 to 56,
57. The release film for a process according to any one of claims 41 to 57, used in a semiconductor encapsulation process.
57. The release film according to any one of claims 41 to 57, for use in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 41 to 56 on the inner surface of the molded metal mold so that the release layer 3A faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the mold metal mold,
Wherein the step of forming the resin-sealed semiconductor comprises the steps of:
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process of claim 55 or 56 on the inner surface of the molded metal mold so that the release layer 3A 'faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the mold metal mold,
Wherein the step of forming the resin-sealed semiconductor comprises the steps of:
A releasing layer 4A and a heat-resisting resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90to 130,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymeric antistatic agent,
Wherein the laminated film has a tensile elastic modulus at 120 DEG C of from 75 MPa to 500 MPa.
63. The release film for a process according to claim 62, wherein a rate of change in thermal dimensional change from 23 deg. C to 120 deg. C in the transverse direction (TD) direction of the laminated film is 3% or less.
The laminated film according to claim 62 or 63, wherein a sum of a thermal dimensional change ratio from 23 deg. C to 120 deg. C in the transverse direction (TD) direction and a thermal dimensional change rate from 23 deg. C to 120 deg. % Or less.
A releasing layer 4A and a heat-resisting resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90to 130,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymeric antistatic agent,
Wherein the laminated film has a tensile modulus at 170 占 폚 of 75 MPa to 500 MPa.
The process for producing a release film according to claim 65, wherein the thermal dimensional change ratio in the transverse direction (TD) direction from 23 ° C to 170 ° C is 4% or less.
The thermosetting resin composition according to claim 65 or 66, wherein the ratio of the thermal dimensional change from 23 DEG C to 170 DEG C in the transverse direction (TD) direction and the thermal dimensional change rate from 23 DEG C to 170 DEG C in the longitudinal (MD) % Or less.
67. The release film for a process according to any one of claims 62 to 67, wherein the heat-resistant resin layer 4B comprises a layer 4B1 containing a polymeric antistatic agent and an adhesive layer 4B2 comprising an adhesive.
67. The release film for a process according to any one of claims 62 to 67, wherein the heat-resistant resin layer 4B comprises a layer 4B3 containing a polymeric antistatic agent and an adhesive.
The process for producing a release film for a process according to any one of claims 62 to 69, wherein a thermal dimensional change ratio in the transverse (TD) direction of the heat-resistant resin layer 4B from 23 캜 to 120 캜 is 3% or less.
The thermosetting resin composition according to claim 70, wherein the sum of the thermal dimensional change ratio from 23 DEG C to 120 DEG C in the transverse (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 DEG C to 120 DEG C in the longitudinal (MD) , Release film for process.
71. The release film for a process according to any one of claims 62 to 69, wherein the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse (TD) direction of the heat-resistant resin layer 4B is 3% or less.
72. The thermoplastic resin composition according to claim 72, wherein the sum of the thermal dimensional change ratio from 23 DEG C to 170 DEG C in the transverse (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change from 23 DEG C to 170 DEG C in the longitudinal (MD) , Release film for process.
73. The method according to any one of claims 62 to 73, wherein the release layer 4A comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- Release film.
74. The release film for a process according to any one of claims 62 to 74, wherein the heat-resistant resin layer 4B comprises a stretched film.
77. The release film of claim 75, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
76. The method according to any one of claims 62 to 76, wherein the heat of crystal fusion in the first heating-up step of the heat-resistant resin layer 4B measured by a differential scanning calorimeter (DSC) according to JIS K7221 is 20 J / g Or more and 100 J / g or less.
77. The release film for a process according to any one of claims 62 to 77, wherein the release layer 4A has a surface resistivity of 1 x 10 < ¹³ >
79. The laminated film according to any one of claims 62 to 78, wherein the laminated film further has a release layer 4A ', and further comprises the release layer 4A, the heat-resistant resin layer 4B and the release layer 4A'
Wherein the release layer 4A 'has a contact angle with water of 90 ° to 130 °.
80. The method according to claim 79, wherein at least one of the release layer 4A and the release layer 4A 'comprises a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer and a polystyrene- Release film.
The process for producing a release film according to claim 79 or 80, wherein the release layer 4A 'has a surface resistivity of 1 x 10 < ¹³ >
83. The method according to any one of claims 62 to 81, wherein the release film for processing used in the sealing step with the thermosetting resin
83. The release film according to any one of claims 62 to 82, used in the semiconductor encapsulation process.
83. The release film according to any one of claims 62 to 82, for use in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 62 to 83 on the inner surface of the molded metal mold so that the release layer 4A faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the mold metal mold,
Wherein the step of forming the resin-sealed semiconductor comprises the steps of:
A method for producing a resin-sealed semiconductor,
Disposing a resin-sealed semiconductor device at a predetermined position in a molding metal mold;
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 79 to 81 on the inner surface of the molded metal mold so that the release layer 4A 'faces the semiconductor device;
A step of injecting and molding a sealing resin between the semiconductor device and the release film for semiconductor encapsulation process after molding the mold metal mold,
Wherein the step of forming the resin-sealed semiconductor comprises the steps of:

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