JP2018176695A - Releasing film for process, application thereof, and method of producing resin-sealed semiconductor using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a releasing film for process, comprising: a capability of releasing a molded article after resin sealing without depending on a structure of a mold and an amount of a releasing agent; a capability of obtaining a molded article having no defective appearance such as wrinkles and chips; and a capability of effectively suppressing contamination of the mold.SOLUTION: There is provided a releasing film for process being a laminated film, comprising: a releasing layer A; a heat-resistant resin layer B; and optionally, a releasing layer A', and the releasing film for process has a contact angle in the releasing layer A (and optionally the releasing layer A') with respect to water of 90° to 130°, and a thermal dimensional change rate in a transverse (TD) direction of the laminated film at 23°C to 120°C is 3% or less, an oxygen permeability measured under conditions at a temperature of 20°C and at a humidity of 50% RH is 1000 mL/mday MPa or less according to JIS K7126, or an out gas permeability measured according to a predetermined procedure is 1.0% by weight or less.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a mold release film for a process, preferably a mold release film for a semiconductor encapsulation process, and in particular, when a semiconductor chip or the like is disposed in a mold and a resin is injected and molded, the semiconductor chip or the like and the inner surface of the mold And a method of manufacturing a resin-sealed semiconductor using the same.

  In recent years, with the reduction in size and weight of semiconductor packages and the like, it has been studied to reduce the amount of sealing resin used. And in order to be able to adhere firmly to the interface of a semiconductor chip etc. and resin, even if it reduces the usage-amount of sealing resin, to reduce the quantity of the mold release agent contained in sealing resin is desired. . For this reason, as a method of obtaining releasability between the sealing resin and the mold after curing and molding, a method of disposing a release film between the inner surface of the mold and the semiconductor chip or the like is adopted.

  As such a release film, a fluorine-based resin film (for example, Patent Documents 1 and 2), a poly 4-methyl-1-pentene resin film (for example, Patent Document 3), and the like, which are excellent in releasability and heat resistance Proposed. However, these mold release films are prone to wrinkles when mounted on the inner surface of the mold, and the wrinkles are transferred to the surface of the molded product to cause appearance defects.

  On the other hand, a laminated release film having a release layer and a heat-resistant layer has been proposed. These release films are intended to obtain releasability in the release layer and to suppress wrinkles in the heat-resistant layer. The representative ones of these proposals focus on the relationship between the release modulus and the storage elastic modulus of the heat-resistant layer (see, for example, Patent Documents 4 and 5). For example, Patent Document 4 discloses a laminated release film having a configuration in which the storage elastic modulus of the release layer is relatively low and the storage elastic modulus of the heat-resistant layer is relatively high, more specifically, at 175 ° C. of the release layer. A release film for semiconductor encapsulation process is described in which the storage elastic modulus E 'is 45 MPa or more and 105 MPa or less, and the storage elastic modulus E' at 175 ° C. of the heat-resistant layer is 100 MPa or more and 250 MPa or less.

However, with the development of the relevant technical field, the level of requirement for process release films such as release films for semiconductor encapsulation processes is increasing year by year, and process release for processes with suppressed generation of wrinkles even under more severe process conditions. There is a need for a mold film, and in particular, there is a strong demand for a process release film in which the mold releasability, the suppression of wrinkles, and the mold followability are balanced at an even higher level.
In addition, depending on the type of semiconductor sealing resin, low molecular weight gas such as oligomers generated from the sealing resin heated during molding (hereinafter referred to as "outgas") permeates the mold release film and contaminates the mold. May have occurred, and its suppression has been sought. In particular, when wrinkles occur in the release film for semiconductor encapsulation process, for example, when a release film having an inorganic film or an organic film is used as the gas permeation suppression layer, the gas permeation suppression layer itself is thinner than the film. Because of the presence of wrinkles in the release film, the gas permeation suppressing layer is likely to be cracked or broken, or a hole or the like. As a result, outgas may permeate through the film from a portion where a hole or the like is likely to be generated from the sealing resin generated by heating, and may be deposited on the mold surface, causing localized contamination of the mold. Since the progress of such contamination of the mold tends to cause wrinkles in the film, the cleaning cycle of the mold becomes short, and in view of the decrease in production efficiency of the semiconductor package process, the production cost, etc. There was a need to prevent mold contamination. (See, for example, Patent Document 6)

JP 2001-310336 A Japanese Patent Application Laid-Open No. 2002-110722 JP, 2002-361643, A JP, 2010-208104, A International Publication No. 2015/133631 A1 brochure WO 2007/125834 A1 brochure

  The present invention has been made in view of such circumstances, and the molded product after resin sealing can be easily released without depending on the mold structure and the amount of the release agent, and the appearance such as wrinkles and chips. An object of the present invention is to provide a process release film capable of obtaining a molded product free of defects and capable of effectively suppressing mold contamination.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the thermal dimensional change rate of a process release film at a specific temperature, in particular, the TD direction of a laminated film constituting the process release film (film In the plane of the film, a direction perpendicular to the longitudinal direction during film production, hereinafter also referred to as “lateral direction”, appropriately control the thermal dimensional change rate, and the oxygen permeability of the laminated film Since the outgassing permeability from the sealing resin of the laminated film can be controlled to a predetermined value or less as a result of controlling the film thickness to a predetermined value or less, suppression of wrinkles when mounted on the inner surface of the mold and It has been found that it is important for the control of mold contamination, and the present invention has been completed.
That is, the present invention and each aspect thereof are as described in the following [1] to [17].

[1]
A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less,
According to JIS K 7126 of the laminated film, temperature 20 ° C., humidity 50% R.H. H. The release film for process whose oxygen permeability measured on condition of is 1000 ml / m <2> * day * MPa or less.
[2]
A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less,
The release film for the above process wherein the outgassing permeability measured according to the following procedures (1) to (3) of the laminated film is 1.0% by weight or less:
(1) Put 10 mg of sealing resin in vial 1, seal with cap and rubber stopper, heat at 120 ° C. for 30 minutes, perform GC-MS measurement by static head space method, outgassing in vial 1. Measure amount 1;
(2) Put 10 mg of sealing resin in vial 1 and cover the opening of vial 1 with a mold release film covered and sealed. The vial 2 is prepared, and the vial 1 is stored in the vial 2, sealed with a cap and a rubber stopper, heated at 120 ° C. for 30 minutes, and subjected to GC-MS measurement by a static head space method, Measure the amount of outgassing 2 in the vial 2 which has permeated the process release film;
(3) The outgassing permeability of the process release film is calculated according to the following (equation 1).
Permeability of outgassing = Outgas amount 2 / Outgas amount 1 x 100 (% by weight) (Equation 1)
[3]
The sum of the thermal dimensional change 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 of the laminated film is 6% or less [1 ] Or the release film for processes as described in [2].
[4]
The mold release film for a process according to any one of [1] to [3], wherein the heat dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is 3% or less .
[5]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the lateral (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer B is 6% or less The release film for process according to [4].
[6]
In any one of [1] to [5], wherein the release layer A contains a resin selected from the group consisting of a fluorine resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Process release film as described.
[7]
The process release film according to any one of [1] to [6], wherein a gas barrier layer C is laminated on the heat-resistant resin layer B.
[8]
The mold release film for a process as described in [7] whose said gas barrier layer C is an inorganic layer or an organic layer.
[9]
The process release film according to [7] or [8], wherein a protective resin layer D which is an organic coating is laminated on the gas barrier layer C.
[10]
[1] to [9], which is 15 J / g or more and 60 J / g or less of heat of crystal fusion in the first temperature raising step measured by differential scanning calorimetry (DSC) according to JIS K 7221 of the heat-resistant resin layer B The release film for process according to any one of the preceding claims.
[11]
The laminated film further has a release layer A ′, and includes the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order,
The process release film according to any one of [1] to [10], wherein the contact angle to water of the release layer A ′ is 90 ° to 130 °.
[12]
At least one of the release layer A and the release layer A ′ contains a resin selected from the group consisting of a fluorocarbon resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin [11] The release film for process described in.
[13]
The mold release film for a process [14] according to any one of [1] to [12], which is used in a sealing process with a thermosetting resin.
The process release film as described in any one of [1] to [13] used for a semiconductor sealing process.
[15]
The process release film according to any one of [1] to [12], which is used in a fiber reinforced plastic molding process or a plastic lens molding process.
[16]
A method of manufacturing a resin-sealed semiconductor, comprising
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die;
Arranging the mold release film according to any one of [1] to [14] on the inner surface of the molding die such that the mold release layer A faces the semiconductor device;
Injecting and molding a sealing resin between the semiconductor device and the process release film after clamping the molding die;
The manufacturing method of the said resin-sealed semiconductor which has.
[17]
A method of manufacturing a resin-sealed semiconductor, comprising
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die;
Arranging the process release film according to [11] or [12] on the inner surface of the molding die such that the release layer A ′ faces the semiconductor device;
Injecting and molding a sealing resin between the semiconductor device and the process release film after clamping the molding die;
The manufacturing method of the said resin-sealed semiconductor which has.

  The process release film of the present invention has a high level of releasability, wrinkle suppression, and mold followability which can not be achieved by the prior art, and can effectively suppress mold contamination, so By using this, it is possible to easily release a molded product obtained by resin-sealing a semiconductor chip or the like and to manufacture a molded product free from appearance defects such as wrinkles and chips at high productivity and at low cost. Can.

It is a schematic diagram which shows an example of the release film for processes of this invention. It is a schematic diagram which shows the other example of the release film for processes of this invention. It is a schematic diagram which shows the other example of the release film for processes of this invention. It is a schematic diagram which shows the other example of the release film for processes of this invention. It is a schematic diagram which shows an example of the manufacturing method of the resin-sealed semiconductor using the release film for processes of this invention. It is a schematic diagram which shows an example of the manufacturing method of the resin-sealed semiconductor using the release film for processes of this invention. It is a schematic diagram which shows an example of the manufacturing method of the resin-sealed semiconductor using the release film for processes of this invention. It is a schematic diagram which shows an example of the resin-sealed semiconductor obtained by the manufacturing method of the resin-sealed semiconductor of FIG. 6A and FIG. 6B. It is a schematic diagram which shows arrangement | positioning in the case of evaluation of mold contamination. It is a schematic diagram which shows arrangement | positioning in the case of the measurement of outgassing permeability.

Process Release Film The process release film of the present invention includes the following two embodiments.
(First aspect)
A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less,
The release film for the above process, wherein the oxygen permeability of the laminated film is 1000 ml / m ² · day · MPa or less. In the present invention, the oxygen permeability in the present invention is OX-TRAN 2/21 ML manufactured by Mocon, according to JIS K 7126, at a temperature of 20.degree. H. Oxygen permeability measured under the conditions of
The oxygen permeability, from the viewpoint of effectively preventing the mold contamination, more preferably at most ^{500ml / m 2 · day · MPa} , and particularly preferably not more than ^{250ml / m 2 · day · MPa} .
It is preferable that the first aspect further includes the following conditions.
A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The mold release film for the above process, wherein the thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film is 4% or less.
(Second aspect)
A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angles of the release layer A and the release layer A ′ to water are 90 ° to 130 °,
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less,
The release film for the above process, wherein the outgassing permeability of the laminated film measured by the method described later is 1.0% by weight or less.
The outgassing permeability is preferably 0.8% by weight or less, more preferably 0.7% by weight or less, and more preferably 0.5% by weight or less from the viewpoint of effectively preventing mold contamination. Being particularly preferred.
It is preferable that the second aspect of the present invention further satisfy the following conditions.
A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The mold release film for the above process, wherein the thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film is 4% or less.
The first and second embodiments may further include a release layer A ′, and may include a release layer A, a heat-resistant resin layer B, and a release layer A ′ in this order. .

  As apparent from each of the above aspects, the process release film of the present invention (hereinafter, also simply referred to as "release film") is a release layer A having release properties for molded articles and molds, and if desired It is a laminated film including a release layer A ′ and a heat-resistant resin layer B supporting the release layer.

The process release film of the present invention is disposed on the inner surface of a molding die when a semiconductor element or the like is resin-sealed inside the molding die. At this time, the mold release layer A of the mold release film (or the mold release layer A ′ when the mold release layer A ′ is present) may be placed on the semiconductor element etc. (molded article) side sealed with resin. It is preferable to arrange. By arranging the release film of the present invention, the resin-sealed semiconductor element and the like can be easily released from the mold.
The contact angle of the release layer A to water is 90 ° to 130 °, and by having such a contact angle, the release layer A has low wettability and adheres to the surface of the cured sealing resin or mold. Thus, the molded article can be easily released.
The contact angle of the release layer A to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.

  As described above, since the mold release layer A (in some cases, the mold release layer A ′) is disposed on the molded product side, the ridges in the mold release layer A (in some cases, the mold release layer A ′) in the resin sealing step It is preferable to suppress the occurrence of It is because there is a high possibility that the generated wrinkles will be transferred to the molded product and the appearance defect of the molded product will occur.

In the present invention, in order to achieve the above object, as a laminated film constituting a process release film, a release layer A (and optionally release layer A '), and a heat resistant resin supporting the release layer A layered film comprising a layer B, wherein the thermal dimensional change in the transverse (TD) direction exhibits a specific value.
That is, the laminated film including the releasing layer A (and optionally releasing layer A ′) and the heat-resistant resin layer B supporting the releasing layer is from 23 ° C. to 120 ° C. in the TD direction (lateral direction) Rate of thermal dimensional change is 3% or less. The thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction) is preferably 4% or less.
The thermal dimensional change from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of the laminated film is 3% or less, and preferably from 23 ° C. to 170 ° C. in the TD direction (lateral direction). By setting the ratio to 4% or less, it is possible to effectively suppress the generation of wrinkles in the release layer in the resin sealing step and the like. The mechanism by which the generation of wrinkles in the release layer is suppressed is not necessarily clear by using a laminate film constituting the process release film in which the thermal dimensional change rate in the transverse (TD) direction exhibits the above-mentioned specific value. Although it is not, it is related to suppression of thermal expansion / contraction of release layer A (or release layer A ') by heating / cooling during the process by using a laminated film with relatively small thermal expansion / contraction. It is presumed that there is something.

The laminated film constituting the process release film of the present invention preferably has a thermal dimensional change of 2.5% or less from 23 ° C. to 120 ° C. in the TD direction (lateral direction), 2.0% It is more preferable that it is the following and it is still more preferable that it is 1.5% or less. On the other hand, the laminated film preferably has a thermal dimensional change of -5.0% or more from 23 ° C to 120 ° C in the TD direction (lateral direction).
The laminated film constituting the process release film of the present invention preferably has a thermal dimensional change of 3.5% or less from 23 ° C. to 170 ° C. in the TD direction (lateral direction), 3.0% It is more preferable that it is the following, and it is still more preferable that it is 2.0% or less. On the other hand, the laminated film preferably has a thermal dimensional change of -5.0% or more from 23 ° C to 170 ° C in the TD direction (lateral direction).

The process release film of the present invention, which is a laminated film including a release layer A (and optionally a release layer A ′) and a heat resistant resin layer B supporting the release layer, has its TD direction (horizontal direction It is preferable that the sum of the rate of thermal dimensional change of the film) and the rate of thermal dimensional change of the MD direction (longitudinal direction at the time of film production; hereinafter, also referred to as "longitudinal direction") is a specific value or less.
That is, the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less On the other hand, the laminated film is preferably the sum of the thermal dimensional change from 23 ° C. to 120 ° C. in the TD direction (lateral direction) and the thermal dimensional change from 23 ° C. to 120 ° C. in the longitudinal (MD) direction. Is preferably -5.0% or more.
Thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction and longitudinal (MD) direction of the laminated film containing the releasing layer A (and optionally releasing layer A ′) and the heat-resistant resin layer B When the sum of the thermal dimensional change rates from 23 ° C. to 120 ° C. is 6% or less, the generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.

In addition, the thermal dimensional change rate and the longitudinal (MD) from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film containing the mold release layer A (and optionally, the mold release layer A ′) and the heat resistant resin layer B The sum of the thermal dimensional change from 23 ° C to 170 ° C in the direction is preferably 7% or less, while the laminated film has a thermal dimension from 23 ° C to 170 ° C in the TD direction (lateral direction) It is preferable that the sum of the rate of change and the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the longitudinal (MD) direction is −5.0% or more.
The sum of the thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the laminated film is 7% or less The generation of wrinkles when mounted on the inner surface of the mold can be further effectively suppressed.

In the second embodiment of the present invention, the outgassing permeability of the laminated film including the release layer A (and optionally the release layer A ′) and the heat-resistant resin layer B is 1.0% by weight or less. From the viewpoint of effectively preventing mold contamination, the outgassing permeability is more preferably 0.7% by weight or less and particularly preferably less than 0.5% by weight.
When the outgassing permeability of the laminated film is 1.0% by weight or less, contamination of the mold in the semiconductor encapsulation process and the like can be effectively suppressed.
In the prior art, it is presumed that readily volatile components and the like from an epoxy resin or the like which is a sealing resin permeate the film and cause contamination of the mold. The component of the outgas is a low molecular weight component which volatilizes from the sealing resin at the time of heating, and among them, it is presumed that a non-volatile substance at normal temperature such as, for example, silicone oil contaminates the mold.
The laminate constituting the process release film according to the second aspect, in which the outgassing permeability is equal to or less than a predetermined value, hardly permeates the contaminants in the outgassing, blocking the contaminants from the sealing resin etc. It is presumed that the substance can be prevented from adhering to the mold.
Here, the sealing resin preferably used in the manufacturing process using the mold release film for process of the present embodiment is not particularly limited, and may be any of a thermoplastic resin and a thermosetting resin. Thermosetting resins are widely used. The material of the resin is not particularly limited, but an epoxy-based thermosetting resin or a silicone sealing resin can be preferably used, and in particular, an epoxy-based sealing resin is preferably used.
(A) epoxy resin, (B) phenol resin, (C) curing accelerator and (D) as an epoxy-based sealing resin which is preferably used particularly preferably in the manufacturing process using the process release film of this embodiment There may be mentioned epoxy resin compositions which are said to contain an inorganic filler.
The epoxy resin (A) used in the above epoxy resin composition refers to all monomers, oligomers and polymers having two or more epoxy groups in one molecule. For example, ortho cresol novolac epoxy resin, phenol novolac epoxy resin, biphenyl epoxy resin, bisphenol epoxy resin, stilbene epoxy resin, triphenolmethane epoxy resin, phenol aralkyl epoxy resin (phenylene skeleton, biphenyl skeleton, etc. Naphthol-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol-type epoxy resin, etc., but it is not limited thereto. Moreover, these may be used individually by 1 type, or may use 2 or more types together. Among these, a crystalline epoxy resin having a low melt viscosity and capable of highly-packing an inorganic filler, which in turn enables low moisture absorption of the epoxy resin composition and can improve solder crack resistance. Is preferred.

  The phenol resin (B) used in the above-mentioned epoxy resin composition refers to all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule. For example, phenol novolac resin, cresol novolac resin, phenol aralkyl resin (including phenylene skeleton, biphenyl skeleton, etc.), naphthol aralkyl resin (including phenylene skeleton, biphenyl skeleton, etc.), triphenolmethane resin, terpene modified phenol resin, dicyclo Although a pentadiene modified phenol resin etc. are mentioned, it is not limited to these. Moreover, these may be used individually by 1 type, or may use 2 or more types together.

  The curing accelerator (C) used in the above epoxy resin composition refers to one that can be a catalyst for the crosslinking reaction of the epoxy resin (A) and the phenol resin (B), and examples thereof include 1,8-diazabicyclo (5,5) 4,0) Diazabicycloalkenes such as undecene-7 and derivatives thereof, amine compounds such as tributylamine and benzyldimethylamine, organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate salt, 2-methyl Although imidazole compounds, such as imidazole, etc. are mentioned, it is not limited to these. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular about the kind of inorganic filler (D) used by the said epoxy resin composition, What is generally used for the sealing material can be used. For example, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber, etc. may be mentioned, and one of them may be used alone or two or more of them may be used in combination. Good. In particular, fused silica is preferred. The fused silica can be used either in a crushed or spherical shape, but in order to increase the blending amount and to suppress the increase in the melt viscosity of the epoxy resin composition, it is more preferable to mainly use spherical silica.

  In the above epoxy resin composition which is preferably used particularly preferably in the manufacturing process using the mold release film for a process of the present embodiment, in addition to the components (A) to (D), inorganic ion exchangers and couplings as needed. Agents, colorants represented by carbon black, natural waxes, synthetic waxes, mold release agents such as higher fatty acids and their metal salts or paraffins, flame retardants such as brominated epoxy resin, antimony oxide, phosphorus compounds, silicone oil, rubber And other additives such as a low stress component such as an antioxidant.

The outgas permeability of the laminated film is more preferably 0.7% by weight or less, particularly preferably less than 0.5% by weight, from the viewpoint of effectively preventing mold contamination.
There is no lower limit to the outgassing permeability of the laminated film, but it is usually 0.01% by weight or more as long as practical materials are used from the viewpoint of economy and availability.

The outgassing permeability of the laminated film can be measured by the following method.
(Measurement of outgassing permeability [% by weight])
Put 10 mg of epoxy sealing resin into vial 1, seal with cap and rubber stopper, heat at 120 ° C for 30 minutes, perform GC-MS measurement by static head space method, and measure the amount of outgassing in vial 1. Measure 1 (Analysis 1)
Subsequently, separately insert 10 mg of epoxy sealing resin into the vial 1 and replace the rubber stopper with the film in the mouth of the vial 1 by covering the film with the cap and preparing a stopper, and then this vial Prepare a vial 2 of a size into which the bottle 1 can be stored, store the vial 1 in the vial 2, seal it with a cap and a rubber stopper, heat at 120 ° C for 30 minutes, and use GC-static head space method MS measurements are performed to assess the amount of outgassing 2 in the vial 2 that has permeated the film. (Analysis 2)
For each film, the outgassing permeability can be calculated from the amount of outgassing 1 obtained in Analysis 1 and the amount of outgassing 2 transmitted through the film obtained in Analysis 2 according to the following (Equation 1).

Permeability of outgassing = Outgas amount 2 / Outgas amount 1 x 100 (% by weight) (Equation 1)

The outgassing permeability of the laminated film is appropriately adjusted by adjusting the outgassing permeability of any of the releasing layer A and the heat-resistant resin layer B constituting the laminating film, and the releasing layer A ′ if present. It is easy and practical to adjust by adjusting the outgassing permeability of the heat-resistant resin layer B as described later.
Also, by providing a layer such as a gas barrier layer C, it is possible to effectively adjust the outgassing permeability of the laminated film.

The oxygen permeability of the laminated film comprising the mold release layer A (and optionally the mold release layer A ′) and the heat resistant resin layer B constituting the process release film of the first aspect of the present invention is 1000 ml / m. It is less than ² · day · MPa.
Here, the oxygen permeability is measured according to JIS K 7126, using OX-TRAN 2/21 ML manufactured by Mocon, at a temperature of 20.degree. H. Measured under the conditions of
When the oxygen permeability of the laminated film is 1000 ml / m ² · day · MPa or less, it is possible to effectively suppress the contamination of the mold in the semiconductor encapsulation process and the like.
The oxygen permeability has a certain positive correlation with the above-mentioned outgassing permeability, and when the oxygen permeability is 1000 ml / m ² · day · MPa or less, the outgassing permeability can also effectively suppress the contamination of the mold. It is likely that the value is as low as, for example, the value as defined in the second aspect of the present invention. Therefore, as in the first embodiment of the present invention, the predetermined outgassing permeability can be measured by using the oxygen permeability which can be measured more simply and which is often measured and known for a commercially available film. The mold release film for the process of the second aspect of the present invention or the member thereof can be designed, manufactured, or obtained more efficiently.

The oxygen permeability of the laminated film is more preferably 500 ml / m ² · day · MPa or less, more preferably 250 ml / m ² · day · MPa or less, and 100 ml / m ² · day · MPa or less Some are more preferable, 75 ml / m ² · day · MPa or less is more preferable, and 50 ml / m ² · day · MPa is particularly preferable.
There is no lower limit to the oxygen permeability of the laminated film, but it is usually 1 ml / m ² · day · MPa or more, as long as practical materials are used from the viewpoint of economy and availability.
The oxygen permeability of the laminated film can be measured, for example, according to JIS K 7126, using a gas barrier test apparatus.
The oxygen permeability of the laminated film is appropriately adjusted by adjusting the oxygen permeability of any one of the releasing layer A and the heat-resistant resin layer B constituting the laminating film, and the releasing layer A ′ if present. It is easy and practical to adjust by adjusting the oxygen permeability of the heat-resistant resin layer B as described later.
The oxygen permeability of the laminated film can be effectively adjusted also by providing a layer such as a gas barrier layer C.

Release layer A
The release layer A constituting the process release film of the present invention has a contact angle to water of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115 °, More preferably, it is 100 ° to 110 °. It is preferable that the resin selected from the group which consists of a fluoro resin, 4-methyl- 1-pentene (co) polymer, and a polystyrene-type resin from the excellent mold release property of a molded article, the ease of acquisition, etc. is included.

  The fluorine resin that can be used for the release layer A may be a resin containing a structural unit derived from tetrafluoroethylene. It may be a homopolymer of tetrafluoroethylene 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, and in such a copolymer, the proportion of constituent units derived from tetrafluoroethylene is 55 to 100% by weight, and ethylene is preferred. It is preferable that the ratio of the structural unit derived from is 0 to 45 weight%.

  The 4-methyl-1-pentene (co) polymer that can be used for the release layer A may be a homopolymer of 4-methyl-1-pentene, and 4-methyl-1-pentene, It may be a copolymer with another olefin having 2 to 20 carbon atoms (hereinafter referred to as "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, the olefin having 2 to 20 carbon atoms to be copolymerized with 4-methyl-1-pentene is 4-methyl. Flexibility can be imparted to -1-pentene. Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1 -Octadecene, 1-eichosen, etc. are included. 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 constitutional unit derived from 4-methyl-1-pentene is 96 to 99% by weight, and other than that It is preferable that the ratio of the structural unit derived from the C2-C20 olefin of 4 is 1 to 4 weight%. By reducing the content of the structural unit derived from the olefin having 2 to 20 carbon atoms, the copolymer can be made hard, that is, the storage elastic modulus E 'can be increased, and the generation of wrinkles in the sealing step or the like can be suppressed It is advantageous to On the other hand, by increasing the content of the structural unit derived from the olefin having 2 to 20 carbon atoms, the copolymer can be softened, that is, the storage elastic modulus E 'can be lowered and mold followability can be improved. It is advantageous to

  The 4-methyl-1-pentene (co) polymers can be prepared by methods known to those skilled in the art. For example, it can be produced by a method using a known catalyst such as a Ziegler-Natta catalyst, a metallocene-based catalyst and the like. The 4-methyl-1-pentene (co) polymer is preferably a highly crystalline (co) polymer. The crystalline copolymer may be any of a copolymer having an isotactic structure and a copolymer having a syndiotactic structure, and in particular, a copolymer having an isotactic structure Is preferable from the viewpoint of physical properties, and it is easy to obtain. Furthermore, 4-methyl-1-pentene (co) polymer can be formed into a film, and stereoregularity and molecular weight are also particularly limited as long as it has strength to endure temperature, pressure and the like at the time of mold molding. I will not. The 4-methyl-1-pentene copolymer may be, for example, a commercially available copolymer such as Mitsui Chemical Co., Ltd. TPX (registered trademark).

Polystyrene resins that can be used for the releasing layer A include homopolymers and copolymers of styrene, and the structural unit derived from styrene contained in the polymer is at least 60% by weight or more Preferably, it is 80% by weight or more.
The polystyrene resin may be isotactic polystyrene or syndiotactic polystyrene, but isotactic polystyrene is preferable from the viewpoints of transparency, availability and the like, and the releasability, heat resistance, etc. From the point of view, syndiotactic polystyrene is preferred. Polystyrene may be used alone or in combination of two or more.

It is preferable that the mold release layer A have heat resistance that can be maintained at the temperature of the mold at molding (typically, 120 to 180 ° C.). From this viewpoint, the release layer A preferably contains a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 190 ° C. or more, and more preferably 200 ° C. or more and 300 ° C. or less.
In order to bring crystallinity to the releasing layer A, for example, in the case of a fluorine resin, it is preferable to include at least a structural unit derived from tetrafluoroethylene, and in the case of 4-methyl-1-pentene (co) polymer, 4-methyl-1 -It is preferable to include at least a structural unit derived from pentene, and it is preferable to include at least syndiotactic polystyrene in a polystyrene resin. Since the resin constituting the releasing layer A contains a crystal component, wrinkles are less likely to be generated in a resin sealing step or the like, which is suitable for suppressing the wrinkles from being transferred to a molded product to cause appearance defects. .

  The resin containing the crystalline component constituting the releasing layer A has a heat of crystal fusion of 15 J / g or more and 60 J / g or less in the first temperature raising step measured by differential scanning calorimetry (DSC) according to JIS K 7221 Is preferably 20 J / g to 50 J / g. In addition to the fact that the heat resistance and the releasability which can endure heat press molding in a resin sealing process etc. can be expressed more effectively as it is 15 J / g or more, the dimensional change rate is also suppressed. Can prevent the occurrence of wrinkles. On the other hand, when the heat of crystal fusion is 60 J / g or less, the mold release layer A has an appropriate hardness, and sufficient followability to the mold of the film can be obtained in the resin sealing step, etc. There is no risk of damage to the film.

  The release layer A may further contain other resins in addition to the fluorocarbon resin, the 4-methyl-1-pentene copolymer, and / or the polystyrene resin. In this case, the hardness of the other resin is preferably relatively high. Examples of other resins include polyamide-6, polyamide-66, polybutylene terephthalate, polyethylene terephthalate. Thus, even when the release layer A contains a large amount of, for example, a soft resin (e.g., a 4-methyl-1-pentene copolymer containing a large amount of an olefin having 2 to 20 carbon atoms), the hardness is relatively high. By further including a high resin, the release layer A can be hardened, which is advantageous for suppressing the generation of wrinkles in the sealing step and the like.

  It is preferable that content of these other resin is 3-30 weight% with respect to the resin component which comprises the mold release layer A. By setting the content of the other resin to 3 weight or more, the effect by the addition can be made substantial, and by setting the content to 30 weight% or less, the releasability to the mold and the molded article is maintained. be able to.

  In addition to the fluorine resin, 4-methyl-1-pentene (co) polymer, and / or polystyrene-based resin, the release layer A is a heat resistant stabilizer, a weather resistant stabilizer, etc., as long as the object of the present invention is not impaired. The composition may contain known additives which are generally blended with resin for films, such as rust inhibitors, copper damage stabilizers, antistatic agents, and the like. The content of these additives can be, for example, 0.0001 to 10 parts by weight with respect to 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

  The thickness of the release layer A is not particularly limited as long as the release property to the molded product is sufficient, but it is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer A may have an uneven shape as needed, whereby the releasability can be improved. Although the method to provide an unevenness | corrugation in the surface of the mold release layer A does not have a restriction | limiting in particular, General methods, such as embossing, are employable.

Release layer A '
The process release film of the present invention may further have a release layer A ′ in addition to the release layer A and the heat-resistant resin layer B. That is, the process release film of the present invention may be a process release film which is a laminated film including the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order.
The contact angle to water of the release layer A ′ which may constitute the release film for process of the present invention is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° It is preferably 115 °, more preferably 100 ° to 110 °. The preferable material, configuration, physical properties, and the like of the release layer A ′ are the same as those described above for the release layer A.

In the case where the process release film is a laminated film including release layer A, heat-resistant resin layer B and release layer A ′ in this order, release layer A and release layer A ′ are the same. It may be a layer of constitution or a layer of different constitution.
The release layer A and the release layer A ′ have the same or substantially the same configuration from the viewpoint of prevention of warpage, ease of handling due to having the same releasability on all surfaces, etc. Preferably, from the viewpoint of designing each of the releasing layer A and the releasing layer A ′ optimally in relation to the process using the releasing layer A and the releasing layer A ′, for example, the releasing layer A is excellent in releasing property from the mold From the viewpoint of making the layer A ′ excellent in releasability from the molded product, etc., it is preferable that the release layer A and the release layer A ′ have different configurations.
When the release layer A and the release layer A ′ have different configurations, the release layer A and the release layer A ′ may be made of the same material and have different configurations such as thickness. Also, the materials and other configurations may be different.

Heat resistant resin layer B
The heat-resistant resin layer B constituting the process release film of the present invention has a function of supporting the release layer A (and optionally release layer A ') and suppressing the occurrence of wrinkles due to the mold temperature or the like.
In the process release film of the present invention, the heat-resistant resin layer B preferably has gas barrier properties, and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is 3 It is preferable that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer B be 3% or less. Furthermore, the heat-resistant resin layer B has a thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction. More preferably, the rate is 3% or less.
By using a resin layer in which the thermal dimensional change rate in the transverse (TD) direction exhibits the above-described specific value as the heat-resistant resin layer B, the mechanism by which the generation of wrinkles in the release layer is more effectively clarified However, by using the heat-resistant resin layer B having a relatively small thermal expansion / contraction, the thermal expansion / contraction of the release layer A (or the release layer A ') due to heating / cooling during the process is suppressed. It is presumed to be related to

Although any resin layer can be used for the heat-resistant resin layer B, including a non-stretched film, it is particularly preferable to include a stretched film.
The stretched film tends to have a low or negative coefficient of thermal expansion under the influence of stretching in the production process, and the thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is It is relatively easy to realize the characteristic that the thermal dimensional change from 23 ° C. to 170 ° C. in the lateral (TD) direction of the heat-resistant resin layer B is 3% or less. The heat-resistant resin layer B can be suitably used.
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is preferably 2% or less, more preferably 1.5% or less, and 1% or less Is more preferable, and on the other hand, is preferably -10% or more.
The heat dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer B is preferably 2% or less, more preferably 1.5% or less, and 1% or less Is more preferable, and on the other hand, is preferably -10% or more.

The stretched film may be a uniaxially stretched film or a biaxially stretched film. When it is a uniaxially stretched film, it may be either longitudinal stretching or transverse stretching, but it is preferable that stretching be performed at least in the transverse (TD) direction.
There is no particular limitation on the method and apparatus for obtaining the stretched film, and the stretching may be performed by a method known in the art. For example, it can extend | stretch with a heating roll or a tenter type extending machine.

  As the stretched film, it is preferable to use a stretched film selected from the group consisting of a stretched polyester film, a stretched polyamide film, a stretched polypropylene film, and a stretched polyethylene film. These stretched films are relatively easy to reduce the thermal expansion coefficient in the transverse (TD) direction or to be negative by stretching, and their mechanical properties are suitable for the application of the present invention, and It is particularly suitable as a stretched film in the heat-resistant resin layer B because it is low cost and relatively easy to obtain.

As the stretched polyester film, a stretched polyethylene terephthalate (PET) film and a stretched polybutylene terephthalate (PBT) film are preferable, and a biaxial stretched polyethylene terephthalate (PET) film is particularly preferable.
The polyamide constituting the stretched polyamide film is not particularly limited, but polyamide-6, polyamide-66 and the like can be preferably used.
As an oriented polypropylene film, a uniaxially oriented polypropylene film, a biaxially oriented polypropylene film, etc. can be used preferably.
As an oriented polyethylene film, a uniaxially oriented polyethylene film, a biaxially oriented polyethylene film, etc. can be used preferably.
The draw ratio is not particularly limited, and the thermal dimensional change rate may be appropriately controlled, and an appropriate value may be appropriately set to achieve suitable mechanical properties. For example, in the case of a stretched polyester film, the longitudinal direction The width is preferably in the range of 2.7 to 8.0 times in both the transverse direction, and in the case of the 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. In the case of a polypropylene film, in the case of a 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 a uniaxially stretched polypropylene film, 1.times. It is preferably in the range of 5 to 10.0 times.

  The heat-resistant resin layer B has heat resistance that can be maintained at the mold temperature (typically 120 to 180 ° C.) at the time of molding from the viewpoint of controlling the strength of the film and its thermal dimensional change to an appropriate range. Is preferred. From such a viewpoint, the heat-resistant resin layer B preferably contains a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 120 ° C. or more, and the melting point is 155 ° C. or more and 300 ° C. or less Is more preferable, 185 or more and 210 ° C. or less is further preferable, and 185 or more and 205 ° C. or less is particularly preferable.

  As described above, the heat-resistant resin layer B preferably contains a crystalline resin having a crystalline component. As crystalline resin contained in heat-resistant resin layer B, crystalline resin, such as polyester resin, polyamide resin, polypropylene resin, polyethylene resin, can be used for the part or all, for example. Specifically, polyethylene terephthalate or polybutylene terephthalate for polyester resin, polyamide 6 or polyamide 66 for polyamide resin, isotactic polypropylene for polypropylene resin, high density polyethylene or low density polyethylene for polyethylene resin, linear low It is preferred to use density polyethylene.

By including the crystal component of the crystalline resin in the heat-resistant resin layer B, wrinkles are less likely to be generated in the resin sealing step and the like, and it is advantageous to suppress the wrinkles from being transferred to the molded product to cause appearance defects. Become.
The resin constituting the heat-resistant resin layer B preferably has a heat of crystal fusion of 20 J / g to 100 J / g in the first temperature raising step measured by differential scanning calorimetry (DSC) according to JIS K 7221. 25 J / g or more and 65 J / g or less is more preferable, 25 J / g or more and 55 J / g or less is more preferable, 28 J / g or more and 50 J / g or less is more preferable, 28 J / g It is more preferably g or more and 40 J / g or less, and still more preferably 28 J / g or more and 35 J / g or less. At 20 J / g or more, the heat resistance and releasability that can endure heat press molding in a resin sealing step etc. can be exhibited effectively, and the dimensional change rate can be suppressed slightly. The occurrence of wrinkles can also be prevented. On the other hand, when the heat quantity of crystal fusion is 100 J / g or less, the heat-resistant resin layer B can be provided with an appropriate hardness, so that the film conforms sufficiently to the mold in the resin sealing step and the like. In addition to being able to do so, there is no risk of the film being prone to breakage. In the present embodiment, the heat of crystal fusion means the heat (J / g) on the vertical axis and the horizontal axis obtained in the first temperature raising step in the measurement by differential scanning calorimetry (DSC) according to JIS K 7221. In a chart showing a relationship with temperature (° C.), it refers to a numerical value determined by the sum of peak areas having peaks at 120 ° C. or higher.
The heat of crystal fusion of the heat-resistant resin layer B can be adjusted by appropriately setting the conditions of heating and cooling at the time of film production and the conditions of stretching.

The thickness of the heat-resistant resin layer B is not particularly limited as long as the film strength can be secured, but it is usually 1 to 1
It is 00 μm, preferably 5 to 50 μm.

In order to impart the required gas barrier properties to the release film of the present invention, the heat-resistant resin layer B (or the heat-resistant resin layer B and layers adjacent thereto) preferably has gas barrier properties, more specifically outgassing Preferably, the degree is 1.0% by weight or less. When the heat resistant resin layer B (or the heat resistant resin layer B and the layer adjacent thereto) has gas barrier properties, the gas barrier properties of the release layer A (and the release layer A ′ if present) are low. Also, the required gas barrier properties can be imparted to the release film of the present invention. In particular, when 4-methyl-1-pentene (co) polymer is used for release layer A and / or release layer A ′, the gas barrier properties of 4-methyl-1-pentene (co) polymer are generally not high. Therefore, it is particularly preferable that the heat-resistant resin layer B (or the heat-resistant resin layer B and the layer adjacent thereto) have high gas barrier properties, whereby the excellent mold release provided by the 4-methyl-1-pentene (co) polymer It is possible to achieve both the properties etc. and the excellent mold contamination resistance provided by the heat-resistant resin layer B (or the heat-resistant resin layer B and the layer adjacent thereto).
The outgassing permeability of the heat-resistant resin layer B (or the heat-resistant resin layer B and layers adjacent thereto) is more preferably 0.7% by weight or less and particularly preferably less than 0.5% by weight.
The method of measuring the oxygen permeability of the heat-resistant resin layer B (or the heat-resistant resin layer B and the layer adjacent thereto) is a laminated film comprising a release layer A, a heat-resistant resin layer B and optionally release layer A '. The oxygen permeation measurement method is the same as that described above.

  The means for imparting preferable gas barrier properties to the heat resistant resin layer B is not particularly limited. For example, the kind of resin constituting the heat resistant resin layer B or the type and amount of the additive added thereto are appropriately selected. The gas barrier properties may be improved, or the gas barrier properties may be improved by stretching the polymer film constituting the heat resistant resin layer B or the like. As a matter of course, by increasing the thickness of the heat resistant resin layer B, the gas barrier properties can be further improved.

Gas barrier layer C
Alternatively, the gas barrier layer C may be laminated on the heat resistant resin layer B to improve the gas barrier properties of the entire heat resistant resin layer B and the gas barrier layer C adjacent thereto.
The gas barrier layer C may be an inorganic layer or an organic layer. The inorganic layer is preferable from the viewpoints of cost, transparency, heat resistance and the like, and the organic layer is preferable from the viewpoints of adhesion to a substrate and cracking resistance, and the inorganic layer and the organic layer are further preferable. By laminating layers, it is possible to make a configuration that makes use of the features of both.

  The inorganic substance forming the suitable inorganic layer is not particularly limited as long as it does not react with other layers by heating at the time of mold molding and the like without decomposition and maintaining the layer, but mold molding is possible even when heated to 165 ° C. Materials that do not react with other layers by heating, etc., do not decompose, and can maintain the layers are preferable, and even if heated to 185 ° C., they do not react with other layers by heating such as during mold molding. It is desirable that the material be a material that does not decompose and can maintain the layer.

  The inorganic layer is preferably a thin film obtained by amorphousizing a metal or an oxide of the metal. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb) A thin film obtained by amorphousizing a metal such as zirconium (Zr) or yttrium (Y) or an oxide of the metal can be used. Among the above, aluminum, silicon, their oxides, and combinations thereof are preferable from the viewpoint of gas barrier properties and the ease of formation of the inorganic layer, and releasability, gas permeability, easiness of production, spreading From the viewpoint of properties (elongation ease), aluminum and its oxide are more preferable.

The inorganic layer is preferably formed on the whole of one surface of the heat-resistant resin layer B, and the inorganic layer is preferably formed as a continuous film at least in a portion in contact with the mold.
As a method of forming the inorganic layer, for example, physical vapor deposition (Physical Vapor Deposition, PVD) such as vacuum evaporation, sputtering or ion plating, or plasma chemical vapor deposition, thermal chemical vapor deposition The chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as phase growth method and photochemical vapor deposition method can be mentioned.

  In the present embodiment, the method of forming the inorganic layer will be specifically described. A vacuum evaporation method in which the metal or metal oxide as described above is used as a raw material, which is heated and vapor-deposited on the heat-resistant resin layer B; Alternatively, an oxidation reaction deposition method in which metal or metal oxide is used as a raw material, oxygen gas or the like is introduced to oxidize, and vapor deposition is carried out on the heat resistant resin layer B, and a plasma assisted oxidation reaction which further assists the oxidation reaction with plasma. The inorganic layer can be formed by evaporation or the like. In the present invention, when forming a vapor-deposited film of silicon oxide, the inorganic layer can be formed using plasma chemical vapor deposition using organosiloxane as a raw material.

The thickness of the inorganic layer varies depending on the material to be used, but is usually 5 to 200 nm. When the thickness is 5 nm or more, the outgassing permeability is low, and mold contamination and blocking of a vacuum line for film adsorption can be effectively suppressed. Moreover, it is easy to prevent the fall of metal mold following property as it is 200 nm or less.
The thickness of the inorganic layer is preferably 5 to 200 nm, more preferably 8 to 180 nm, and still more preferably 10 to 150 nm.
Also when using an aluminum layer as an inorganic layer, 5-200 nm is preferable, More preferably, it is 8-180 nm, More preferably, it is 10-150 nm.

The organic substance forming the suitable organic layer is not particularly limited, but, for example, a polymer having a vinyl alcohol unit (hereinafter, also referred to as “polymer (a)”) and a polymer having a vinylidene chloride unit (hereinafter, At least one polymer selected from the group consisting of “polymer (a)” can be particularly preferably used.
In addition, a "vinyl alcohol unit" is a unit by which the acetoxy group of the vinyl acetate unit was converted into the hydroxyl group by chemically converting the polymer obtained by superposition | polymerization of vinyl acetate.
The polymer may or may not have a crosslinked structure.

The polymer (a) may be composed only of a vinyl alcohol unit or may further have a unit other than a vinyl alcohol unit.
The proportion of vinyl alcohol units in the polymer (a) is not particularly limited, but is preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more, based on the total of all units. If the proportion of the vinyl alcohol unit is equal to or more than the above lower limit value, the gas barrier property is more excellent.

As a polymer (a), the following polymer (a1) or a polymer (a 2) is mentioned.
Polymer (A1): A polymer having a vinyl alcohol unit and having no crosslinked structure.
Polymer (A2): A polymer having a vinyl alcohol unit and having a crosslinked structure.

The polymer (Al) may be composed only of a vinyl alcohol unit or may further have a unit other than a vinyl alcohol unit.
As the polymer (Al), for example, a copolymer having a polyvinyl alcohol (hereinafter also referred to as "PVA"), a vinyl alcohol unit, and a unit other than a vinyl alcohol unit and a vinyl acetate unit (hereinafter referred to as "copolymer" It is also referred to as “coalescence (a 11)”. The copolymer (A11) may further have a vinyl acetate unit. One of these polymers may be used alone, or two or more thereof may be used in combination.

PVA is a polymer which consists only of a vinyl alcohol unit, or a polymer which consists of a vinyl alcohol unit and a vinyl acetate unit.
As PVA, completely saponified polyvinyl acetate (saponification degree: 99 to 100 mol%), semi-completely saponified (saponification degree: 90 to 99 mol%), partially saponified (saponification degree: 70 mol%) More than 90 mol%) etc. are mentioned.
The degree of saponification of PVA is preferably 80 to 100 mol%, more preferably 85 to 100 mol%, and particularly preferably 90 to 100 mol%. As the degree of saponification is higher, the gas barrier properties of the gas barrier layer C tend to be higher.
The degree of saponification is a ratio of acetoxy groups contained in polyvinyl acetate, which is a raw material of PVA, converted to hydroxyl groups by saponification as a unit ratio (mol%), and is defined by the following formula. The degree of saponification can be determined by the method defined in JIS K 6726: 1994.
Saponification degree (mol%) = {(number of hydroxyl groups) / (number of hydroxyl groups + number of acetoxy groups)} × 100

  Examples of other units in the copolymer (A11) include units having a dihydroxyalkyl group, acetoacetyl group, oxyalkylene group, carboxy group, alkoxycarbonyl group and the like, and units derived from an olefin such as ethylene and the like. The other unit that the copolymer (A11) has may be one type or two or more types.

The polymer (B) may be composed only of vinylidene chloride units, or may further have units other than vinylidene chloride units.

  70 mol% or more is preferable with respect to the sum total of all the units, and, as for the ratio of the vinylidene chloride unit in a polymer (i), 80 mol% or more is especially preferable. If the proportion of vinylidene chloride units is equal to or more than the above lower limit value, the gas barrier properties of the gas barrier layer C are more excellent.

As a polymer (i), the following polymer (i) or a polymer (ii) is mentioned.
Polymer (i): A polymer having a vinylidene chloride unit and having no crosslinked structure.
Polymer (B): A polymer having a vinylidene chloride unit and having a crosslinked structure.

Examples of the polymer (i) include polyvinylidene chloride and vinylidene chloride-alkyl acrylate copolymer.
Examples of the polymer (ii) include polymers obtained by reacting the polymer (ii) with a crosslinking agent.
The crosslinking agent is preferably a water-soluble crosslinking agent that reacts with a halogen group or a functional group bonded to an alkyl acrylate to form a crosslinked structure. Specific examples thereof include organic metal compounds, isocyanate compounds having two or more isocyanate groups, and bisvinylsulfone compounds. Specific examples of these crosslinking agents include those described above.

Furthermore, as the organic layer, a layer formed by heating and curing a liquid mixture of a polycarboxylic acid such as polyacrylic acid and polymethacrylic acid and a polyamine compound such as polyethyleneimine and polyallylimine may be used. At this time, from the viewpoint of preventing gelation of the mixed solution, it is preferable to set the neutralization degree to 50 to 100 equivalent%.
In addition, the ratio of polycarboxylic acid polyacrylic acid to polyamine compound is (the number of moles of -COO- group contained in polycarboxylic acid in the gas barrier coating material) / (amino group contained in the polyamine compound in the gas barrier coating material) Is preferably 100/22, more preferably 100/25 or more, and particularly preferably 100/29 or more. On the other hand, (the number of moles of -COO- group contained in polycarboxylic acid in the coating material for gas barrier) / (the number of moles of amino group contained in the polyamine compound in the coating material for gas barrier) is preferably 100/99 or less More preferably, it is 100/86 or less, especially preferably 100/75 or less.
The molecular weight of the polycarboxylic acid is usually 5000-100000, preferably 10000-100000.
On the other hand, the polymerization average molecular weight of the polyamine compound is usually 1,500 to 100,000, preferably 1,500 to 500,000, more preferably 1,500 to 2,500,000 and particularly preferably 1,500 to 100,000.

  In the process release film of the present invention, the protective resin layer D is formed on the gas barrier layer C for protection from external impact and the like when the gas barrier layer C is made of metal or metal oxide. Is also a preferred embodiment.

  The material of the protective resin layer D is not particularly limited as long as it can be formed on the gas barrier layer C formed on the heat-resistant resin layer B by, for example, coating means such as coating, printing, and dipping. For example, resins such as urethane resin, melamine resin, acrylic resin, polyvinylidene chloride, ethylene-vinyl alcohol resin and polyvinyl alcohol resin, metal acrylate resin, polyamide cross-linked resin, and the like are mentioned as preferable ones. Among these, a urethane resin, or a metal salt of acrylic acid resin, and a polyamide cross-linked resin are more preferable, and a metal salt of acrylic acid metal resin and a polyamide cross-linked resin are most preferable.

Other Layers The process release film of the present invention has layers other than the release layer A, the heat-resistant resin layer B, the release layer A ′, and the gas barrier layer C, as long as the object of the present invention is not violated. It may be For example, the protective resin layer D described above may be provided on the gas barrier layer C, and an adhesive layer may be provided between the release layer A (or release layer A ′) and the heat-resistant resin layer B, as necessary. May be included. The material used for the adhesive layer is not particularly limited as long as it can firmly bond the release layer A and the heat-resistant resin layer B and does not peel off even in the resin sealing step or the release step.

  For example, when the release layer A (or release layer A ′) contains a 4-methyl-1-pentene copolymer, the adhesive layer is modified 4-methyl-1 which is graft-modified with an unsaturated carboxylic acid or the like. -Pentene-based copolymer resin, and olefin-based adhesive resin composed of 4-methyl-1-pentene-based copolymer and α-olefin-based copolymer are preferable. When the release layer A (or release layer A ′) contains a fluorocarbon resin, the adhesive layer is preferably a polyester-based, acrylic-based, fluororubber-based adhesive, or the like. The thickness of the adhesive layer is not particularly limited as long as the adhesion between the release layer A (or release layer A ′) and the heat-resistant resin layer B can be improved, and is, for example, 0.5 to 10 μm.

  Although there is no restriction | limiting in particular in the total thickness of the release film for processes of this invention, For example, it is preferable that it is 10-300 micrometers, and it is more preferable that it is 30-150 micrometers. When the total thickness of the release film is in the above-mentioned range, it is preferable because the handling property at the time of using it as a roll is good and the amount of waste of the film is small.

  Hereinafter, the preferred embodiment of the process release film of the present invention will be described more specifically. FIG. 1 is a schematic view showing an example of a three-layered 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 of the release film 16 with an adhesive layer 14 interposed therebetween.

The release layer 16 is the above-mentioned release layer A, the heat-resistant resin layer 12 is the above-mentioned heat-resistant resin layer B, and the adhesive layer 14 is the above-mentioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing process; the heat-resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the mold in the sealing process.
Further, as shown in FIG. 3, the gas barrier layer 17 may be provided adjacent to the heat-resistant resin layer 12.

  FIG. 2 is a schematic view showing an example of a five-layered process release film. Members having the same functions as those in FIG. 1 are given the same reference numerals. As shown in FIG. 2, the release film 20 has a heat resistant resin layer 12 and release layers 16A and release layers 16B formed on both sides of the heat resistant resin layer 12 with an adhesive layer 14 interposed therebetween. The release layer 16A is the above-mentioned release layer A, the heat-resistant resin layer 12 is the above-mentioned heat-resistant resin layer B, the release layer 16B is the above-mentioned release layer A ', and the adhesive layer 14 is each It is an adhesive layer.

The compositions of the release layers 16A and 16B may be the same or different. The thicknesses of the release layers 16A and 16B may also be the same or different. However, it is preferable that the release layers 16A and 16B have the same composition and thickness, because they have a symmetrical structure and the release film itself does not easily warp. In particular, since stress may be generated in the release film of the present invention by heating in the sealing process, it is preferable to suppress warpage. As described above, it is preferable that the release layers 16A and 16B be formed on both sides of the heat-resistant resin layer 12, because good release properties can be obtained in any of the molded article and the inner surface of the mold.
Further, as shown in FIG. 4, the gas barrier layer 17 may be provided adjacent to the heat-resistant resin layer 12.

The sealing resin preferably used in the manufacturing process using the release film for process of the present invention is not particularly limited, and may be any of a thermoplastic resin and a thermosetting resin. Curable resins are widely used. The material of the resin is not particularly limited, but an epoxy-based thermosetting resin or a silicone sealing resin can be preferably used, and in particular, an epoxy-based sealing resin is preferably used.
(A) epoxy resin, (B) phenolic resin, (C) curing accelerator and (D) as an epoxy-based sealing resin which is preferably used particularly preferably in the manufacturing process using the process release film of the present invention There may be mentioned epoxy resin compositions which are said to contain an inorganic filler.
The epoxy resin (A) used in the above epoxy resin composition refers to all monomers, oligomers and polymers having two or more epoxy groups in one molecule. For example, ortho cresol novolac epoxy resin, phenol novolac epoxy resin, biphenyl epoxy resin, bisphenol epoxy resin, stilbene epoxy resin, triphenolmethane epoxy resin, phenol aralkyl epoxy resin (phenylene skeleton, biphenyl skeleton, etc. Naphthol-type epoxy resin, alkyl-modified triphenolmethane-type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol-type epoxy resin, etc., but it is not limited thereto. Moreover, these may be used individually by 1 type, or may use 2 or more types together. Among these, a crystalline epoxy resin having a low melt viscosity and capable of highly-packing an inorganic filler, which in turn enables low moisture absorption of the epoxy resin composition and can improve solder crack resistance. Is preferred.

  The phenol resin (B) used in the above-mentioned epoxy resin composition refers to all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule. For example, phenol novolac resin, cresol novolac resin, phenol aralkyl resin (including phenylene skeleton, biphenyl skeleton, etc.), naphthol aralkyl resin (including phenylene skeleton, biphenyl skeleton, etc.), triphenolmethane resin, terpene modified phenol resin, dicyclo Although a pentadiene modified phenol resin etc. are mentioned, it is not limited to these. Moreover, these may be used individually by 1 type, or may use 2 or more types together.

  The curing accelerator (C) used in the above epoxy resin composition refers to one that can be a catalyst for the crosslinking reaction of the epoxy resin (A) and the phenol resin (B), and examples thereof include 1,8-diazabicyclo (5,5) 4,0) Diazabicycloalkenes such as undecene-7 and derivatives thereof, amine compounds such as tributylamine and benzyldimethylamine, organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate salt, 2-methyl Although imidazole compounds, such as imidazole, etc. are mentioned, it is not limited to these. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular about the kind of inorganic filler (D) used by the said epoxy resin composition, What is generally used for the sealing material can be used. For example, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber, etc. may be mentioned, and one of them may be used alone or two or more of them may be used in combination. Good. In particular, fused silica is preferred. The fused silica can be used either in a crushed or spherical shape, but in order to increase the blending amount and to suppress the increase in the melt viscosity of the epoxy resin composition, it is more preferable to mainly use spherical silica.

  The epoxy resin composition preferably and particularly preferably used in the production process using the mold release film for a process of the present invention includes, in addition to the components (A) to (D), inorganic ion exchangers and couplings as needed. Agents, colorants represented by carbon black, natural waxes, synthetic waxes, mold release agents such as higher fatty acids and their metal salts or paraffins, flame retardants such as brominated epoxy resin, antimony oxide, phosphorus compounds, silicone oil, rubber And other additives such as a low stress component such as an antioxidant.

Method for Producing Process Release Film The process release film of the present invention may be produced by any method. For example, 1) A method for producing a process release film by coextrusion molding of a release layer A and a heat-resistant resin layer B (co-extrusion method), 2) On a film to be a heat-resistant resin layer B By applying and drying a molten resin of the resin to be the release layer A and the adhesive layer, or applying and drying a resin solution in which the resin to be the release layer A and the adhesive layer is dissolved in a solvent. A method of producing a mold release film for a process (coating method), 3) manufacturing a film to be a mold release layer A and a film to be a heat-resistant resin layer B in advance, and laminating (laminating) these films And the like (a laminating method) for producing a process release film.

In the method 3), as a method of laminating each resin film, various known laminating methods can be adopted, and examples thereof include an extrusion laminating method, a dry laminating method, a thermal laminating method and the like.
In the dry lamination method, each resin film is laminated using an adhesive. As the adhesive, those known as adhesives for dry lamination can be used. For example, polyvinyl acetate adhesives; homopolymers or copolymers of acrylic esters (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or acrylic esters and other monomers (methacrylic acid) Polyacrylic acid ester adhesive made of copolymer with methyl, acrylonitrile, styrene, etc .; cyanoacrylate adhesive; ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid) Etc.) ethylene copolymer-based adhesive comprising copolymer etc .; cellulose-based adhesive; polyester-based adhesive; polyamide-based adhesive; polyimide-based adhesive; amino resin-based comprising urea resin or melamine resin etc. Adhesive; Phenolic resin adhesive; Epoxy adhesive; Polyol (polyetherpolyol , Polyurethane-based adhesives crosslinking with polyester polyols etc. and isocyanates and / or isocyanurates; reactive (meth) acrylic-based adhesives; rubber-based adhesives comprising chloroprene rubber, nitrile rubber, styrene-butadiene rubber etc .; silicone-based Adhesives: Inorganic adhesives made of alkali metal silicate, low melting point glass, etc .; and other adhesives can be used. The resin film to be laminated by the method 3) may be a commercially available one, or one produced by a known production method may be used. The resin film may be subjected to surface treatment such as corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, primer coating treatment and the like. It does not specifically limit as a manufacturing method of a resin film, A well-known manufacturing method can be utilized.

  1) The co-extrusion molding method is preferable in that defects such as foreign matter biting between the resin layer to be the release layer A and the resin layer to be the heat-resistant resin layer B and the warp of the release film are less likely to occur. . 3) The laminating method is a preferable manufacturing method when using a stretched film for the heat-resistant resin layer B. In this case, it is preferable to form an appropriate adhesive layer at the interface between the films as necessary. In order to enhance the adhesion between the films, the interface between the films may be subjected to surface treatment such as corona discharge treatment, if necessary.

  The process release film may be uniaxially or biaxially stretched as needed, whereby the film strength of the film can be increased.

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

Manufacturing Process The mold release film for process of the present invention can be used by being disposed between a semiconductor chip or the like and the inner surface of the mold when the semiconductor chip or the like is disposed in a mold and the resin is injected and molded. . By using the process release film of the present invention, it is possible to effectively prevent mold release defects, burrs and the like from the mold.
The resin used in the above manufacturing process may be either a thermoplastic resin or a thermosetting resin, but in the relevant technical field, thermosetting resins are widely used, and in particular epoxy-based thermosetting resins. It is preferred to use.
As the above manufacturing process, the sealing of a semiconductor chip is most representative, but it is not limited to this, and the present invention can be applied to a fiber reinforced plastic molding process, a plastic lens molding process, etc. .

FIG. 5, FIG. 6A and FIG. 6B are schematic diagrams which show an example of the manufacturing method of the resin-sealed semiconductor using the release film of this invention.
As shown in FIG. 5a, the release film 1 of the present invention is fed from the roll-shaped roll into the forming mold 2 by the rolls 1-2 and 1-3. Next, the release film 1 is placed on the inner surface of the upper mold 2. If necessary, the inner surface of the upper mold 2 may be vacuumed to cause the release film 1 to be in close contact with the inner surface of the upper mold 2. A semiconductor chip 6 disposed on a substrate is disposed in the lower mold 5 of the molding molding apparatus, and a sealing resin is disposed on the semiconductor chip 6 or a liquid sealing resin is applied so as to cover the semiconductor chip 6. As a result, the sealing resin 4 is accommodated between the upper mold 2 and the lower metal mold 5 on which the mold release film 1 which has been evacuated and closely attached is disposed. Next, as shown in FIG. 5 b, the upper mold 2 and the lower mold 5 are closed via the release film 1 of the present invention to cure the sealing resin 4.

  As shown in FIG. 5 c, the sealing resin 4 is fluidized in the mold by the mold closing and curing, and the sealing resin 4 flows into the space and is filled so as to surround the side surface of the semiconductor chip 6, and the semiconductor is sealed. The upper mold 2 and the lower mold 5 open the chip 6 and take it out. After the mold is opened and the molded product is taken out, the mold release film 1 is repeatedly used a plurality of times, or a new mold release film is supplied and subjected to the next resin molding.

The mold release film of the present invention is brought into close contact with the upper mold, interposed between the mold and the sealing resin, and resin molded to prevent adhesion of the resin to the mold and stain the resin mold surface of the mold. And, the molded product can be easily released.
The release film may be supplied newly for each resin molding operation to carry out resin molding, or may be supplied newly for each resin molding operation for a plurality of times to carry out resin molding.

The sealing resin may be a liquid resin or a solid resin at normal temperature, but a sealing material such as one that becomes liquid at the time of resin sealing can be adopted as appropriate. Specifically, epoxy resin (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolac epoxy resin, etc.) is mainly used as the sealing resin material, and polyimide resin (other than epoxy resin) is mainly used. It is possible to use one which is usually used as a sealing resin such as a bismaleimide-based resin, a silicone-based resin (thermosetting addition type) and the like. Moreover, as resin sealing conditions, although it changes with sealing resin to be used, setting suitably in the range of hardening temperature 120 degreeC-180 degreeC, molding pressure 10-50kg / cm < ² >, hardening time 1-60 minutes, for example it can.

  Before and after the step of arranging the mold release film 1 on the inner surface of the molding die 8 and the step of arranging the semiconductor chip 6 in the molding die 8 are not particularly limited, and may be performed simultaneously. After placement, the release film 1 may be placed, or after the release film 1 is placed, the semiconductor chip 6 may be placed.

  As described above, since the release film 1 has the release layer A (and the release layer A ′ if desired) having high release property, the semiconductor package 4-2 can be released easily. In addition, since the mold release film 1 has appropriate flexibility, it is difficult to get wrinkled by the heat of the molding die 8 while having excellent followability to the mold shape. For this reason, a sealed semiconductor package having a good appearance without any wrinkles being transferred to the resin-sealed surface of the sealed semiconductor package 4-2 or a portion not filled with the resin (a resin chip) being generated. 4-2 can be obtained.

  In addition to the compression molding method for pressure heating the solid sealing resin material 4 as shown in FIG. 5, the transfer molding method for injecting the flowing sealing resin material as described later is adopted. It is also good.

  6A and 6B are schematic views showing a transfer molding method which is an example of a method of manufacturing a resin-encapsulated semiconductor using the release film of the present invention.

  As shown in FIG. 6A, the release film 22 of the present invention is supplied from the roll-shaped roll by the roll 24 and the roll 26 into the molding die 28 (step a). Next, the release film 22 is disposed on the inner surface 30A of the upper mold 30 (step b). If necessary, the upper mold inner surface 30A may be vacuum drawn to bring the release film 22 into close contact with the upper mold inner surface 30A. Next, the semiconductor chip 34 (the semiconductor chip 34 fixed to the substrate 34A) to be resin-sealed is disposed in the molding die 28, and the sealing resin material 36 is set (step c) and clamped (step c). Step d).

  Next, as shown in FIG. 6B, the sealing resin material 36 is injected into the molding die 28 under predetermined heating and pressurizing conditions (step e). The temperature (molding temperature) of the molding die 28 at this time is, for example, 165 to 185 ° C., the molding pressure is, for example, 7 to 12 MPa, and the molding time is, for example, about 90 seconds. Then, after holding for a predetermined time, the upper mold 30 and the lower mold 32 are opened, and the resin-sealed semiconductor package 40 and the mold release film 22 are simultaneously or sequentially released (step f).

  Then, as shown in FIG. 7, by removing the excess resin portion 42 of the obtained semiconductor package 40, the desired semiconductor package 44 can be obtained. The mold release film 22 may be used as it is for resin sealing of other semiconductor chips, but every time molding is completed, the roll is operated to feed the film, and the mold release film 22 is newly molded. It is preferable to supply 28.

  Before and after the step of disposing the mold release film 22 on the inner surface of the molding die 28 and the step of disposing the semiconductor chip 34 in the molding die 28 are not particularly limited, and may be performed simultaneously. After placement, the release film 22 may be placed, or after the release film 22 is placed, the semiconductor chip 34 may be placed.

  As described above, since the release film 22 has the release layer A (and optionally, the release layer A ′) having a high release property, the semiconductor package 40 can be easily released. Further, since the release film 22 has appropriate flexibility, it is difficult to get wrinkled by the heat of the molding die 28 while having excellent followability to the shape of the die. For this reason, the semiconductor package 40 having a good appearance can be obtained without the wrinkles being transferred to the resin sealing surface of the semiconductor package 40 and the part not filled with the resin (the resin chipping) being generated.

The mold release film of the present invention is not limited to the process of resin sealing a semiconductor element, but is a process of molding and releasing various molded articles using a molding die, such as fiber reinforced plastic molding and mold release process, plastic lens molding It can be preferably used also in the mold release step and the like.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

In the following examples / comparative examples, evaluation of physical properties / properties was performed by the following methods.
(Thermal dimensional change rate)
A film sample is cut into a length of 20 mm and a width of 4 mm in the longitudinal direction and width direction of the film, respectively, using a TA Instruments TMA (Thermal mechanical analyzer, product name: Q400) and a chuck distance of 8 mm of 0.005 N After holding at 23 ° C for 5 minutes while applying a load, the temperature is raised from 23 ° C to 120 ° C at a heating rate of 10 ° C / min, and the dimensional change in each direction is measured. The rate was calculated.

Thermal dimensional change rate (%) (23 → 120 ° C.) = {[(L ₂ −L ₁ ) / L ₁ ] × 100}
... (1)
L ₁ : sample length at 23 ° C (mm)
L ₂ : sample length at 120 ° C (mm)

Contact angle to water (water contact angle)
The water contact angle of the surface of the release layers A and A ′ was measured using a contact angle measurement device (FACECA-W, manufactured by Kyowa Interface Science, Inc.) in accordance with JIS R3257.

(Melting point (Tm), heat of crystal fusion)
Approximately 5 mg of a polymer sample is precisely weighed using a Q100 product manufactured by TA Instruments as a differential scanning calorimeter (DSC), and a nitrogen gas inflow of 50 ml / min according to JIS K 7121. The temperature was raised to 280 ° C. at a heating rate of 10 ° C./min to measure the thermal melting curve, and the melting point (Tm) and the heat of crystal melting of the sample were determined from the obtained thermal melting curve.

(Removal property)
After placing the process release film prepared in each example / comparative example while applying a tension of 10 N between the upper mold and the lower mold as shown in FIG. 5, the upper mold parting Vacuum adsorbed on the surface. Next, after filling a sealing resin (trade name: R4212-2C, manufactured by Nagase Sangyo Co., Ltd.) on the substrate so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in a lower mold and clamped. At this time, the temperature (molding temperature) of the molding die was 120 ° C., the molding pressure was 10 MPa, and the molding time was 400 seconds. Then, as shown in FIG. 5c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film.
The releasability of the release film was evaluated based on the following criteria.
○: The release film is naturally peeled off simultaneously with the opening of the mold.
Δ: The release film does not peel off naturally, but it is easily peeled off when it is pulled by hand (when tension is applied).
X: The mold release film is in close contact with the resin sealing surface of the semiconductor package and can not be peeled off by hand.

(Wear resistance)
The state of wrinkles of the mold release film and the resin sealing surface of the semiconductor package after mold release in the above process was evaluated based on the following criteria.
Good: There is no wrinkle in any of the release film and the semiconductor package.
Δ: There is slight wrinkles in the release film, but there is no transfer of wrinkles to the semiconductor package.
×: There are many defects in the semiconductor package as well as the release film.

(Mold followability)
The mold followability of the release film when the release was performed in the above process was evaluated according to the following criteria.
:: There is no resin chip (a part not filled with resin) in the semiconductor package.
:: slight resin chipping at the end of the semiconductor package (except for chipping due to defects) ×: many resin chipping at the edge of the semiconductor package (but excluding chipping due to the defects)

(Mold contamination)
As shown in FIG. 8, a 0.3 mm thick Al plate, a 0.5 mm thick SUS frame (inner frame 100 mm square) shaped in a V shape, and the process release film prepared in each example / comparative example And two 0.3 mm thick Al plates were sequentially stacked. Furthermore, a sealing resin for semiconductors (trade name: R4212-2C, manufactured by Nagase Sangyo Co., Ltd.) is used as a spacer between two mold release films using a 0.1 mm thick SUS frame cut into a square shape. And hot pressed with a flat plate under an environment of 120.degree. C. and 10 MPa for 400 seconds. After pressing, the 0.3 mm thick Al plate was repeatedly used, and press molding was repeated 1000 times under the above conditions except the above, and the stain attached to the surface of the Al plate was evaluated as mold stain according to the following criteria. The arrangement at the time of evaluation is shown in FIG.
○: no stain on the Al surface was observed ×: stain on the Al surface was observed

(Measurement of outgassing permeability [% by weight])
As shown in FIG. 9 (a), 10 mg of the above-mentioned semiconductor sealing resin (trade name: R4212-2C, manufactured by Nagase Sangyo Co., Ltd.) is placed in the vial 1 and sealed with a cap and a rubber stopper. It heated for 30 minutes and performed GC-MS measurement by a static head space method, and measured the outgassing amount 1 in the vial 1. (Analysis 1)
<Analytical conditions>
Pretreatment device: Head space sampler (manufactured by Agilent Technologies)
Measuring device: GC-MS (manufactured by Agilent Technologies)
Injection method: split method (10: 1)
Column: DB-5MS (30m x 250μm x 0.25μm)
Temperature rising condition: 40 ° C (0 min hold) → 320 ° C (0 min hold) (10 ° C / min)
Measurement mode: SCAN (m / z = 30 to 600)
Subsequently, as shown in FIG. 9 (b), 10 mg of epoxy sealing resin (trade name: R4212-2C, manufactured by Nagase Sangyo Co., Ltd.) is separately placed in the vial 1 and each example is replaced with a rubber stopper. / The mold release film prepared in the comparative example is put on the bottle neck of the vial 1 and the one sealed with the mold release film and the cap is prepared, and then the vial 2 of the size into which the vial 1 is inserted The vial 1 is stored in the vial 2, sealed with a cap and a rubber stopper, heated at 120 ° C. for 30 minutes, and subjected to a GC-MS measurement by a static head space method. The amount of outgas 2 in the vial 2 which permeated the mold film was measured. (Analysis 2)
From the release film quantity 1 obtained in analysis 1 and the release gas quantity 2 transmitted through the release film for process obtained in analysis 2 for the release films for process prepared in each example / comparative example, the following (Equation 1) The outgassing permeability was calculated according to.
Permeability of outgassing = Outgas amount 2 / Outgas amount 1 x 100 (% by weight) (Equation 1)

(Measurement of oxygen permeability [ml / (m ² · day · MPa)])
According to JIS K 7126, the release film for process prepared in each of the examples / comparative examples was a temperature of 20 ° C. and a humidity of 50%, using OX-TRAN 2/21 ML manufactured by Mocon Corporation. H. It measured on condition of.

Example 1
Biaxially stretched PET (polyethylene terephthalate) film B1 (Mitsui Chemicals Tosoh Co., Ltd., product name) with a film thickness of 12 μm with aluminum oxide (ALO film) deposited on one side of the film as heat resistant resin layer B laminated with inorganic gas barrier layer C : TL-PET H) was used. The thermal dimensional change from 23 ° C. to 120 ° C. of the film B1 was 0.1% in the longitudinal (MD) direction and 0.4% in the transverse (TD) direction. The melting point of the biaxially stretched PET film was 260 ° C., and the heat of crystal fusion was 38 J / g.

As the release layers A and A ′, a non-stretched 4-methyl-1-pentene copolymer resin film A1 was used. Specifically, a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022, melting point: 229 ° C., heat of crystal fusion: 22 J / g) manufactured by Mitsui Chemicals, Inc. is melted and extruded at 270 ° C. By adjusting the slit width of the T-die, a non-stretched film with a thickness of 15 μm was used.
The non-stretched 4-methyl-1-pentene copolymer resin film had a surface water contact angle of 105 °, but one film surface had a water contact angle based on JIS R 3257 of 30 ° or less Then, corona treatment was applied from the viewpoint of adhesion improvement by the adhesive.
The thermal dimensional change from 23 ° C. to 120 ° C. of the 4-methyl-1-pentene copolymer resin film was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction. .

(adhesive)
The following urethane adhesives were used as an adhesive used by the dry lamination process which bonds each film together.
[Urethane-based adhesive]
Main agent: Takelac A-616 (made by Mitsui Chemicals, Inc.). Hardening agent: Takenate A-65 (manufactured by Mitsui Chemicals, Inc.). The main agent and the curing agent were mixed such that the weight ratio (main agent: curing agent) was 16: 1, and ethyl acetate was used as a diluent.

(Production of mold release film)
The urethane adhesive is coated at 1.5 g / m ² by gravure coating on one surface of a biaxially stretched PET (polyethylene terephthalate) film B1 on which the inorganic gas barrier layer C is laminated, and it is not stretched 4-methyl- After laminating the corona-treated surface of the 1-pentene copolymer resin film by dry lamination, subsequently, 1.5 g / m of a urethane adhesive is applied to the side of the biaxially stretched PET (polyethylene terephthalate) film surface of this laminated film. ^2. Apply by ² and bond the corona-treated side of the non-stretched 4-methyl-1-pentene copolymer resin film by dry lamination to form a 5-layer structure (releasing layer A / adhesive layer / gas barrier layer C / heat resistant A release film for processing of resin layer B / adhesive layer / releasing layer A ′) was obtained.
The dry laminating conditions were a substrate width of 900 mm, a conveying speed of 30 m / min, a drying temperature of 50 to 60 ° C., a laminating roll temperature of 50 ° C., and a roll pressure of 3.0 MPa.

The thermal dimensional change from 23 ° C. to 120 ° C. of the process release film was 0.8% in the longitudinal (MD) direction and 1.2% in the transverse (TD) direction. Further, the oxygen permeability at 25 ° C. and 50% relative humidity was 15 ml / m ² · day · MPa, and the outgassing permeability was less than 0.5% by weight.
The evaluation results of mold releasability, mold, mold followability, and mold contamination are shown in Table 1. The release film exhibits a good releasability such that the release film naturally peels off simultaneously with the opening of the mold, and neither the release film nor the semiconductor package has any wrinkles, that is, the wrinkles are sufficiently suppressed, and the resin package chipped in the semiconductor package Showed no good mold followability. Also, no mold contamination was observed. That is, the process release film of Example 1 is excellent in the releasability, the suppression of wrinkles, and the mold followability, and the process release film capable of effectively suppressing the contamination of the mold. Met.

Example 2
An OPP (biaxially stretched polypropylene) film B2 (film thickness 20 μm) laminated with an organic gas barrier layer C containing polyvinyl alcohol instead of the biaxially stretched PET (polyethylene terephthalate) film B1 laminated with the inorganic gas barrier layer C Using a gas barrier film B2 (Mitsui Chemicals Tosoh Co., Ltd. product name: A-OP AG) having a polyvinyl alcohol copolymer gas barrier layer C formed on one side of the film, a corona is formed on the other side of the organic gas barrier layer C A release film for a process was produced in the same manner as in Example 1 except that the treatment was performed, and sealing and release were performed to evaluate the characteristics. The thermal dimensional change of the film B2 from 23 ° C. to 120 ° C. was 0.2% in the longitudinal (MD) direction and -0.3% in the transverse (TD) direction. The melting point of the OPP film B2 was 161 ° C., and the heat of crystal fusion was 93 J / g.
The thermal dimensional change from 23 ° C. to 120 ° C. of the produced process release film was 2.4% in the longitudinal (MD) direction and 0.4% in the transverse (TD) direction. In addition, the oxygen permeability at 25 ° C. and 50% relative humidity was 10 ml / m ² · day · MPa, and the outgassing permeability was less than 0.5% by weight.
The evaluation results of mold releasability, mold, mold followability, and mold contamination are shown in Table 1. The release film exhibits a good releasability such that the release film naturally peels off simultaneously with the opening of the mold, and neither the release film nor the semiconductor package has any wrinkles, that is, the wrinkles are sufficiently suppressed, and the resin package chipped in the semiconductor package Showed no good mold followability. Also, no mold contamination was observed. That is, the process release film of Example 2 is excellent in the releasability, the suppression of wrinkles, and the mold followability, and the process release film capable of effectively suppressing the contamination of the mold. Met.

[Example 3]
Gas barrier film B3 (Mitsui Chemicals Tosoh Co., Ltd. product name: V-OP OLE) (melting point) in which a polyvinylidene chloride copolymer is formed on one side of a 20 μm thick biaxially oriented polypropylene film instead of B2 as the heat resistant resin layer B A release film for a process was prepared, sealed and released in the same manner as in Example 2 except that 160 ° C. and heat of crystal fusion: 91 J / g were used, and the characteristics were evaluated. The thermal dimensional change from 23 ° C. to 120 ° C. of the film B3 was 0.4% in the longitudinal (MD) direction and 0.7% in the transverse (TD) direction. The melting point of the OPP film B2 was 160 ° C., and the heat of crystal fusion was 91 J / g.
The thermal dimensional change from 23 ° C. to 120 ° C. of the produced process release film was 2.6% in the longitudinal (MD) direction and 0.7% in the transverse (TD) direction. In addition, the oxygen permeability at 25 ° C. and 50% relative humidity was 50 ml / m ² · day · MPa, and the outgassing permeability was less than 0.5% by weight.
The evaluation results of mold releasability, mold, mold followability, and mold contamination are shown in Table 1. The release film exhibits a good releasability such that the release film naturally peels off simultaneously with the opening of the mold, and neither the release film nor the semiconductor package has any wrinkles, that is, the wrinkles are sufficiently suppressed, and the resin package chipped in the semiconductor package Showed no good mold followability. Also, no mold contamination was observed. That is, the process release film of Example 3 is excellent in the releasability, the suppression of wrinkles, and the mold followability, and the process release film capable of effectively suppressing the contamination of the mold. Met.
Comparative Example 1
OPP (biaxially oriented polypropylene) film B4 (film thickness 20 μm) biaxially oriented polypropylene film (Mitsui Chemicals Higashi Cello Co., Ltd.) having no gas barrier layer in place of biaxially oriented PET (polyethylene terephthalate) film B1 laminated with an inorganic gas barrier layer A release film for a process was produced in the same manner as in Example 1 except that company-made product name: U-2) was used, and sealing and demolding were performed to evaluate characteristics. The thermal dimensional change from 23 ° C. to 120 ° C. of the OPP film B4 was 0.3% in the longitudinal (MD) direction and -0.4% in the transverse (TD) direction. The melting point of the OPP film B4 was 161 ° C., and the heat of crystal fusion was 92 J / g.
The thermal dimensional change from 23 ° C. to 120 ° C. of the produced process release film was 2.1% in the longitudinal (MD) direction and 1.3% in the transverse (TD) direction. The oxygen permeability at 25 ° C. and 50% relative humidity was 15,000 ml / m ² · day · MPa, and the outgassing permeability was 1.3% by weight.
The evaluation results of mold releasability, mold, mold followability, and mold contamination are shown in Table 1. The release film exhibits a good releasability such that the release film naturally peels off simultaneously with the opening of the mold, and neither the release film nor the semiconductor package has any wrinkles, that is, the wrinkles are sufficiently suppressed, and the resin package chipped in the semiconductor package There was no good mold followability, but there was contamination of the mold. That is, although the mold release film for processing of Comparative Example 1 was good in the mold releasability, the suppression of wrinkles, and the mold followability, the contamination of the mold could not be effectively suppressed.

Comparative Example 2
No biaxially oriented PET (polyethylene terephthalate) film B1 and a film A2 (Mitsui Chemical Co., Ltd. 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022)) with a thickness of 50 μm A film obtained by forming a stretched film (melting point: 229 ° C., heat of crystal fusion: 21.7 J / g) alone is used as a release film for process, and sealing and release are carried out in the same manner as in Example 1. Conducted and evaluated the characteristics. The thermal dimensional change of the unstretched 4-methyl-1-pentene copolymer resin film A2 at 23 ° C. to 120 ° C. is 7.2% in the longitudinal (MD) direction and 3.% in the transverse (TD) direction. It was 6%. The oxygen permeability at 25 ° C. and 50% relative humidity was 300,000 ml / m ² · day · MPa, and the outgassing permeability was 30% by weight.
The evaluation results of mold releasability, mold, mold followability, and mold contamination are shown in Table 1. Although the mold release film showed a good mold release property that peels off naturally simultaneously with the opening of the mold and showed a good mold followability with no resin chipping in the semiconductor package, the mold release film as well as the semiconductor package There were also many wrinkles, and the wrinkles could not be suppressed sufficiently. Also, the mold was contaminated. That is, although the mold release film for processing of Comparative Example 2 was good in the mold releasability and the mold followability, the contamination of the crucible and the mold could not be effectively suppressed.
Comparative Example 3
Non-stretched polypropylene film B5 (a non-stretched polypropylene film with a film thickness of 20 μm (product name made by Mitsui Chemicals Tosoh Co., Ltd., product name) in which an inorganic gas barrier layer is laminated instead of a biaxially stretched PET (polyethylene terephthalate) film B1 laminated with an inorganic gas barrier layer A release film for processing in the same manner as in Example 1 except that a corona treatment is applied to both surfaces of S)) and a gas barrier film having a 10 nm thick aluminum oxide vapor deposited film (ALO film) applied to one surface thereof. Were prepared, sealed, and demolded to evaluate the characteristics. The thermal dimensional change from 23 ° C. to 120 ° C. of the non-oriented polypropylene film B5 in which the inorganic gas barrier layer is laminated is 5.7% in the longitudinal (MD) direction and 6.2% in the transverse (TD) direction. The Further, the melting point of the non-oriented polypropylene film B5 was 162 ° C., and the heat of crystal fusion was 114 J / g.
The thermal dimensional change from 23 ° C. to 120 ° C. of the produced process release film was 6.8% in the longitudinal (MD) direction and 7.2% in the transverse (TD) direction. In addition, the oxygen permeability at 25 ° C. and 50% relative humidity was 30 ml / m ² · day · MPa, and the outgassing permeability was less than 0.5% by weight.
The evaluation results of mold releasability, mold, mold followability, and mold contamination are shown in Table 1. Although the mold releasability was good, the occurrence of wrinkles could not be effectively suppressed, and the evaluation of mold contamination was evaluated as x. As a result of the gas barrier property lowering at the place where the wrinkles were generated in the film, it is presumed that the outgassing permeability becomes large and the dirt becomes apparent.

The process release film of the present invention has high level of releasability, wrinkle suppression, and mold following ability which can not be realized by the prior art, and can effectively suppress the contamination of the mold. By using it, molded articles obtained by resin-sealing semiconductor chips etc. can be easily released, and molded articles free from appearance defects such as wrinkles and chips can be produced at high productivity and at relatively low cost. It brings about a technical effect having a practically high value that it can be manufactured, and has high availability in each field of industry including the semiconductor process industry.
In addition, the mold release film of the present invention is not limited to semiconductor packages, but can be used for molding of various molds in fiber reinforced plastic molding processes, plastic lens molding processes, etc. It also has high availability in each sector of the industry that

1, 1-2, 1-3: mold release film 2: upper mold 3: suction port 4: sealing resin 4-2: semiconductor package 5: lower mold 6: semiconductor chip 7: substrate 8: molding mold 10, 20, 30, 40, 22: Release film 12: Heat-resistant resin layer B
14: Adhesive layer 16, 16A: Release layer A
16B: Release Layer A '
17: Gas barrier layer C
24, 26: Roll 28: Mold 30: Upper mold 32: Lower mold 34: Semiconductor chip 34A: Substrate 36: Sealing resin 40, 44: Semiconductor package 51: Al plate 52, 65: Release film 53: SUS Frame 54, 66: Sealing resin 61: Vial 1
62: vial 2
63: Cap 64: rubber stopper

Claims (17)

A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less,
According to JIS K 7126 of the laminated film, temperature 20 ° C., humidity 50% R.H. H. The mold release film for processes whose oxygen permeability measured on condition of is 1000 ml / m < ² > * day * MPa or less. A process release film which is a laminated film including a release layer A and a heat-resistant resin layer B,
The contact angle of the release layer A to water is 90 ° to 130 °,
The thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the laminated film is 3% or less,
The release film for the above process wherein the outgassing permeability measured according to the following procedures (1) to (3) of the laminated film is 1.0% by weight or less:
(1) Place 10 mg of epoxy sealing resin composition in vial 1, close the container with a cap and a rubber stopper, heat at 120 ° C for 30 minutes, and carry out GC-MS measurement by static head space method. Measure outgassing volume 1 during 1;
(2) Put 10 mg of sealing resin in vial 1 and cover the opening of vial 1 with a mold release film covered and sealed. The vial 2 is prepared, and the vial 1 is stored in the vial 2, sealed with a cap and a rubber stopper, heated at 120 ° C. for 30 minutes, and subjected to GC-MS measurement by a static head space method, Measure the amount of outgassing 2 in the vial 2 which has permeated the process release film;
(3) The outgassing permeability of the process release film is calculated according to the following (equation 1).
Permeability of outgassing = Outgas amount 2 / Outgas amount 1 x 100 (% by weight) (Equation 1)   The sum of the thermal dimensional change 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 of the laminated film is 6% or less. The process release film as described in 1 or 2.   The process release film according to any one of claims 1 to 3, wherein a thermal dimensional change rate from 23 ° C to 120 ° C in a transverse (TD) direction of the heat-resistant resin layer B is 3% or less.   The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the lateral (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer B is 6% or less The process release film according to claim 4.   The release layer A according to any one of claims 1 to 5, wherein the release layer A contains a resin selected from the group consisting of a fluorocarbon resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process.   The process release film according to any one of claims 1 to 6, wherein a gas barrier layer C is laminated on the heat-resistant resin layer B.   The process release film according to claim 7, wherein the gas barrier layer C is an inorganic layer or an organic layer.   The process release film according to claim 7 or 8, wherein a protective resin layer D which is an organic coating is laminated on the gas barrier layer C.   10. The heat of crystal fusion in the first temperature raising step measured by differential scanning calorimetry (DSC) according to JIS K 7221 of the heat-resistant resin layer B is 15 J / g or more and 60 J / g or less. The release film for a process according to one aspect. The laminated film further has a release layer A ′, and includes the release layer A, the heat-resistant resin layer B, and the release layer A ′ in this order,
The process release film according to any one of claims 1 to 10, wherein the contact angle of the release layer A 'to water is 90 ° to 130 °.   12. The method according to claim 11, wherein at least one of the release layer A and the release layer A ′ contains a resin selected from the group consisting of a fluorocarbon resin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. The release film for process described in.   The process release film according to any one of claims 1 to 12, which is used in a thermosetting resin sealing process.   The process release film according to any one of claims 1 to 13, which is used in a semiconductor encapsulation process.   The process release film according to any one of claims 1 to 12, which is used in a fiber reinforced plastic molding process or a plastic lens molding process. A method of manufacturing a resin-sealed semiconductor, comprising
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die;
Placing the mold release film according to any one of claims 1 to 14 on the inner surface of the molding die such that the mold release layer A faces the semiconductor device;
Injecting and molding a sealing resin between the semiconductor device and the process release film after clamping the molding die;
The manufacturing method of the said resin-sealed semiconductor which has. A method of manufacturing a resin-sealed semiconductor, comprising
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die;
Arranging the release film for process according to claim 11 or 12 on the inner surface of the molding die such that the release layer A ′ faces the semiconductor device;
Injecting and molding a sealing resin between the semiconductor device and the process release film after clamping the molding die;
The manufacturing method of the said resin-sealed semiconductor which has.