WO2013094752A1

WO2013094752A1 - Mold release film

Info

Publication number: WO2013094752A1
Application number: PCT/JP2012/083337
Authority: WO
Inventors: 洋和小森; 達也樋口; 政二小森; 辰也村上; 勝史奥村; 剛志稲葉
Original assignee: ダイキン工業株式会社
Priority date: 2011-12-22
Filing date: 2012-12-21
Publication date: 2013-06-27
Also published as: KR20140106691A; JP5752106B2; JP2013147026A; CN103917347A; TW201341145A

Abstract

Provided is a mold release film, which does not have uneven thickness resulting from inhomogeneous stretching during drawing when molded with a die. The mold release film obtained from a fluorine-containing resin is characterized in that for the mold release film, the difference between the stress in the longitudinal direction of the film and the stress in the transverse direction is 1.80 MPa or less, the stress being a value obtained with a method conforming to ASTM D1708-02a under the conditions of a 120°C atmospheric temperature and a 100 mm/min pulling speed.

Description

Release film

The present invention relates to a release film.

The mold release film is sandwiched between the mold and the resin in order to release the resin (sealing material) from the mold after molding in the molding process of the resin using a molding apparatus. Used to release the molded resin and the mold.

However, when a general-purpose PET film or a highly heat-resistant polyimide film is used as the release film, the film elongation is small and the followability to the mold becomes insufficient, and the film is likely to be wrinkled. . In addition, the wrinkles of the generated film are transferred to the mold resin, the surface of the product is roughened, and the yield is reduced.

For the purpose of improving productivity and yield, a mold release film for resin molding made of a thermoplastic tetrafluoroethylene copolymer has been proposed (see Patent Document 1). Further, a release film for sealing a semiconductor chip is proposed, which is a laminated film in which a film made of a fluororesin is laminated on at least one surface of a base film made of a stretched polyester resin film (patent) Reference 2).

In addition, a release laminated film having a layer made of a modified polyolefin resin and a layer made of an adhesive fluororesin laminated on at least one surface of the layer and interposed between a press plate of a press machine and a printed substrate. Has been proposed (see Patent Document 3). This release film is a release film for laminated press molding that presses a thermosetting adhesive at the time of laminate molding of a wiring board at a high temperature and high pressure to mold the laminated product without deviation, so the press pressure is uniform. In order to prevent the prepreg from flowing out, it is necessary to have cushioning properties, and the film thickness is about 0.1 mm.

Also, as a release film having excellent conformity and strength to the shape of the mold and having low gas permeability, there are three layers: a fluorine-containing polymer layer, a fluorine-free polymer layer, and a fluorine-containing polymer layer. A release film having a specific thickness and a fluorine-containing polymer having a specific adhesive functional group has been proposed (see Patent Document 4).

JP 2001-310336 A JP 2006-49850 A International Publication No. 2005/115751 Pamphlet JP 2009-285990 A

However, such a conventional release film has improved followability to the shape of the mold, but when the film is stretched at the time of molding, the film stretches unevenly and thickness unevenness occurs. As a result, the thickness unevenness of the film is transferred to the molded product, the surface is roughened, a molded product having a desired surface shape cannot be obtained, and the yield is reduced.

An object of the present invention is to provide a release film in which thickness unevenness due to non-uniform elongation does not occur when stretched in molding by a mold in view of the above-described present situation.

The present invention is a release film made of a fluorine-containing resin, and the release film has a difference between the stress in the longitudinal direction of the film and the stress in the width direction of 1.80 MPa or less, and the stress is measured according to ASTM D1708. A release film characterized in that it is a value obtained by measurement under the conditions of an atmospheric temperature of 120 ° C. and a tensile speed of 100 mm / min by a method based on −02a.
The release film preferably has a stretch ratio in the longitudinal direction and the width direction of the film of 0.50% or less.
The fluororesin is at least one selected from the group consisting of a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and an ethylene-tetrafluoroethylene copolymer. Preferably it is a seed.
The fluororesin is preferably an ethylene-tetrafluoroethylene copolymer.
The release film preferably has a tetrafluoroethylene unit content of 50 mol% or more based on all monomer units constituting the ethylene-tetrafluoroethylene copolymer.
The release film is preferably used for molding a light emitting diode sealing material.

In the release film, when the difference in stress between the longitudinal direction and the width direction is below a certain level, the present inventors prevent uneven thickness of the film from occurring when the film is molded with a mold. As a result, it has been found that a molded product having a desired surface shape can be obtained, and the present invention has been completed.

Since the release film of the present invention is uniformly stretched during molding of the resin with a mold and is less likely to cause unevenness in thickness, it is possible to suitably obtain a molded product of a resin having a desired surface shape without roughening. it can.

It is the figure which showed the method of prescribing | regulating the value of stress from a stress-strain curve.

The present invention is a release film made of a fluorine-containing resin, and the release film has a difference between the stress in the longitudinal direction of the film and the stress in the width direction of 1.80 MPa or less, and the stress is measured according to ASTM D1708. A release film characterized in that it is a value obtained under the conditions of an atmospheric temperature of 120 ° C. and a tensile speed of 100 mm / min by a method based on −02a.
For this reason, the release film of the present invention is uniformly stretched when stretched by molding with a mold and does not cause unevenness in thickness.

In the release film of the present invention, the difference between the stress in the longitudinal direction (also referred to as “MD”) and the stress in the width direction (also referred to as “TD”) is 1.80 MPa or less.
If the difference in stress exceeds 1.80 MPa, there is a risk of uneven thickness when stretched in molding with a mold or the like.
The difference in stress is preferably 1.20 MPa or less, more preferably 0.85 MPa or less, and even more preferably 0.70 MPa or less, because the surface of the molded product obtained by molding at high temperature is less likely to be rough. 0.50 MPa or less is still more preferred, 0.30 MPa or less is particularly preferred, and 0.10 MPa or less is most preferred.

The stress in the longitudinal direction and the stress in the width direction are values obtained by measurement under the conditions of an atmospheric temperature of 120 ° C. and a tensile speed of 100 mm / min, respectively, in accordance with ASTM D1708-02a. Specifically, as shown in FIG. 1, a stress-strain curve (SS curve) is prepared by the above-described method, and the X-axis strain (elongation) of the curve is 60% (a). Is the value (b) of the stress on the Y-axis. The stress difference is the absolute value of the difference between these values.
The stress in the longitudinal direction and the stress in the width direction are preferably 7.3 MPa or less, more preferably 6.0 MPa or less, and 3.0 MPa or less in terms of the ability to follow the mold during evacuation. More preferably.

The release film of the present invention also has the above-described stress-strain in the longitudinal and width directions in that the surface of the molded product does not become rough even when the release film is stretched using a mold having a more complicated shape. In the curve, the Y-axis stress value when the longitudinal X-axis strain (elongation) is 120%, and the Y-axis stress value when the width-direction X-axis strain (elongation) is 120%. The difference is preferably 1.80 MPa or less.
In the stress-strain curves in the longitudinal direction and the width direction, the value of the Y-axis stress when the X-axis strain (elongation) is 180% in the longitudinal direction and the X-axis strain (elongation) in the width direction. ) The difference from the Y-axis stress value at 180% is preferably 1.80 MPa or less.

In the release film of the present invention, the stretch ratio in the longitudinal direction (MD) and the width direction (TD) of the film is preferably 0.50% or less, and more preferably 0.30% or less. If the expansion / contraction ratio exceeds 0.50%, the surface of the molded body may be roughened.
The expansion / contraction rate is more preferably 0.50 to −1.60%.
The said expansion / contraction rate is a value obtained by the method (115 degreeC x 10 minutes) based on JISK7133.

The release film of the present invention is made of a fluorine-containing resin.
The fluorine-containing resin is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing ethylenic monomer, and is a polymer having melt processability.

The fluorine-containing ethylenic monomer is an olefinically unsaturated monomer having at least one fluorine atom. Specific examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene [TFE], vinylidene fluoride [VDF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene. Formula (1):
CH ₂ = CX ¹ (CF ₂ ) _n X ² (1)
(Wherein, X ¹ is H or F, X ² is H, F or Cl, and n is an integer of 1 to 10), and perfluoro (alkyl vinyl ether) Can be mentioned.

Examples of the perfluoro (alkyl vinyl ether) [PAVE] include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro ( Butyl vinyl ether) and the like.

The fluorine-containing resin may be a copolymer having the fluorine-containing ethylenic monomer unit and an ethylenic monomer unit having no fluorine.

The ethylenic monomer having no fluorine is preferably an ethylenic monomer having 5 or less carbon atoms from the viewpoint of good heat resistance and chemical resistance, specifically, ethylene, propylene, 1-butene. 2-butene, vinyl chloride, vinylidene chloride and the like.

Examples of the fluororesin include polytetrafluoroethylene [PTFE], polychlorotrifluoroethylene [PCTFE], ethylene [Et] -TFE copolymer [ETFE], Et-chlorotrifluoroethylene [CTFE] copolymer, It should be at least one selected from the group consisting of CTFE-TFE copolymer, TFE-HFP copolymer [FEP], TFE-PAVE copolymer [PFA], and polyvinylidene fluoride [PVdF]. preferable.

The fluorine-containing resin is more preferably at least one fluorine-containing copolymer selected from the group consisting of PFA, FEP, and ETFE, and more preferably ETFE.

PFA is not particularly limited, but a copolymer having a molar ratio of TFE units to PAVE units (TFE units / PAVE units) of 70 to 99/30 to 1 is preferable. A more preferred molar ratio is 80 to 98.5 / 20 to 1.5. When there are too few TFE units, there exists a tendency for a mechanical physical property to fall, and when too much, melting | fusing point becomes high too much and there exists a tendency for a moldability to fall.

PFA has a monomer unit derived from a monomer copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol%, and a total of 90 to 99.9 mol% of TFE units and PAVE units. A polymer is also preferred.
Monomers copolymerizable with TFE and PAVE include HFP, CZ ¹ Z ² = CZ ³ (CF ₂ ) _n Z ⁴ (wherein Z ¹ , Z ^2, and Z ³ are the same or different, hydrogen An atom or a fluorine atom, Z ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10), and CF ₂ ═CF—OCH Examples include alkyl perfluorovinyl ether derivatives represented by _2- Rf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms).

FEP is not particularly limited, but a copolymer having a molar ratio of TFE units to HFP units (TFE units / HFP units) of 70 to 99/30 to 1 is preferable. A more preferred molar ratio is 80 to 97/20 to 3. When there are too few TFE units, there exists a tendency for a mechanical physical property to fall, and when too much, melting | fusing point becomes high too much and there exists a tendency for a moldability to fall.

FEP has a monomer unit derived from a monomer copolymerizable with TFE and HFP in an amount of 0.1 to 10 mol%, and a total of 90 to 99.9 mol% of TFE units and HFP units. A polymer is also preferred. Examples of the monomer copolymerizable with TFE and HFP include PAVE and alkyl perfluorovinyl ether derivatives.

ETFE is preferably a copolymer having a molar ratio of TFE units to ethylene units (TFE units / ethylene units) of 20 to 90/80 to 10. A more preferred molar ratio is 37 to 85/63 to 15, and a still more preferred molar ratio is 38 to 80/62 to 20.

ETFE may be a copolymer composed of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene.
As a monomer copolymerizable with TFE and ethylene, the following formulas CH ₂ = CX ³ Rf ² , CF ₂ = CFRf ² , CF ₂ = CFORf ² , CH ₂ = C (Rf ² ) ₂
(Wherein, X ³ represents a hydrogen atom or a fluorine atom, and Rf ² represents a fluoroalkyl group which may contain an ether-bonded oxygen atom), among which CF ₂ = CFRf ² , CF ₂ = CFORf ² and CH ₂ = CX ³ It is preferably at least one selected from the group consisting of fluorine-containing vinyl monomers represented by Rf ² , HFP, CF ₂ = CF-ORf ³ (In the formula, Rf ³ represents a perfluoroalkyl group having 1 to 5 carbon atoms) and perfluoro (alkyl vinyl ether) [PAVE] represented by the formula (1) and Rf ⁴ is a fluoroalkyl group having 1 to 8 carbon atoms. ₂ = At least one selected from the group consisting of fluorine-containing vinyl monomers represented by CX ³ Rf ⁴ is more preferable.
Examples of the fluorine-containing vinyl monomer include CH ₂ ═CH—C ₄ F ₉ , CH ₂ ═CF—CF ₂ —CF ₂ —CF ₂ H, CH ₂ ═CH—C ₆ F _{13, and the} like.
The monomer copolymerizable with TFE and ethylene may be an aliphatic unsaturated carboxylic acid such as itaconic acid or itaconic anhydride.
The monomer copolymerizable with TFE and ethylene is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, particularly preferably from 0.2 to 4 mol%, based on the fluoropolymer. preferable.

ETFE is preferable in that the content of TFE units with respect to all monomer units constituting ETFE is 50 mol% or more, more preferably 55 mol% or more, in terms of good releasability. More preferably, it is 65 mol% or more.

The content of each monomer in the copolymer described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The fluororesin preferably has a melt flow rate (MFR) of 60 g / 10 min or less. If it exceeds 60 g / 10 min, when the resin (sealing material) is removed from the mold after molding, the releasability between the resin and the release film may be reduced. The MFR is more preferably 45 g / 10 min or less, further preferably 30 g / 10 min or less, particularly preferably less than 25 g / 10, and most preferably 18 g / 10 min or less.
The MFR is preferably 1.5 g / 10 min or more, more preferably 4 g / 10 min or more, and even more preferably 10 g / 10 min or more in that the surface of the molded product does not become rough even at high stretch. 20 g / 10 min or more is particularly preferable.
The MFR is a value obtained by measurement by a method according to ASTM D 3159.

The fluororesin preferably has a melting point of 180 to 270 ° C.
The melting point of the fluororesin is preferably 230 to 270 ° C. from the viewpoint of heat resistance, more preferably 200 to 230 ° C. from the viewpoint of low elastic modulus, and 190 to 230 ° C. More preferably it is.
The melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].

The release film of the present invention may contain other components as necessary within a range not impairing the effects of the present invention. Examples of other components include various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide, or carbon, pigments, ultraviolet absorbers, other optional additives, other fluorine-containing polymers and thermoplastics. Examples thereof include resins such as resins and thermosetting resins, and synthetic rubbers. By blending these, it is possible to improve mechanical properties, improve weather resistance, impart design properties, prevent static electricity, improve moldability, and the like.

The release film comprising the fluororesin of the present invention may be a release film comprising a single layer or a release film having a laminated structure. The release film having a laminated structure may be composed of two or more layers made of a fluorine-containing resin, or a layer made of one or more fluorine-containing resins and one or more resins other than the fluorine-containing resin. It may consist of a layer consisting of The release film of the present invention is preferably composed of a single layer.

The release film of the present invention preferably has a thickness of 15 to 100 μm. If it is less than 15 μm, the strength is not sufficient, and the release film may be loosened or broken during stretching. If it exceeds 100 μm, the followability to the mold is lowered, and there is a risk that wrinkles are likely to occur in the molded product.
The thickness is a value obtained according to the JIS K 7130 A method.

The release film of the present invention preferably has an elastic modulus at 25 ° C. of 350 to 600 MPa in the longitudinal direction (MD) and 350 to 550 MPa in the width direction (TD).
The release film of the present invention preferably has an elastic modulus at 120 ° C. of 20 to 70 MPa in the longitudinal direction (MD) and 20 to 75 MPa in the width direction (TD).
The above elastic modulus is a value obtained by measurement according to ASTM D-1708.

The release film of the present invention can be produced by molding the fluorine-containing resin alone or a mixture of the fluorine-containing resin and the other components into a film shape.
Examples of the mixing method of the fluororesin and the other components include a melt kneading method.
Examples of the method for forming the film include a melt extrusion method, an inflation method, and a T-die method. The T-die method is preferable in terms of high film thickness accuracy.

In the T-die method, the molten resin is stretched in the extrusion direction (MD direction) when being formed into a film while being wound with a roll. When the release film of the present invention is produced by such a T-die method, the film is formed by reducing the orientation of the formed film as much as possible by narrowing the lip width of the die or shortening the air gap. It is preferable.
For example, when the lip width of the die is narrowed, the lip width is preferably less than 1.5 mm.
When the air gap is shortened, the air gap is preferably 145 mm or less.
The air gap refers to the distance from the die outlet until the molten resin contacts the cooling roll.

The release film of the present invention can be suitably applied as a release film for resin molding that is used when a molded product is produced by molding a resin. A molded product produced using the release film of the present invention has little surface roughness and a high yield.
In general, the molding of the semiconductor sealing material is performed at a molding temperature of 170 to 180 ° C., and the molding of the light emitting diode sealing material is performed at a molding temperature of 100 to 150 ° C. Since the release film of the present invention hardly causes thickness unevenness even at high temperatures, it is suitably used in the molding of a semiconductor sealing material or a light emitting diode sealing material performed in the above-described molding temperature range.
Specifically, the release film of the present invention is sandwiched between a sealing material and a mold of a molding machine in the molding of a semiconductor sealing material or a light emitting diode sealing material. It can apply especially suitably as a mold release film for resin mold formation for releasing.
In particular, the release film of the present invention is less likely to cause thickness unevenness even when a mold having a plurality of bowl-shaped depressions provided at equal intervals is pressed. For this reason, it is especially preferable that the release film of the present invention is used in molding of a light emitting diode sealing material.

EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited only to these Examples.

Example 1
Using ETFE (1) (neoflon ETFE EP-610 (trade name), melting point 223 ° C., MFR 30.0 g / 10 min, manufactured by Daikin Industries, Ltd.), by using a T-die method using a T-die, The mold was extruded and melt-molded at a die temperature of 305 ° C. under a condition in which the lip width was narrowed (0.8 mm) and the orientation of the resin in the extrusion direction was suppressed. MD: -1.15%, TD: 0.25%).

(Example 2)
In Example 1, ETFE (2) (neoflon ETFE EP-543 (trade name), melting point 258 ° C., MFR 6.0 g / 10 min, manufactured by Daikin Industries, Ltd.) was used instead of ETFE (1). A release film (thickness 50 μm, stretch rate (115 ° C., 10 minutes) MD: −0.65%, TD: −0.66%) was obtained in the same manner as in Example 1 except that the temperature was 340 ° C. It was.

(Example 3)
In Example 1, ETFE (3) (neoflon ETFE EP-546 (trade name), melting point 253 ° C., MFR 6.0 g / 10 min, manufactured by Daikin Industries, Ltd.) was used instead of ETFE (1). A release film (thickness 50 μm, stretch rate (115 ° C., 10 minutes) MD: −0.82%, TD: 0.29%) was obtained in the same manner as in Example 1 except that the temperature was 340 ° C. .

(Example 4)
In Example 1, FEP (neoflon FEP NP-120 (trade name), melting point 265 ° C., MFR 7.0 g / 10 min, manufactured by Daikin Industries, Ltd.) was used instead of ETFE (1), and the die temperature was 360. A release film (thickness 50 μm, stretch rate (115 ° C., 10 minutes) MD: 0.21%, TD: −1.52%) was obtained in the same manner as in Example 1 except that the temperature was changed to 0 ° C.

(Comparative Example 1)
A release film (thickness: 50 μm, stretch rate (115 ° C., 10 minutes) MD: −4.64 in the same manner as in Example 1, except that the lip width was widened (1.5 mm) in Example 3. %, TD: 0.20%).

About the obtained release film, the following items were evaluated. The obtained results are shown in Table 1.
<Measurement of stress in longitudinal direction (MD) and width direction (TD)>
Measurements were made according to ASTM D1708-02a, except that the atmospheric temperature was 120 ° C. and the tensile speed was 100 mm / min, and respective stress-strain curves (SS curves) in the longitudinal direction and the width direction were obtained. Then, the value of each stress-strain curve obtained when the strain (elongation) was 60% was taken as the value of each stress.
Further, in the obtained stress-strain curve, the difference in stress value between the longitudinal direction and the width direction when the strain was 120% and 180% was calculated.

<Breaking strength and breaking elongation>
The breaking strength and breaking elongation in the longitudinal direction and the width direction of the obtained release film were measured using Autograph AG-1KNIS (manufactured by Shimadzu Corporation) under the following conditions.
As for the tension conditions at 28 ° C., the sample shape was a strip shape (10 mm width), and the tensile speed was 500 mm / min (based on JIS K 7127).
The tensile conditions at 120 ° C. were that the sample shape was a micro dumbbell (thickness 50 μm) and the tensile speed was 100 mm / min (according to ASTM D1708-02a).

<Mold moldability>
Using the release film obtained above, molding was performed under the following conditions, and the obtained molded product was evaluated according to the following criteria.
(Molding condition)
Release mold (A4 size: 30cm x 20cm wide sheet film) on a mold (mold formed with bowl-shaped depressions with a diameter of 2.6mm) at a constant temperature (115 ° C) by resin molding (The roll film may be set in a roll-to-roll manner), and vacuum suction was performed to cause the release film to follow the mold. An uncured silicone resin for sealing (trade name OE-6370HF (manufactured by Toray Dow Corning)) is flowed there and held for 120 to 300 seconds to cure the resin. Was demolded, and the release film was peeled off.
(Evaluation methods)
The surface of the obtained molded product was observed using a microscope (DIGITAL MICROSCOPE VHX-900, manufactured by Keyence Corporation, magnification: 25 to 100 times) and evaluated according to the following criteria.
(Evaluation criteria)
○: No roughness was observed on the surface.
X: Roughness was observed on the surface.

From Table 1, it can be seen that, by using the release film of the example, a resin molded body having a good surface state can be obtained in the resin molding process using the molding apparatus.

The release film of the present invention can be suitably applied as a mold release film for releasing a resin from a mold during molding.

Claims

A release film made of a fluorine-containing resin,
In the release film, the difference between the stress in the longitudinal direction and the stress in the width direction of the film is 1.80 MPa or less, and the stress is a method according to ASTM D1708-02a, and the ambient temperature is 120 ° C. and the tensile speed is 100 mm. A release film characterized by having a value obtained by measurement under the conditions of / min.
The release film according to claim 1, wherein the stretch ratio in the longitudinal direction and the width direction of the film is 0.50% or less.
The fluorine-containing resin is at least one selected from the group consisting of a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and an ethylene-tetrafluoroethylene copolymer. The release film according to claim 1 or 2.
4. The release film according to claim 1, wherein the fluororesin is an ethylene-tetrafluoroethylene copolymer.
The release film according to claim 4, wherein the content of the tetrafluoroethylene unit with respect to all monomer units constituting the ethylene-tetrafluoroethylene copolymer is 50 mol% or more.
6. A release film according to claim 1, which is used for molding a light emitting diode sealing material.