JP2012066447A - Mold release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mold release film which is excellent in releasability from a mold and a molded article obtained by molding a mold resin, is excellent in followability to the mold, and exhibits heat-resistance and mechanical strength in an operating temperature around 180°C.SOLUTION: A base film is formed by applying ionizing radiation and cross-linking a film obtained by extruding a resin composition formed by mixing polyethylene-based resin of 25-400 pts.mass with ethylene-based copolymer rubber of 100 pts.mass. A fluoro-silicone compound layer obtained by coating a mold releasing composition containing a fluoro-silicone compound having a silyl group containing a hydrolyzable part in a molecule and drying it is formed on at least one surface of the base film.

Description

  The present invention relates to a release film used at the time of resin molding or at the time of manufacturing a printed wiring board or a flexible printed wiring board.

  For example, semiconductor devices such as transistors, ICs, LSIs, and ultra LSIs, and optical semiconductor devices such as LEDs, photoisolators, phototransistors, photodiodes, CCDs, and CMOSs, use an epoxy resin composition or a silicone resin composition as a sealing material. It is sealed by resin molding.

  A molding apparatus is used for sealing the above-described semiconductor element and optical semiconductor element, and a sealing material made of an epoxy resin composition or a silicone resin composition is injected into the mold as a molding resin and molded.

  As a method for releasing the mold from the molded product, for example, a method in which a release film is interposed between the mold and the mold resin has been put into practical use (see Patent Document 1). ). The mold release film is supplied Roll-to-Roll in the mold forming apparatus, enters the mold mold adjusted to the molding processing temperature, is sucked in vacuum and adheres to the mold mold, and then filled with mold resin. Is done. When the mold die is opened when the mold resin is cured after a certain time, the molded product is peeled off from the mold release film while the mold release film is sucked into the mold die. The release film includes, for example, a single layer made of a thermoplastic fluororesin tetrafluoroethylene-ethylene copolymer resin (ETFE resin) or a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP resin). A film is used (see Patent Document 2).

  However, such a mold release film is excellent in releasability from a mold or a molded product, but is hard and difficult to stretch, so for mold molds that are fine or complicated in shape, When the release film is adsorbed in a vacuum, it stretches without breaking along the shape of the mold, and also adheres to the fine parts of the mold, that is, the followability is insufficient. There arises a problem that the film is torn and the mold resin leaks to contaminate the mold and that the shape of the mold is not sufficiently transferred to the molded product.

  In order to solve such problems, conventionally, as a release film, a method of using a film made of a resin composition containing a crystalline aromatic polyester containing butylene terephthalate as a crystal component is known (patent document). 3).

JP-A-8-142105 JP 2001-310336 A JP 2007-224311 A

  However, as shown in Patent Document 3, when a film made of a crystalline aromatic polyester-containing resin composition containing butylene terephthalate is used as a release film, the shape is fine because it is soft and easily stretched. Although the followability is improved with respect to a complicated mold mold, a new problem arises that the mold mold or the molded product lacks releasability. For this reason, the film which consists of other than a thermoplastic fluororesin cannot actually be used suitably as a film for mold release in resin molding.

  The present invention has been made in view of the above, and is excellent in releasability from a molded product obtained by molding a mold or a molding resin, and has excellent followability to a mold, and further, 180 ° C. It aims at providing the film for mold release which also has the heat resistant strength (heat resistance and mechanical strength) in the use temperature before and behind.

  Such an object is achieved by the present inventions (1) to (24) below.

  (1) A film obtained by extrusion molding a resin composition obtained by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber is crosslinked by irradiating ionizing radiation. A fluorosilicone compound layer obtained by applying and drying a release composition containing a fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule is formed on at least one surface of the base film. A mold release film.

(2) The ethylene copolymer rubber contains 40 to 90% by mass of ethylene and 0.5 to 8.0% by mass of non-conjugated diene, and has a Mooney viscosity ML _{1 + 4} (125 ° C.) of 10 to 100. The release film as described in (1), which is characterized in that

  (3) Non-conjugated dienes are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4- One or more selected from the group consisting of hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, and dicyclopentadiene The release film as described in (2) above.

(4) The polyethylene-based resin has a linear low density having a density of 0.855 to 0.925 g / cm ³ and an MFR (190 ° C./2.16 kgf) of 0.5 to 10.0 g / 10 min. The release film as described in (1), which is polyethylene.

  (5) The resin composition further includes one or more selected from the group consisting of a lubricant, an antiblocking agent, a phenolic antioxidant, a phosphorus antioxidant, and an antistatic agent as an additive. The release film according to (1).

  (6) Irradiation with ionizing radiation is performed at a dose of 50 to 250 kGy using one selected from the group consisting of α rays, β rays, electron rays, neutron rays, X rays, and γ rays of cobalt 60 sources. The release film as set forth in (1), which is performed.

  (7) The release film according to (1), wherein the base film is a single layer film or a multilayer film having two or more layers.

  (8) The mold release composition is selected from the group consisting of an organic titanium compound, an organic zirconium compound and an organic silicon compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. The film for release according to any one of (1) to (7), which is a composition comprising one or more compounds in the range of 0.05 to 20 parts by mass.

  (9) The release composition is one or more selected from the group consisting of an organic titanium compound and an organic zirconium compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. The film for release according to any one of (1) to (8), which is a composition comprising a compound in a range of 0.05 to 20 parts by mass.

  (10) One or more selected from the group consisting of an organic titanium compound and an organic zirconium compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. (1) to (9), wherein the composition is a composition comprising 0.05 to 20 parts by mass of the compound and further containing an organosilicon compound in the range of 0.05 to 20 parts by mass. The film for mold release in any one of).

  (11) A film obtained by extruding a resin composition obtained by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber is crosslinked by irradiating ionizing radiation. A mold release composition comprising a fluorosilicone compound having a silyl group in the molecule, wherein the thickness of a single-layer base film or a multilayer base film of two or more layers is in the range of 5 to 500 μm and contains a hydrolyzable moiety The film for release according to any one of (1) to (10), wherein the thickness of the fluorosilicone compound layer obtained by coating and drying is in the range of 0.05 to 10 μm.

  (12) In the dynamic viscoelasticity measurement of the release film, the loss tangent tan δ at 180 ° C. measured under the conditions of a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 5 ° C./min is The release film according to any one of (1) to (11), wherein both in the longitudinal and lateral directions are in the range of 0.05 to 0.20.

  (13) A step of mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber, a step of obtaining a resin composition by extruding the resin composition, and a step of ionizing the film A step of obtaining a base film by irradiating with actinic radiation, and applying a release composition containing a fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule to at least one surface of the base film And a step of forming a fluorosilicone compound layer by drying, and a method for producing a mold release film.

(14) The ethylene-based copolymer rubber contains 40 to 90% by mass of ethylene and 0.5 to 8.0% by mass of non-conjugated diene, and has a Mooney viscosity ML _{1 + 4} (125 ° C.) of 10 to 100. (13) The method for producing a release film according to (13).

  (15) Non-conjugated dienes are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4- One or more selected from the group consisting of hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, and dicyclopentadiene (14) The manufacturing method of the film for mold release as described in (14) characterized by the above-mentioned.

(16) The polyethylene-based resin has a linear low density having a density of 0.855 to 0.925 g / cm ³ and an MFR (190 ° C./2.16 kgf) of 0.5 to 10.0 g / 10 min. It is polyethylene, The manufacturing method of the film for mold release as described in (13) characterized by the above-mentioned.

  (17) The resin composition further includes one or more selected from the group consisting of a lubricant, an antiblocking agent, a phenolic antioxidant, a phosphorus antioxidant, and an antistatic agent as an additive. The manufacturing method of the film for mold release as described in (13).

  (18) Irradiation with ionizing radiation is performed at a dose of 50 to 250 kGy using one selected from the group consisting of α rays, β rays, electron rays, neutron rays, X rays, and γ rays of cobalt 60 radiation sources. (13) The manufacturing method of the film for mold release as described in (13) characterized by performing.

  (19) The method for producing a release film as described in (13), wherein the base film comprises a single layer film or a multilayer film having two or more layers.

  (20) The mold release composition is selected from the group consisting of an organic titanium compound, an organic zirconium compound and an organic silicon compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. The method for producing a release film according to any one of (13) to (19), wherein the composition comprises one or more compounds in a range of 0.05 to 20 parts by mass.

  (21) The release composition is one or more selected from the group consisting of an organic titanium compound and an organic zirconium compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. The method for producing a release film according to any one of (13) to (20), which is a composition comprising a compound in a range of 0.05 to 20 parts by mass.

  (22) One or more selected from the group consisting of an organic titanium compound and an organic zirconium compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. (13) to (21), wherein the composition is a composition comprising 0.05 to 20 parts by mass of the compound and further containing an organosilicon compound in the range of 0.05 to 20 parts by mass. ). A method for producing a release film according to any one of the above.

  (23) A film obtained by extruding a resin composition obtained by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber is crosslinked by irradiating ionizing radiation. A mold release composition comprising a fluorosilicone compound having a silyl group in the molecule, wherein the thickness of a single-layer base film or a multilayer base film of two or more layers is in the range of 5 to 500 μm and contains a hydrolyzable moiety The method for producing a release film according to any one of (13) to (22), wherein the thickness of the fluorosilicone compound layer obtained by coating and drying is in the range of 0.05 to 10 μm.

  According to the mold release film of the present invention, it is excellent in releasability from a molded product obtained by molding a mold and a molding resin, has excellent followability to the mold, and has heat resistance. Can do.

It is sectional drawing which shows one Embodiment of the film for mold release of this invention. It is a figure which shows schematic structure of one Embodiment of the film manufacturing apparatus which manufactures the film for mold release of this invention. It is sectional drawing which shows the periphery of the material insertion hopper of the film manufacturing apparatus shown in FIG.

  As a result of various investigations to achieve the above object, the present inventors prepared a resin composition by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber. A fluorosilicone having a silyl group containing a hydrolyzable moiety in the molecule on at least one surface of a base film that has been extruded using an article and then cross-linked by irradiating ionized radiation to the extruded film By applying and drying a release composition containing a compound to form a fluorosilicone compound layer, the mold is excellent in releasability from a molded product obtained by molding a mold or a molding resin, and the mold It was determined that a release film having excellent conformability to the mold and having heat resistance strength can be obtained. Hereinafter, the extrusion molded film irradiated with ionizing radiation and crosslinked before applying the release material composition is referred to as a base film.

  Furthermore, as a result of the study, the release composition is selected from the group consisting of an organic titanium compound, an organic zirconium compound and an organic silicon compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. In order to complete the present invention, the present invention has been found to be more effective by making a composition containing one selected compound or two or more compounds in a total range of 0.05 to 20 parts by mass. It came.

  Examples of ethylene copolymer rubber include elastomers copolymerized with ethylene and α-olefins such as propylene, 1-butene and 1-pentene, or ethylene copolymer rubbers obtained by copolymerizing these with non-conjugated dienes. Can be given. Specifically, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-butene-nonconjugated diene copolymer rubber, ethylene -Propylene-1-butene copolymer rubber and the like. Among these, ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) is preferable from the viewpoint of versatility.

  Non-conjugated dienes in ethylene copolymer rubber include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl -1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene and the like.

The Mooney viscosity ML _{1 + 4} (125 ° C.) (ASTM D-1646) of the ethylene copolymer rubber is 10 to 100, preferably 15 to 75. In particular, when it is in the range of 15 to 75, it is possible to balance the elastic deformability of the release film and the processability of extrusion molding during production. The ethylene copolymer rubber has an ethylene content of 40 to 90% by weight, preferably 45 to 85% by weight. In particular, when it is in the range of 45 to 85% by weight, the compatibility with the polyethylene resin to be mixed and the elastic deformability of the release film can be balanced.

  The non-conjugated diene content of the ethylene copolymer rubber is suitably in the range of 0.5 to 8.0% by weight, preferably 4.0 to 8.0% by weight. In particular, if it is in the range of 4.0 to 8.0% by weight, the crosslinking point density is appropriate. Therefore, when crosslinked by irradiation with ionizing radiation, the mechanical strength of the release film at a high temperature around 180 ° C., that is, The heat resistance strength can be improved.

  The polyethylene resin is mixed for the purpose of imparting toughness and plastic deformability to the ethylene copolymer rubber having elastic deformability. This polyethylene resin is mixed in an amount of 25 to 400 parts by mass, preferably 30 to 400 parts by mass, and more preferably 50 to 400 parts by mass with respect to 100 parts by mass of the ethylene copolymer rubber.

  This is because when the amount is less than 25 parts by mass, the toughness of the polyethylene-based resin is insufficient, so that winding of the release film at the time of manufacture becomes unstable, and film formation stability cannot be obtained. This is because the processability of molding deteriorates. Further, the elastic deformation property of the copolymer rubber is too strong, the followability of the release film to the mold die is deteriorated, and the shape of the mold die is not transferred to the mold resin, resulting in molding failure. On the other hand, when it exceeds 400 parts by mass, the plastic deformation property of the polyethylene resin is too strong, and the release film is torn during use, and the heat resistance strength cannot be obtained.

  As the polyethylene resin, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene are used, and among these, linear low-density from the viewpoint of compatibility with ethylene copolymer rubber and mechanical strength. The use of polyethylene is preferred. Linear low density polyethylene is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms, and is a polyethylene polymerized using a Ziegler-Natta catalyst or a single-site catalyst. Polyethylene polymerized using a single-site catalyst is preferable in that the α-olefin distribution in the polymer becomes uniform. The α-olefin copolymerized with ethylene has 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.

The density of the linear low density polyethylene (JIS K 7112) is 0.855 to 0.925 g / cm ³ , preferably 0.875 to 0.925 g / cm ³ , and more preferably 0.895 to 0.925 g / cm ³ . cm ³ , more preferably 0.905 to 0.925 g / cm ³ is preferable. This is based on the reason that when the density is less than 0.855 g / cm ³ , the melting point of the linear low-density polyethylene is low, so that the release film melts at the time of use and the heat resistance strength cannot be obtained. . On the other hand, when the density exceeds 0.925 g / cm ³ , the melting point of the linear low-density polyethylene is increased, which is based on the reason that the compatibility with the ethylene copolymer rubber is deteriorated.

  The MFR (190 ° C./2.16 kgf) (JIS K 6922-2) of the linear low density polyethylene is 0.5 to 10.0 g / 10 minutes, preferably 1.0 to 8.0 g / 10 minutes. . This is based on the reason that when it is less than 0.5 g / 10 minutes, the processability at the time of extrusion molding deteriorates or the compatibility with the ethylene copolymer rubber deteriorates. On the other hand, when it exceeds 10.0 g / 10 minutes, the release film is torn during use, and this is based on the reason that the heat resistance strength cannot be obtained.

  In a resin composition prepared by mixing a polyethylene-based resin with an ethylene-based copolymer rubber, various additives are mixed as necessary within a range that does not impair the object of the present invention. Specifically, lubricants such as calcium stearate, antiblocking agents such as silica, phenolic antioxidants that function as radical scavengers, phosphorus antioxidants that function as peroxide decomposers, glycerin fatty acid esters, poly Antistatic agents such as glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene, and alkyl ether are selectively mixed.

  The release composition of the present invention is a composition containing a fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule, and various compounds have been proposed as the fluorosilicone compound. These fluorosilicone compounds are usually used by being applied to a mold. However, these fluorosilicone compounds are characterized in that they can be applied to the surface of a film to form a fluorosilicone compound layer. FIG. 1 is a cross-sectional view showing an embodiment of a release film configured as described above. In the figure, reference numeral 20 denotes a base film, and reference numeral 30 denotes a release composition. Here, the base film 20 may be a single layer film or a multilayer film having two or more layers. Moreover, the mold release composition 30 may be formed in the other surface of the base film 20, and may be formed in both surfaces.

Examples of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule in the present invention include a compound represented by the following chemical formula [1].
…… [1]

Here, in the formula of the chemical formula [1], R ^{1 to} R ¹⁰ are preferably C _1-20 , more preferably C _1-20 substituted or unsubstituted alkyl groups, or C _6-20 more A C _6-12 substituted or unsubstituted aryl group is preferable. The alkyl group may be substituted with a halogen atom such as a chlorine atom. The aryl group may be substituted with a halogen atom such as a chlorine atom or a C _1-10 alkyl group such as a methyl group. R ^{1 to} R ¹⁰ are, for example, an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group and a dodecyl group; a substituted alkyl group such as a chloromethyl group; and an unsubstituted aryl group such as a phenyl group and a naphthyl group Substituted aryl groups such as 4-chlorophenyl group and 2-methylphenyl group are included. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group is more preferable.

R ³ and R ¹⁰ may be Rf—X— or Z—Y—, and X and Y may be the same or different from each other and are composed of a divalent organic group. Rf is a C _1-6 fluoroalkyl group, and Z is a silyl group containing a hydrolyzable moiety.

X and Y are preferably a C _1-20 divalent organic group, more preferably a C _1-12 divalent organic group. Examples of divalent organic groups are preferably C _1-12 alkylene groups such as ethylene, propylene, methylethylene, octylene and decylene groups, and preferably C _2-12 alkyleneoxyalkylene groups. For example, an ethyleneoxymethylene group, a propyleneoxymethylene group, a propyleneoxyethylene group, and an ethyleneoxybutylene group. Further, X is preferably a C _1-12 alkylene amide group, such as an ethylene amide group, a propylene amide group, and a decylene amide group. Preferably X and Y are — (CH ₂ ) r—. Here, in the formula, r is 2 to 200, particularly 2 to 12.

  Rf is a fluoroalkyl group, preferably a perfluoroalkyl group, containing 1 to 6 carbon atoms, for example 1 to 5 carbon atoms, in particular 1 to 4 carbon atoms. Specifically, Rf is trifluoromethyl group, pentafluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-trifluoromethyl-perfluoroethyl group, perfluorobutyl group, perfluoropentyl. Group and perfluorohexyl group, and pentafluoroethyl group is preferable.

Z is, for example, a silyl group containing a hydrolyzable moiety that may have 1 to 60 carbon atoms. Z is —Si (R ¹¹ ) q (X ′) ₃ —q (R ¹¹ ) is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, X ′ is a hydrolyzable moiety, q is 0, 1 or 2. ). Further, Z ^{is, - (Si (R 11)} 2 O) r-Si (R 11) q (X ') 3 (R 11) is 1 to 20 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms X ′ is a hydrolyzable moiety and r is 1 to 200. ). R ¹¹ may be a methyl group, an ethyl group, a propyl group, a hexyl group or a dodecyl group, most preferably a methyl group. X ′ which is a hydrolyzable moiety is, for example, a halogen such as chlorine and bromine; an alkoxy group having preferably 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a methoxyethoxy group and a butoxy group; Preferably an acyloxy group having 1 to 12 carbon atoms such as a propionyloxy group and a benzoyloxy group; an alkenyloxy group such as an isopropenyloxy group and an isobutenyloxy group; a dimethylketoxime group, a methylethylketoxime group, diethyl Preferably an iminooxime group having 1 to 12 carbon atoms such as a ketoxime group and a cyclohexaneoxime group; preferably having 1 to 12 carbon atoms such as an ethylamino group, a diethylamino group and a dimethylamino group, and at least one A substituted amino group substituted with an alkyl group; Preferably an amide group having 1 to 12 carbon atoms such as an N-methylacetamide group and an N-ethylacetamide group; preferably having 1 to 12 carbon atoms such as a dimethylamineoxy group and a diethylamineoxy group, and at least It includes a substituted amineoxy group substituted with one, preferably an alkyl group having 1 to 4 carbon atoms.

  Here, m is 1 to 100, n is 1 to 50, and o is 0 to 200. Preferably, m is 1-50, n is 3-20, and o is 0-100. More preferably, m can be 2 to 50, n can be 3 to 20, and o can be 1 to 100.

A specific example of the above compound is a compound represented by the chemical formula [2], in which A is — (CH ₂ ) ₃ OCH ₂ CF ₂ CF ₃ or — (CH ₂ ) ₃ OCH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₃ and a compound in which B is — (CH ₂ ) ₃ Si (OCH ₃ ) ₃ .
…… [2]
Here, in the formula, Me means a methyl group. x is 1 to 100, y is 1 to 50, and z is 0 to 200.

In the present invention, the above-mentioned fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) may be a compound represented by the chemical formula (3).
…… [3]

The compound of the chemical formula [3] has a silylalkylene group represented by the general formula: —R ¹ —SiR ² _(3-m) X _m bonded to the silicon atom of the main chain, and the general formula: —R ¹ —C _n. One or more fluorine-containing organic groups represented by F _{(2n + 1)} are contained in each molecule. In the above formula, R ¹ is an alkylene group or an alkyleneoxyalkylene group. Examples of the alkylene group include ethylene group, methylethylene group, ethylethylene group, propylethylene group, butylethylene group, propylene group, butylene group, 1 -Methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group. Examples of the alkyleneoxyalkylene group include ethyleneoxyethylene group, ethyleneoxypropylene group, ethyleneoxybutylene group, propyleneoxyethylene group, propyleneoxypropylene group, propyleneoxybutylene group, butyleneoxyethylene group, butyleneoxypropylene group. It is done. R ² is a group selected from the group consisting of the same or different alkyl group, aryl group, and 3,3,3-trifluoropropyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a hexadecyl group, and an octadecyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. X is a halogen atom or an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. Here, m is an integer of 1 to 3. n is an integer greater than or equal to 4, Preferably it is an integer of 4-12. Examples of the fluorine-containing organic group represented by the above formula include nonafluorohexyl group, tridecafluoroisooctyl group, tridecafluorooctyl group, heptadecafluorodecyl group, nonafluorobutylethyloxyethyl group, nonafluorobutylethyl Examples thereof include oxypropyl group, nonafluorobutylethyloxybutyl group, undecafluoropentylethyloxyethyl group, and undecafluoropentylethyloxypropyl group. The bonding position of the silylalkylene group and the fluorine-containing organic group represented by the above formula may be at the molecular chain end, at the side chain, or both. Examples of the group bonded to the silicon atom other than these groups include a monovalent hydrocarbon group, specifically, the groups exemplified for the above R ² . The organopolysiloxane constituting the main chain is preferably linear. However, some may be branched, annular, or net-like. The organopolysiloxane is preferably liquid at room temperature, and the preferred viscosity at 25 ° C. is in the range of 5 to 100,000 centistokes. As this component, one kind of the above-mentioned organopolysiloxane may be used, or a mixture of two or more kinds may be used.

In the formula, R ³ is a group consisting of the same or different alkyl group, aryl group, 3,3,3-trifluoropropyl group, and a fluorine-containing organic group represented by the general formula: —R ¹ —C _n F _{(2n + 1)} And at least one of them is a fluorine-containing organic group represented by the above formula. Examples of the alkyl group, aryl group and fluorine-containing organic group include the same groups as described above. R ¹ , R ² , X, m and n are the same as described above. Here, d is an integer of 1 to 10,000, preferably an integer of 1 to 1,000. E is an integer of 1 to 1,000, preferably an integer of 1 to 100.

  In the present invention, among the above-mentioned fluorosilicone compounds (having a silyl group containing a hydrolyzable moiety in the molecule), the compound represented by the chemical formula [2] is preferably used.

The release composition applied in the present invention must contain a fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. As a mold release composition, if a fluorosilicone compound that does not contain a silyl group containing a hydrolyzable moiety in the molecule is used, when the molded product is peeled from the mold release film when used as a mold release film, This is because the release composition is also peeled off from the film surface and transferred to the surface of the molded product, resulting in a problem of contaminating the molded product. In contrast, when a fluorosilicone compound having a silyl group containing a hydrolyzable site in the molecule is used, it crosslinks with the film surface to form a chemical bond. The trouble which peels off and contaminates the surface of a molded article can be avoided. In the present invention, the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule is not limited to those described above, and is represented by, for example, chemical formula [4] and chemical formula [5]. Compounds.
…… [4]
Here, in the formula, q is an integer of 1 to 3. m, n, and o are each an integer of 0-200. p is 1 or 2. X is oxygen or a divalent organic group. r is an integer of 2-20. R ¹ is a C _1-22 linear or branched hydrocarbon group. a is an integer of 0-2. X ′ is a hydrolyzable group. In addition, when a is 0 or 1, z is an integer of 0 to 10.
…… [5]
Here, in the formula, q is an integer of 1 to 3. m, n, and o are each an integer of 0-200. p is 0, 1 or 2; X is oxygen or a divalent organic group. X ″ is a divalent organosilicone spacer group. X ′ is a hydrolyzable group. When a is 0 or 1, z is an integer of 0 to 10.

  The above-mentioned fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) is preferably used as a solution after being dissolved in an organic solvent or the like. Specific examples of the solvent include aliphatic saturated hydrocarbon solvents such as hexane, isohexane, heptane, octane and isooctane, aliphatic solvents such as cyclohexane, methylcyclohexane and dimethylcyclohexane, and aromatic solvents such as benzene, toluene and xylene. Solvents, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as ethanol and isopropyl alcohol, chlorine solvents such as trichloroethylene, chloroform and m-xylene hexachloride, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone Ether solvents such as diethyl ether, diisopropyl ether and tetrahydrofuran; fluorine solvents such as methyl perfluorobutyl ether and ethyl perfluorobutyl ether; Distearate siloxanes, silicone solvents such as hexamethylcyclotrisiloxane and heptamethyltrisiloxane and the like.

  The mold release composition described above may contain an organic titanium compound, an organic zirconium compound, and an organic silicon compound. These compounds function as a crosslinking agent between the film surface and a fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) and a fluorosilicone compound (a silyl group containing a hydrolyzable moiety is incorporated in the molecule). It has a function as a cross-linking curing agent between each other. Moreover, these compounds can be used in one or more combinations.

  Here, the organic titanium compound is, for example, titanium diisopropoxybis (ethyl acetoacetate), titanium dioctyloxybis (octylene glycolate), titanium tetraacetylacetonate, titanium diisopropoxybis (acetylacetonate), etc. Titanium chelates and titanium alkoxides such as titanium tetra-2-ethylhexoxide, titanium butoxy dimer, titanium tetranormal butoxide and titanium tetraisopropoxide, and the stability of the compound itself, crosslinking speed and crosslinking curing It can be appropriately selected and used in consideration of speed and the like. Of these, titanium diisopropoxybis (ethyl acetoacetate), titanium tetra-2-ethylhexoxide, titanium tetraisopropoxide and the like are preferably used.

  Examples of the organic zirconium compound include zirconium tetraacetylacetonate, zirconium dibutoxybis (ethylacetoacetate), zirconium monobutoxyacetylacetonatebis (ethylacetoacetate), zirconium tributoxymonoacetylacetonate and zirconium tetraacetylacetate. Zirconium chelates such as nates, and zirconium alkoxides such as zirconium tetranormal butoxide and zirconium tetranormal propoxide, etc., which are appropriately selected in consideration of the stability of the compound itself, the crosslinking rate and the crosslinking curing rate, etc. Can do.

  The organic titanium compound and the organic zirconium compound described above mainly function as a crosslinking agent between the surface of the base film and the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule). The addition amount thereof is in the range of 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule). It may be added in the range of 0.1 part by mass, more preferably in the range of 0.1-10 parts by mass. In this case, if the addition amount is less than 0.05 parts by mass, crosslinking between the surface of the base film and the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) is not preferable. Moreover, if added in excess of 20 parts by mass, the base film surface and the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) are sufficient for crosslinking, and an unreacted organotitanium compound Alternatively, the organic zirconium compound or both may remain, which is not preferable.

  As the organosilicon compound, a compound generally called a silane coupling agent can be used. Examples of the organosilicon compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltriethoxysilane. 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-phenylaminopropyltrimethoxysilane and N- (p-vinyl) Benzyl) -N- (trimethoxysilylpropyl) ethylenediamine-containing silane coupling agent, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-glycidoxypropi Epoxy group-containing silane coupling agents such as rumethyldiethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, and Vinyl group-containing silane coupling agents such as vinyltrichlorosilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-methacryloxypropylmethyldiethoxysilane A methacryl group-containing silane coupling agent, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and -Mercapto group-containing silane coupling agents such as mercaptopropylmethyldiethoxysilane, allyl group-containing silane coupling agents such as allyltrimethoxysilane and diallyldimethylsilane, bis (3- (triethoxysilyl) propyl) disulfide and bis ( Examples thereof include sulfide group-containing silane coupling agents such as 3- (triethoxysilyl) propyl) tetrasulfide. Among these compounds, amino group-containing silane coupling agents and epoxy group-containing silane coupling agents are preferable, and 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-amino) are more preferable. Ethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropylmethyldiethoxysilane, more preferably 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane .

  The organosilicon compound mainly functions as a cross-linking curing agent between fluorosilicone compounds (having a silyl group containing a hydrolyzable moiety in the molecule). The addition amount thereof is in the range of 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule). It may be added in a range of 0.1 to 10 parts by mass, more preferably in a range of 0.1 to 10 parts by mass. In this case, if the addition amount is less than 0.05 parts by mass, curing of the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) is insufficient, which is not preferable. Moreover, even if added in excess of 20 parts by mass, the cross-linking cure of the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule) is sufficient, and the unreacted organosilicon compound is Since it may remain, it is not preferable.

  In the release composition in the present application, it is desirable to use one or more compounds selected from the group consisting of an organic titanium compound and an organic zirconium compound in combination with an organic silicon compound. The organotitanium compound and the organozirconium compound mainly promote crosslinking between the base film surface and the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule), and the organosilicon compound is mainly a fluorosilicone compound. Accelerates cross-linking curing (having a silyl group containing a hydrolyzable moiety in the molecule). Therefore, by using these together, the fluorosilicone compound (silyl group containing a hydrolyzable moiety) is crosslinked with the surface of the base film and the fluorosilicone compound (having a silyl group containing a hydrolyzable moiety in the molecule). Having a group in the molecule) are crosslinked to form a network structure. Thereby, when used as a release film, even when the base film is stretched, the coating film made of the fluorosilicone compound is stretched following the base film, and the coating film is maintained without being destroyed. Therefore, the releasability with respect to the mold resin is maintained, and the fluorosilicone compound having the coating film does not migrate to the molded product. Moreover, in the manufacturing stage, the secondary effect that the drying time after application | coating can be shortened is also acquired.

The resin composition prepared by mixing 25 to 400 parts by mass of polyethylene resin with 100 parts by mass of ethylene copolymer rubber described above is molded by a conventionally known method such as a melt extrusion method or a melt cast method. be able to.
In the following example, a method of forming a base film by a melt extrusion method using, for example, a T die will be cited.

  The base film obtained by such a method uses a resin composition prepared by mixing 25 to 400 parts by mass of polyethylene resin with 100 parts by mass using an extruder such as a single screw extruder or a twin screw extruder. Depending on the properties of the resin composition, melt and knead in an atmosphere in which the air present in the gap between the extruder and the molding material is replaced with nitrogen gas, and melt from the lip portion at the tip of the T die placed at the tip of the extruder The extruded film is cooled by being sandwiched between a pressure-bonding roll and a cooling roll in the take-up machine, then irradiated with ionizing radiation, and then taken up sequentially on a take-up tube by a winder.

  FIG. 2 is a configuration diagram showing an outline of a film manufacturing apparatus for manufacturing a base film by the above-described method. FIG. 3 is a sectional view of the periphery of the material charging hopper of the film manufacturing apparatus shown in FIG. In FIG. 2, the film manufacturing apparatus is generally configured to include a material charging hopper 2, an extruder 1, a T die 7, a take-up machine 11, and a winder 15. The material input hopper 2 is configured to input a molding material. As shown in FIG. 3, the material input hopper 2 is connected to the extruder 1 of the material input hopper 2, and the nitrogen gas supply pipe 3 passes through the spacer 3a. Inserted. The nitrogen gas supply pipe 3 is bent so as to be substantially along the central axis of the material charging port 1 c, and the tip thereof extends to the vicinity of the outer periphery of the extrusion screw 1 a in the extruder 1. Oxygen contained in the molding material fed from the material feeding hopper 2 or in the extruder 1 is supplied to the nitrogen gas supply pipe 3 when the molding material is mixed and stirred by the extrusion screw 1a of the extruder 1. It will be replaced with nitrogen gas.

  The extruder 1 mixes and stirs the molding material with the extrusion screw 1a, conveys it in the direction of arrow B, and heats and melts the molding material by electric heating means incorporated in the cylinder 1b of the extruder 1. The molding material thus melted and conveyed is fed to the filter means 5 through the connecting pipe 4 shown in FIG. The unmelted molding material is separated by the filter means 5 and the molten molding material is fed to the gear pump 6. In the gear pump 6, the molten molding material is pushed out to the T die 7 while increasing the pressure of the molten molding material. In the T die 7, the melt molding material is extruded at a predetermined pressure, and a film 8 having a predetermined thickness and a predetermined width is formed from the lip portion 7 a of the T die 7. The film 8 formed in this manner is adjusted to a predetermined thickness by the pressure-bonding roll 9 while being drawn on the outer peripheral surface of the cooling roll 10 of the take-up machine 11, and further cooled and solidified. It is conveyed to the winder 15.

  In the winder 15, the film 8 is guided by the guide rolls 15 a, 15 b, and 15 c and is wound by the winding tube 16. In addition, a thickness measuring device 14 is disposed between the conveying roll pairs 12 and 13 and the guide roll 15a, and the thickness measured by the thickness measuring device 14 is set so as to obtain a desired thickness. Based on this, the peripheral speed of the cooling roll 10 is adjusted and controlled.

  Extruded film is cross-linked by irradiating with ionizing radiation to form a base film, thereby improving the mechanical strength of the release film at a high temperature of around 180 ° C., that is, heat resistance strength, and further suitable. Viscoelasticity is imparted. Examples of the ionizing radiation include α rays, β rays, electron rays, neutron rays, X rays, and γ rays from a cobalt 60 radiation source. Generally, electron rays and γ rays are preferable. The ionizing radiation can be irradiated by a known method. For example, in one embodiment of the present invention, as shown by the ionizing radiation irradiation device 17 in FIG. 2, the extruded film is continuously irradiated with an electron beam as ionizing radiation in-line during extrusion molding. Although the base film is used, the wound film may be irradiated with ionizing radiation offline in a batch manner.

The radiation dose is 50 to 250 kGy, preferably 100 to 200 kGy. This is because when the dose of radiation is less than 50 kGy, the dose is insufficient and crosslinking is insufficient, and the heat resistance required for the release film cannot be obtained. Conversely, when the radiation dose exceeds 250 kGy, the molecular chain scission of the ethylene copolymer rubber and polyethylene resin in the film exceeds the cross-linking reaction, resulting in deterioration and tearing of the release film during use. Because it will end up.

  In the present invention, a single-layer film is exemplified as the base film, but it is co-extruded with another resin composition at the time of extrusion molding to be formed into a multilayer film, or another resin composition is added to the extruded film. A multilayer film may be produced by laminating a film made of a material and irradiating the laminated laminate with ionizing radiation. As the resin composition used in this case, a resin composition containing a resin composed of an aromatic polyester and a polyether is suitable.

  A resin composition containing a resin composed of an aromatic polyester and a polyether is a composition containing a polyester / polyether copolymer as an essential component, an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a low molecular weight An esterification reaction is carried out using an aliphatic diol and a high molecular weight diol, followed by a polycondensation reaction.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, etc., and these ester-forming derivatives Examples thereof include dimethyl terephthalate, dimethyl isophthalate, and dimethyl orthophthalate. These are used singly or in combination of two or more, and terephthalic acid and / or ester-forming derivatives thereof are particularly preferable.

  Specific examples of the low molecular weight aliphatic diol include ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol And decamethylene glycol. These may be used alone or in combination of two or more, and 1,4-butanediol is particularly preferable.

  Specific examples of the high molecular weight aliphatic diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like. These are used alone or in combination of two or more, and polytetramethylene glycol is particularly preferable.

  Specific examples of the polyester / polyether copolymer comprising the above components include a butanediol terephthalate polytetramethylene glycol polymer and a butanediol terephthalate polypropylene glycol polymer. These resin compositions have a crystal phase composed of a crystalline aromatic polyester not containing a polyether skeleton in the main chain and an amorphous phase composed of a polyester having a polyether skeleton in the main chain. The melting point is flexible.

  The melting point of the polyester / polyether copolymer is 160 ° C. or higher, preferably 165 ° C. or higher, more preferably 170 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of heat resistance of the release multilayer film. This is based on the reason that when the melting point is lower than 160 ° C., the film is melted during use.

  A release film using a base film made of a resin composition containing a resin composed of an aromatic polyester and a polyether has a good tensile elastic modulus in addition to flexibility at high temperatures, and is superior to a mold mold. Has peelability.

  The base film should just form the surface shape of a film according to the surface shape of a molded article. For example, since ICs and LSIs form fine irregularities on the surface thereof, a release film having fine irregularities formed on the surface of the base film is used. Moreover, when the surface becomes a mirror surface by LED etc., the film for mold release which made the surface of the base film the mirror surface is used.

  As a method for forming the surface shape of the base film, when forming fine irregularities on the surface, fine irregularities are formed on the outer peripheral surface of the metal cooling roll described above, and the cooling roll is in a molten state. When a certain film is pressure-bonded by a pressure-bonding roll, a method of transferring fine irregularities formed on the outer peripheral surface of the cooling roll to the film surface may be simple. In addition, when the surface is a mirror surface, the surface of the metal cooling roll described above is made a mirror surface, and a film in a molten state is pressure-bonded to the cooling roll with a pressure roller, and the surface of the base film is adjusted to a mirror surface. It is easy to do.

  Thereafter, the release composition is applied to at least one surface of the base film and dried to form a fluorosilicone compound layer. A conventionally known coating method can be used for coating the release composition. For example, bar coater, reverse roll coater, forward rotation roll coater, gravure coater, kiss coater, cast coater, spray coater, curtain coater, die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, etc. Can be used.

  In the release film of the present invention, the thickness of the base film is in the range of 5 μm to 500 μm, preferably in the range of 10 μm to 400 μm, and may be appropriately selected according to the shape of the mold used. When the thickness of the base film is less than 5 μm, it is not preferable because the release film is stretched and thinned when it follows the mold during use, or it is broken by the pressure of the mold resin. . In addition, when the thickness exceeds 500 μm, the thickness of the release film becomes an obstacle, and it becomes impossible to follow the mold mold having a fine structure, or the complicated shape of the mold mold is not transferred to the molded product. Therefore, it is not preferable. The thickness of the fluorosilicone compound layer is in the range of 0.05 μm to 10 μm, preferably in the range of 0.1 μm to 5 μm. When the thickness of the fluorosilicone compound layer is less than 0.05 μm, there is a problem that the fluorosilicone compound layer is destroyed and loses peelability when following the mold during use. On the other hand, if the thickness exceeds 10 μm, further improvement in peelability cannot be expected, and it takes a long time for drying after coating, which is not preferable because productivity decreases. Furthermore, the flexibility of the fluorosilicone compound layer itself is not preferable because there is a problem that waviness occurs in the flat portion of the molded product.

Hereinafter, Examples 1 to 13 of the release film of the present invention will be described with reference to Tables 1 to 3.
Table 1 shows the contents of Examples 1 to 5 in the horizontal direction in the table, Table 2 shows the contents of Examples 6 to 10 in the horizontal direction in the table, and Table 3 shows the contents of Examples 11 to 13 in the horizontal direction in the table. Each content is shown. In Tables 1, 2, and 3, the base film, the release composition, and the release film evaluation are sequentially classified in the vertical direction in the table. In the section of the base film, the blending amount of the ethylene copolymer rubber and the polyethylene resin, the base film thickness, the type and dose of the ionizing radiation are classified and shown, and the section of the release composition includes the composition, The wet film thickness and the film thickness after drying are classified and shown. In the section of composition, solid content (parts by mass), organic titanium compound (parts by mass), organic zirconium compound (parts by mass), and organosilicon compound (parts by mass) are shown. In the section of film release evaluation, followability, heat resistance, water vapor barrier properties, peelability, and practical use are classified. Further, the followability term indicates tan δ in both the vertical and horizontal directions, the heat resistance term indicates the E ′ (Pa) in the vertical and horizontal directions, the water vapor barrier property indicates the water vapor transmission rate, In the releasability section, dry 2 minutes, dry 5 minutes, dry 10 minutes, and dry 15 minutes are classified. The release film according to the present invention is not limited to Examples 1 to 13.

  Here, the following materials are used for the ethylene copolymer rubber, polyethylene resin, fluorosilicone compound, organic titanium compound, organic zirconium compound, and organic silicon compound shown in Tables 1 to 3. Tables 4 and 5 show comparative examples (Comparative Examples 1 to 10) corresponding to the examples of the present invention together with their evaluations.

(Ethylene copolymer rubber)
Nordel IP 4770R: trade name, manufactured by DuPont Dow Elastomers, ethylene-propylene-nonconjugated diene copolymer rubber, Mooney viscosity ML _{1 + 4} (125 ° C.): 70, ethylene content: 70 mass%, nonconjugated diene content: 4.9% by mass
(Polyethylene resin)
Harmolex NF444A: trade name, manufactured by Nippon Polyethylene, linear low density polyethylene of ethylene-1-hexene copolymer, density: 0.912 g / cm ³ , MFR (190 ° C./2.16 kgf): 2.0 g / 10 minutes (fluorosilicone compound)
In the above chemical formula [2], A is — (CH ₂ ) ₃ OCH ₂ CF ₂ CF ₃ , B is — (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , x is 21, y is 5 and z A fluorosilicone compound having an A of 38 was prepared and used.
(Organic titanium compound)
ORGATICS TC-750: Trade name, manufactured by Matsumoto Trading Co., Ltd., titanium diisopropoxybis (ethyl acetoacetate)
(Organic zirconium compound)
Olga Chicks ZC-580: trade name, manufactured by Matsumoto Trading Co., Ltd., zirconium dibutoxybis (ethyl acetoacetate)
(Organic silicon compound)
KBM-903: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane

  Hereinafter, the production of the base film, the preparation of the release composition, the application and drying of the release composition, the followability, the heat resistance, the water vapor barrier property, the peelability and the practical use will be described in detail based on Tables 1 to 3. . In addition, these items are the contents similarly applied also in Comparative Examples 1 to 10 in Tables 4 and 5.

(Preparation of base film)
The resin composition is supplied to a single-screw extruder (made by IK Corporation) having a diameter of 40 mm and L / D = 25, and a cylinder temperature of 160 ° C. to 220 ° C. using a full flight extrusion screw with a compression ratio of 2.5. The mixture was melt-kneaded under the conditions described above, and continuously extruded from a T die having a width of 400 mm under the conditions of a die temperature of 220 ° C. to 240 ° C. In Examples 1 to 6, 8 to 13 and Comparative Examples 2 to 8 and 10, the extruded film was cooled by being sandwiched between a pressure-bonding roll and a cooling roll in the take-up machine, and then ionized radiation irradiation apparatus. By continuously irradiating with a predetermined dose of an electron beam to crosslink, then cutting both ends with a slit blade in a winder and winding it on a winder tube, the thicknesses shown in Tables 1 to 3 are obtained. A base film having a width of 250 mm and a length of 50 m was produced.

  In Example 7, instead of irradiating the film immediately after cooling with radiation, the cooled film was wound around a winding core with a winder, and then the γ-rays of a cobalt 60 radiation source were applied to the wound film. The base film was crosslinked by irradiation in a batch manner. In Comparative Examples 1 and 9, no ionizing radiation was applied.

(Preparation of mold release composition)
The above fluorosilicone compound was diluted with isopropyl alcohol to prepare a solution having a solid content concentration of 10% by mass. Next, an organotitanium compound, an organozirconium compound, and an organosilicon compound were added to the solid content of the solution in the compositions described in Tables 1 to 5 to prepare release compositions.

(Application and drying of release composition)
The mold release composition was applied to one side of the produced base film using a bar coater so as to have a wet film thickness described in Tables 1 to 5. The bar coater selected the wire number so that the desired wet film thickness was obtained. Subsequently, it dried in the hot air oven with an exhaust port adjusted to 150 degreeC. The release time was 2 minutes, 5 minutes, 10 minutes, and 15 minutes, respectively, and release films were prepared. Here, the film thickness after drying described in Tables 1 to 5 is a calculated value calculated from the wet film thickness and the solid content concentration of the release composition.

(Followability to mold)
The followability is evaluated by loss tangent tan δ in both the vertical and horizontal directions at a temperature of 180 ° C. in the dynamic viscoelasticity measurement of the base film. The reason for this is that, generally, a release film attached in a molding apparatus enters a mold mold temperature-controlled at 160 ° C. to 180 ° C., and is sucked in vacuum to adhere to the mold mold. Therefore, it is based on the fact that the dynamic viscoelastic behavior at 180 ° C. is suitable as an indicator of followability. Here, the loss tangent tan δ is a ratio E ″ / E ′ between the storage elastic modulus E ′ and the loss elastic modulus E ″ in the dynamic viscoelasticity measurement.

Specifically, a film at a temperature of 180 ° C. measured under the conditions of a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 5 ° C./min using a SOLIDS ANALYZER RSAII (trade name) manufactured by Rheometrics. When the loss tangent tan δ in both the longitudinal and lateral directions and the storage elastic modulus E ′ is 1.0 × 10 ⁷ Pa or more, the loss tangent tan δ is preferably 0.05 to 0.20, more preferably 0.06 to 0.00. 15. This is because when the loss tangent tan δ is less than 0.05, the elastic deformation ratio of the release film becomes too strong, and the followability to the mold is insufficient. On the other hand, if it exceeds 0.20, the followability to the mold is sufficient, but the rate of plastic deformation becomes too strong, and the film becomes loose and wrinkled. This is because it causes the formation of defective molding.

  Furthermore, in the present invention, it is important that tan δ is in the range of 0.05 to 0.20 in both the vertical and horizontal directions of the film. This is because the release film is stretched in both the vertical and horizontal directions of the film in the mold.

(Heat resistance strength)
Furthermore, in terms of heat resistance strength, the storage elastic modulus E ′ must be 5.0 × 10 ⁵ Pa or more in both the vertical and horizontal directions of the film. When the storage elastic modulus E ′ is less than 5.0 × 10 ⁵ Pa, the film is broken by the pressure of the mold resin during use, and the heat resistance strength is insufficient.

(Water vapor barrier property)
The water vapor barrier property was evaluated by the water vapor transmission rate. This water vapor transmission rate is JIS
It is a value measured by Z0208 and is 100 g / m ² · 24 h or less, preferably 60 g / m ² · 24 h or less, more preferably 40 g / m ² · 24 h or less. This is because when the water vapor transmission rate exceeds 100 g / m ² · 24 h, the water vapor barrier property becomes insufficient, and the water vapor generated from the mold resin permeates the release film and causes contamination of the mold. It is.

(Peelability)
For the peelability, the peelability between the release film and the epoxy resin used as the mold resin was evaluated. An epoxy resin sealing material KMC-3580 (manufactured by Shin-Etsu Chemical Co., Ltd.) is placed on the film surface to which the release composition of the release film is applied, and these are two flat plate molds whose inner surfaces are hard chrome plated. The laminate was subjected to hot press molding and the molded laminate was evaluated for peelability between the release film and the epoxy resin.

Hot press molding was performed under conditions of a temperature of 180 ° C. and a pressure of 50 kg / cm ² for 3 minutes. The evaluation of peelability was indicated as “◯” when the solidified epoxy resin could be peeled off without remaining on the film, and “X” when the solidified epoxy resin remained on the release film.

(Actual usability)
The actual usability was confirmed and evaluated by resin molding with a molding apparatus. Specifically, the molding device G-LINE manual press (trade name) manufactured by Apic Yamada is used as the molding device, and the epoxy resin sealing material KMC-3580 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the mold resin. Usability was confirmed visually.

  The evaluation of actual usability is that the molded product has no molding defects such as waviness of the flat part, tears and tears in the release film, there is no mold resin residue, and the mold mold is not soiled. The case where there was a crab defect was marked as “x”.

  From the results regarding Comparative Examples 1 to 10 shown in Tables 4 and 5, the following became clear. (A) In Comparative Example 1 in which the polyethylene resin content in the resin composition of the base film is small with respect to 100 parts by mass of the ethylene copolymer rubber, the production of the film, that is, the film formation is performed. It was impossible. (B) With respect to 100 parts by mass of the ethylene-based copolymer rubber, 420 parts by mass of the polyethylene-based resin, and in Comparative Example 2 in which the polyethylene-based resin content in the resin composition of the base film is large, no peelability was obtained. . (C) In Comparative Example 3 where the electron beam irradiation dose was as low as 30 kGy, it was impossible to measure the followability, heat resistance strength, and peelability. (D) In Comparative Example 4 where the electron beam irradiation dose was as high as 270 kGy, the peelability could not be measured. (E) In the composition of the release composition, Comparative Example 5 containing 0.01 part by mass of an organic titanium compound, Comparative Example 6 containing 0.01 part by mass of an organic zirconium compound, and organic, with respect to 100 parts by mass of the solid content Comparative Example 7 containing 0.01 parts by mass of a titanium compound and 0.01 parts by mass of an organic zirconium compound, and Comparative Examples 5 to 7 having a low content of an organic titanium compound and / or an organic zirconium compound and no organosilicon compound In this case, no peelability was obtained. (F) In the comparative example 8 in which the wet film thickness of the release composition was 120 μm and the film thickness after drying was 12 μm, both of them were not peelable. (G) No irradiation with ionizing radiation, ETFE film manufactured by Asahi Glass Co., Ltd., Aflex (trade name) is used as a base film, and in Comparative Example 9 where no release composition is applied, the followability is poor. Actual usability was not obtained. (F) In Comparative Example 10 in which a release agent made by Daikin Industries, Die Free GF-6332 (trade name, solid content concentration of 3% by mass) was used as the release composition, peelability was not obtained.

  On the other hand, the following became clear from the results regarding Examples 1 to 13 shown in Tables 1 to 3. (Ii) In Examples 8 to 10 in which the release composition does not contain an organosilicon compound, the release property cannot be obtained in 2 minutes and 5 minutes after coating and drying of the release composition, but 10 minutes after coating and drying; In 15 minutes, peelability is obtained. (B) In Example 13 where the wet film thickness of the release composition is 40 μm and the post-drying film thickness is 4 μm, in Example 13, peelability is obtained 2 minutes and 5 minutes after application and drying of the release composition. Although not present, peelability was obtained 10 minutes and 15 minutes after coating and drying. (Ni) In Examples 1 to 7, 11, and 12, peelability was obtained. (E) In all of Examples 1 to 13, followability, heat resistance strength, water vapor barrier property, and actual usability are obtained.

  From the results relating to Examples 1 to 13 shown in Tables 1 to 3 and the results relating to Comparative Examples 1 to 10 shown in Tables 4 and 5, according to the present invention, molded products obtained by molding a mold resin and It has been clarified that it is possible to obtain a release film having excellent heat release strength and water vapor barrier properties as well as excellent mold releasability and excellent conformability to a mold.

  As mentioned above, although this invention was demonstrated using embodiment, it cannot be overemphasized that the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiments. Further, it is apparent from the scope of the claims that embodiments with such changes or improvements can also be included in the technical scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Extruder 2 Material input hopper 3 Nitrogen gas supply pipe 4 Connection pipe 5 Filter 6 Gear pump 7 T die 7a Lip part 8 Film 9 Crimp roll 10 Cooling roll 11 Take-up machine 12, 13 Conveying roll pair 14 Thickness measuring device 16 rolls Intake tube 17 Ionizing radiation irradiation device 20 Base film 30 Mold release composition

Claims (23)

  A base film obtained by crosslinking a film obtained by extruding a resin composition obtained by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber and irradiating with ionizing radiation. It is characterized in that a fluorosilicone compound layer obtained by applying and drying a release composition containing a fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule is formed on at least one surface. Release film. The ethylene copolymer rubber contains 40 to 90% by mass of ethylene and 0.5 to 8.0% by mass of non-conjugated diene, and has a Mooney viscosity ML _{1 + 4} (125 ° C.) of 10 to 100. The release film according to claim 1.     The non-conjugated diene is 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4-hexadiene, It is one or more selected from the group consisting of 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene The release film according to claim 2, wherein the release film is a film. The polyethylene resin is a linear low density polyethylene having a density of 0.855 to 0.925 g / cm ³ and an MFR (190 ° C./2.16 kgf) of 0.5 to 10.0 g / 10 min. The release film according to claim 1, wherein the release film is provided.   The resin composition further includes, as an additive, one or more selected from the group consisting of a lubricant, an anti-blocking agent, a phenolic antioxidant, a phosphorus antioxidant, and an antistatic agent. Item 2. The release film according to Item 1.   The ionizing radiation is irradiated at a dose of 50 to 250 kGy using one selected from the group consisting of α rays, β rays, electron rays, neutron rays, X rays, and γ rays of a cobalt 60 radiation source. The release film according to claim 1.   The release film according to claim 1, wherein the base film is a single layer film or a multilayer film having two or more layers.   The release composition is one selected from the group consisting of an organic titanium compound, an organic zirconium compound and an organic silicon compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. The release film according to any one of claims 1 to 7, wherein the release film is a composition comprising a plurality of compounds in a range of 0.05 to 20 parts by mass.   The mold release composition contains one or more compounds selected from the group consisting of organic titanium compounds and organic zirconium compounds with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. It is a composition formed by containing in the range of 0.05-20 mass parts, The film for mold release of any one of Claims 1-8 characterized by the above-mentioned.   One or more compounds selected from the group consisting of an organic titanium compound and an organic zirconium compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. In the range of 0.05-20 mass parts, Furthermore, it is a composition formed by containing an organosilicon compound in the range of 0.05-20 mass parts. The release film as described in Item 1.   A single-layer base formed by extruding a resin composition obtained by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber, and irradiating with ionizing radiation. A release composition comprising a fluorosilicone compound having a silyl group in the molecule and having a thickness of a film or a multilayer base film of two or more layers in the range of 5 μm to 500 μm and dried. The film for release according to any one of claims 1 to 10, wherein the thickness of the fluorosilicone compound layer obtained in the above range is in the range of 0.05 µm to 10 µm.   In the dynamic viscoelasticity measurement of the release film, the loss tangent tan δ at 180 ° C. measured under conditions of a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 5 ° C./min is the length and width of the release film. The release film according to any one of claims 1 to 11, wherein the film is in a range of 0.05 to 0.20 in both directions. Mixing 25 to 400 parts by mass of polyethylene resin to 100 parts by mass of ethylene copolymer rubber to obtain a resin composition;
Extruding the resin composition to obtain a film;
Irradiating the film with ionizing radiation and crosslinking to obtain a base film;
Applying a release composition containing a fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule to at least one surface of the base film, and drying to form a fluorosilicone compound layer;
The manufacturing method of the film for mold release characterized by including. The ethylene copolymer rubber contains 40 to 90% by mass of ethylene and 0.5 to 8.0% by mass of non-conjugated diene, and has a Mooney viscosity ML _{1 + 4} (125 ° C.) of 10 to 100. The method for producing a release film according to claim 13.     The non-conjugated diene is 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4-hexadiene, It is one or more selected from the group consisting of 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene The manufacturing method of the film for mold release of Claim 14 characterized by the above-mentioned. The polyethylene resin is a linear low density polyethylene having a density of 0.855 to 0.925 g / cm ³ and an MFR (190 ° C./2.16 kgf) of 0.5 to 10.0 g / 10 min. 14. The method for producing a release film according to claim 13, wherein the film is for release.   The resin composition further includes, as an additive, one or more selected from the group consisting of a lubricant, an anti-blocking agent, a phenolic antioxidant, a phosphorus antioxidant, and an antistatic agent. Item 14. A method for producing a release film according to Item 13.   The ionizing radiation is irradiated at a dose of 50 to 250 kGy using one selected from the group consisting of α rays, β rays, electron rays, neutron rays, X rays, and γ rays of a cobalt 60 radiation source. The method for producing a release film according to claim 13.   The method for producing a release film according to claim 13, wherein the base film is a single layer film or a multilayer film having two or more layers.   The release composition is one selected from the group consisting of an organic titanium compound, an organic zirconium compound and an organic silicon compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. The method for producing a release film according to any one of claims 13 to 19, which is a composition comprising a plurality of compounds in a range of 0.05 to 20 parts by mass.   The mold release composition contains one or more compounds selected from the group consisting of organic titanium compounds and organic zirconium compounds with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. 21. The method for producing a release film according to any one of claims 13 to 20, wherein the composition is contained in a range of 0.05 to 20 parts by mass.   One or more compounds selected from the group consisting of an organic titanium compound and an organic zirconium compound with respect to 100 parts by mass of the fluorosilicone compound having a silyl group containing a hydrolyzable moiety in the molecule. 22 to 20 parts by mass and further containing an organosilicon compound in the range of 0.05 to 20 parts by mass. The manufacturing method of the film for mold release of 1 item | term. A single-layer base formed by extruding a resin composition obtained by mixing 25 to 400 parts by mass of a polyethylene resin with 100 parts by mass of an ethylene copolymer rubber, and irradiating with ionizing radiation. A release composition comprising a fluorosilicone compound having a silyl group in the molecule and having a thickness of a film or a multilayer base film of two or more layers in the range of 5 μm to 500 μm and dried. 23. The method for producing a release film according to any one of claims 13 to 22, wherein the thickness of the fluorosilicone compound layer obtained in this manner is in the range of 0.05 to 10 [mu] m.