TW201334938A - Release film - Google Patents

Abstract

The purpose of this invention is to provide a release film which has excellent peeling property for a mold or a molded article, has excellent mold shape transfer property for transferring the mold shape to the molded article according to design, and is capable of obtaining surface smoothness of the molded article, thereby also having thermal resistance to a working temperature around 140 DEG C. The release film of this invention comprises the following two components: 100 parts by mass of polyurethane with a JIS A hardness of 70 or above and a Vicat softening temperature of 100 to 180 DEG C; and 1 to 400 parts by mass of thermoplastic elastomer containing thermoplastic fluororesin.

Description

Release film

The present invention relates to a release film, for example, used in the molding of an optical semiconductor element or a semiconductor element, particularly in the molding of an LED (light-emitting diode) lens. Release film.

For example, an optical semiconductor element including an LED, an optical isolator, a photoelectric crystal, a photodiode, a CCD (Charge Coupled Device), a CMOS (Complementary Metal Oxide Semiconductor), or a transistor, A semiconductor element such as an IC (Integrated Circuit), an LSI (Large Scale Integrated Circuit), or a super LSI uses a polyoxyethylene rubber composition or an epoxy resin composition as a sealing material by a mold. It is formed by casting and sealing.

A die-casting apparatus is used for sealing such an optical semiconductor element or a semiconductor element, and a polyoxyxylene rubber composition or an epoxy resin composition is filled in a mold of the mold-forming apparatus as a sealing material and molded.

In this case, as a method of releasing the mold from the molded article, for example, a method in which the release film is interposed between the mold and the sealing material filled in the mold has been put into practical use (see Patent Document 1). The release film is supplied by a roll-to-roll in a die-casting apparatus, and placed in a mold whose temperature is adjusted to a molding temperature, and is suctioned by vacuum to adhere to the mold, and then filled with a sealing material. . When the mold is opened after a certain period of time, the film for release film The molded article is peeled off from the release film in a state of being attracted to the mold. As the film for release film, for example, a tetrafluoroethylene-ethylene copolymer resin (ETFE) containing a thermoplastic fluororesin or a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP (fluorinated ethylene) is used. A single layer film of propylene (fluorinated ethylene propylene) resin (refer to Patent Document 2).

However, when such a release film is used for the formation of an LED lens using a polyoxyethylene rubber composition as a sealing material, for example, the bottom surface is A shape of a cannonball lens of about 6 mm and a height of about 4 mm has the following disadvantages: the release film may not be stretched even if it is attracted by vacuum, and even if it is extended, it is not closely adhered to the mold, so that it cannot be obtained according to design. LED lens. Further, when the thickness of the release film is made thin and it is easily stretched, it may cause a problem that the release film is damaged by the edge of the mold when suction is performed by vacuum.

On the other hand, as a release film, as disclosed in the following Patent Document 3, there is known a method of using a film comprising a resin composition containing butylene terephthalate in a crystal component. Crystalline aromatic polyester.

However, when a film composed of a resin composition containing a crystalline aromatic polyester containing butylene terephthalate is used for the formation of an LED lens, the release film is adhered while being sucked by vacuum. On the mold, since it extends beyond the point of undulation, the film for release film is locally thinned, and defects such as irregularities or wrinkles are formed on the surface of the formed LED lens. Moreover, as a polyoxyxene rubber composition, an additive liquid polymerization is used. Oxide rubber, but the following problems occur: the compound present in the film for release molding is a catalytic poison of the addition-form liquid polyoxyethylene rubber, and the hardening is inhibited, and the contact surface with the release film is not hardened and the gel remains. Adhesive. Therefore, in the molding of an LED lens using an additive liquid polyoxyethylene rubber, it is practical that there is no film which can be preferably used as a film for release film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-142105

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-310336

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-224311

The present invention has been made in view of such a situation, and an object of the present invention is to provide a release film which is excellent in peelability from a mold or a molded article in die casting using an LED lens in which a liquid polyoxyethylene rubber is added.

Moreover, an object of the present invention is to provide a release film which is excellent in mold transferability by transferring a shape of a mold to a molded article.

Moreover, an object of the present invention is to provide a release film which does not leave a gel-like adhesive on the surface of a molded article and obtains surface smoothness of the molded article.

Further, an object of the present invention is to provide a release film having heat resistance at a use temperature of about 140 °C.

In order to achieve such an object, the present invention is constituted by a thermoplastic fluororesin contained in a thermoplastic polyurethane elastomer, which is a thermoplastic urethane. The JIS A hardness of the elastomer is 70 or more, the Vickers softening temperature is 100 to 180 ° C, and the thermoplastic fluororesin is contained in an amount of 1 to 400 parts by mass based on 100 parts by mass of the thermoplastic polyurethane elastomer. Within the scope.

The present invention can be understood by the following constitution.

(1) The film for release film of the present invention is characterized in that it is composed of 100 parts by mass of a thermoplastic polyurethane elastomer having a hardness of 70 or more and a Vickers softening temperature of 100 to 180 ° C with respect to JIS A. A thermoplastic elastomer 2 component composition containing a thermoplastic fluororesin in a range of 400 parts by mass.

(2) The release film of the present invention, wherein the thermoplastic fluororesin is a thermoplastic tetrafluoroethylene copolymer having a melting point of 140 ° C or more and 240 ° C or less.

(3) The film for release film of the present invention having the composition of the thermoplastic elastomer 2 component composition, which is contained in the range of 0.05 to 5.0 parts by mass, selected from the group consisting of (1) or (2) A thermoplastic elastomer 3 component composition of one or a plurality of compounds of a group consisting of a fluorine-containing alcohol compound and a fluorine-containing diol compound.

(4) The film for release film of the present invention having the composition of (2) or (3), wherein the fluorine-containing alcohol compound is a compound represented by the formula (A), and the fluorine-containing diol compound is a pass. a compound of the formula (B), Rf ₁ (CH ₂ ) _m OH (...) (wherein Rf ₁ represents a linear or branched perfluoroalkyl group having a carbon number of 3 to 20 or Perfluoroalkyl ether group, m is an integer from 1 to 5) Rf ₂ (CH ₂ ) _n OCH ₂ CH(OH)CH ₂ OH (...) (wherein Rf ₂ represents a carbon number of 3 to 20 A linear or branched perfluoroalkyl group, n represents an integer of 1 or 2.

(5) The film for release film of the present invention having any one of (1) to (4), wherein the thermoplastic elastomer 2 component composition and the three component composition further comprise a lubricant, an anti-caking agent, and a phenol. It is one of an antioxidant or a phosphorus antioxidant or a plurality of additives.

(6) The release film of the present invention according to any one of (1) to (5), wherein the tensile modulus of the film is in the longitudinal direction of the film (MD, Machine Direction) and the transverse direction of the film (TD, Transverse) Direction) is in the range of 10~500 N/mm ² .

(7) The release film of the present invention according to any one of (1) to (6), wherein the film has a 50% modulus (50% Mo) in the film longitudinal direction (MD) and the film transverse direction (TD). The upper ratio (MD) / (TD) is in the range of 0.9 to 1.2.

(8) The release film of the present invention having any one of (1) to (7), wherein a ratio of a 50% modulus (50% Mo) of the film to a 100% modulus (100% Mo) (100) % Mo) / (50% Mo) is in the range of 1.0 to 1.6 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film.

(9) The release film of the present invention having any one of (1) to (8), wherein the tensile elongation of the film exceeds 350% in both the longitudinal direction (MD) and the transverse direction (TD) of the film. .

(10) The release film of the present invention having any one of (1) to (9), which comprises a film containing a thermoplastic resin or a thermoplastic polyurethane-containing elastomer A multilayer film of a film of a thermoplastic elastomer.

The release film according to the present invention has excellent peelability from a mold or a molded article The shape of the mold is excellent in transferability to the shape of the mold to be transferred to the molded article, and the gel-like adhesive does not remain on the surface of the molded article, so that the surface smoothness of the molded article can be obtained, and heat resistance can be obtained. Sex.

The present inventors have conducted various studies to achieve the above object, and as a result, it has been found that the film for release film comprising the thermoplastic elastomer 2 component composition is excellent in peelability from a mold or a molded article, and the shape of the mold is transferred to the design. The molded article has excellent mold shape transferability, and does not leave a gel-like adhesive on the surface of the molded article, thereby obtaining surface smoothness of the molded article, and also having heat resistance, and the thermoplastic elastomer 2 component composition is relative to 100 parts by mass of a thermoplastic polyurethane elastomer having a JIS A hardness of 70 or more, a specific gravity of 1.05 to 1.30, and a Vickers softening temperature of 100 to 180 ° C in a polyurethane-based elastomer, and containing thermoplastic fluorine The resin is 1 to 400 parts by mass.

The thermoplastic polyurethane-based elastomer of the present invention is a thermoplastic polyurethane-based elastomer obtained by a reaction of three components of a polyisocyanate, a polyol, and a chain extender.

Examples of the polyisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, and 4,4'-. Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl- 4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4 '-Diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl- Aromatic diisocyanates such as 4,4'-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane diisocyanate, trimethylhexamethylene diisocyanate, leucine diisocyanate, etc. Aliphatic diisocyanates, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate Acid ester, hydrogenated diphenylmethane diisocyanate, tetramethyl xylene diisocyanate, lower An alicyclic diisocyanate such as methyl alkane diisocyanate, a diuret, a dimer, a trimer, a dimer-trimer, a carbodiimide, a uretonimine of the above isocyanate An adduct obtained by reacting a difunctional or higher polyhydric alcohol with the above isocyanate or the like. Further, a blocking agent having an active hydrogen in a molecule such as methanol, n-butanol, benzyl alcohol, ethyl acetate, ε-caprolactam, methyl ethyl ketoxime, phenol or cresol may be mentioned. A polyisocyanate which partially stabilizes one of the isocyanate groups. These may be used alone or in combination of two or more.

The polymer polyol having a polyhydric alcohol coefficient and an average molecular weight of 500 to 10,000 may, for example, be a polyester polyol, a polyester decylamine polyol, a polycarbonate polyol, a polyether polyol, a polyether ester polyol, or a poly Olefin polyols and the like. These may be used alone or in combination of two or more.

The polyester polyol and the polyester decylamine polyol are, for example, those obtained by a condensation reaction using a polycarboxylic acid and a polyhydric alcohol, or a diamine or an amino alcohol in combination, if necessary.

Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid, and alkyl phthalate. Esters, trimellitic acid, maleic acid, fumaric acid, itaconic acid, and the like. Further, for example, those obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone, and caprolactone may be mentioned.

Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5- Pentyl glycol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl- 1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-n-hexadecane-1,2-ethane Alcohol, 2-n-eicosane-1,2-ethanediol, 2-n-octadecane-1,2-ethanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol Or an ethylene oxide or propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropanoic acid Low molecular polyols such as esters, trimethylolpropane, glycerin, and pentaerythritol. Examples of the diamine or amino alcohol include low molecular polyamines such as ethylenediamine, hexamethylenediamine, xylylenediamine, and isophorone diamine, and low molecular weights such as monoethanolamine, diethanolamine, and triethanolamine. Amino alcohols. Further, a low molecular weight polyol, a low molecular weight polyamine, and a low molecular weight amino alcohol are used as a starting agent, and ring-opening of a cyclic ester (lactone) monomer such as ε-caprolactone or γ-valerolactone is used. A lactone-based polyester polyol obtained by polymerization.

Examples of the polycarbonate polyol include a low molecular polyol used for the synthesis of the above polyester polyol, and diethyldicarbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. Obtained by alcohol reaction, dephenolization reaction, and the like.

Examples of the polyether polyol include a low molecular polyol, a low molecular polyamine, and a low molecular weight amino alcohol used in the above polyester polyol as an initiator to open ethylene oxide, propylene oxide, tetrahydrofuran, and the like. Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., which are obtained by cyclic polymerization, and polyether polyols obtained by copolymerizing these, and further, the above-mentioned polyester polyol and polycarbonate A polyester ether polyol having a polyol as a starter.

The polyether ester polyol is obtained in the same manner as the above polyester polyol, except that a part or all of the polyol used for the condensation reaction in obtaining the above polyester polyol is used.

Examples of the polyolefin polyol include a hydroxyl group-containing polybutadiene, a hydrogenated hydroxyl group-containing polybutadiene, a hydroxyl group-containing polyisoprene, and a hydrogenated hydroxyl group-containing polyisoprene. Hydroxy-containing chlorinated polypropylene, hydroxyl-containing chlorinated polyethylene, and the like.

Further, the chain extender is a compound containing an active hydrogen having a number average molecular weight of less than 500, and examples thereof include the above low molecular polyols, the above low molecular polyamines, and the above low molecular weight amino alcohols.

In the production of the above thermoplastic polyurethane-based elastomer used in the present invention, a known production method can be employed, and for example, a one-shot method, a prepolymer method, a batch reaction method, or the like can be employed. A continuous reaction method, a method using a kneader, and a method using an extruder.

The hardness of the thermoplastic polyurethane-based elastomer is 70 or more in JIS A hardness measured by the test method of JIS K 7311. Further, when the JIS A hardness is 100 or more, it is preferable to apply the D hardness and set the D hardness to 80 or less as the upper limit. The JIS A hardness is preferably 80 or more, more preferably It is 90 or more. When it is assumed that the JIS A hardness is less than 70, it is confirmed that the rubber property is strong, and when the release film is conveyed in the mold forming apparatus, the release film is stretched to make the conveyance unstable. Moreover, when the D hardness exceeded 80, it was confirmed that the gel derived from the three components of the polyisocyanate, the polyol, and the chain extender of the raw material was generated at the time of extrusion molding.

The Vickers softening temperature of the above thermoplastic polyurethane-based elastomer is measured by the test method of JIS K 7206 and is in the range of 100 to 180 °C. The Vickers softening temperature is preferably in the range of 110 to 180 ° C, more preferably in the range of 120 to 180 ° C, and still more preferably in the range of 130 to 180 ° C. If the Vickers softening temperature is less than 100 ° C, it is confirmed that the film is welded to the polyoxyethylene rubber at the time of use, and the peeling property is lowered. Further, the upper limit of the Vickers softening temperature was set to 180 ° C because the thermoplastic polyurethane elastomer having a Vickers softening temperature of more than 180 ° C could not be obtained.

The thermoplastic fluororesin used in the present invention is a thermoplastic tetrafluoroethylene copolymer. Examples of the thermoplastic tetrafluoroethylene copolymer include a copolymer of tetrafluoroethylene and a copolymerizable monomer copolymerizable with tetrafluoroethylene. Examples of the copolymerizable monomer include olefins such as ethylene, propylene, and butylene; fluoroethylenes such as CF ₂ =CH ₂ and CF ₂ =CFCl; and fluoropropenes such as CF ₂ =CFCF ₃ and CF ₂ =CHCF ₃ . , CF ₃ CF ₂ CF ₂ CF ₂ CH=CH ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF=CH ₂ and other perfluoroalkyl groups having a carbon number of 4 to 12 perfluoroalkyl vinyls, R ^f (OCFXCF ₂ ) _m OCF=CF ₂ (wherein, R ^f represents a perfluoroalkyl group having 1 to 6 carbon atoms, X represents a fluorine atom or a trifluoromethyl group, and m represents an integer of 0 to 5), and the like is a perfluorovinyl ether group. Wait. These copolymerized monomers may be used singly or in combination of two or more.

Specific examples of the thermoplastic tetrafluoroethylene copolymer include an ethylene-tetrafluoroethylene copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a tetrafluoroethylene-perfluoro(propyl vinyl ether) copolymer. , a tetrafluoroethylene-vinylidene fluoride copolymer, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and the like. The melting point of the thermoplastic tetrafluoroethylene copolymer is preferably 140 ° C or higher and 240 ° C or lower. When the melting point is less than 140 ° C, it is confirmed that the film is melted in the mold when it is used as a release film. Further, when a tetrafluoroethylene-based copolymer having a melting point of more than 240 ° C was used, it was confirmed that the unmelted material remained in the film without being melted in the molding processing temperature range of the thermoplastic polyurethane elastomer. Bad situation.

The thermoplastic fluororesin is mixed by imparting releasability to a film or a molded article. The blending amount of the thermoplastic fluororesin is in the range of 1 to 400 parts by mass, preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass based on 100 parts by mass of the thermoplastic polyurethane elastomer. Within the range of the portion, it is preferably in the range of 10 to 100 parts by mass. When the amount of the mixture is less than 1 part by mass, it is confirmed that the effect of mixing is not exerted and the peeling property is not improved. In addition, when the amount is more than 400 parts by mass, it is confirmed that the thermoplastic fluororesin is not uniformly dispersed in the thermoplastic polyurethane elastomer, and is formed by the thermoplastic fluororesin when the film is stretched. Wrinkles are formed on the film due to the influence of the drop point in the tensile properties.

The release of the thermoplastic elastomer 2 component composition comprising the thermoplastic fluororesin blended in the thermoplastic polyurethane elastomer in the above manner The film is excellent in peelability from a mold or a molded article, and the shape of the mold is transferred to the molded article in accordance with the design size, and the mold shape is excellent in transferability and heat resistance. Further, in the case where the film after the production was kept at 40 ° C for 60 days or more, it was confirmed that the catalytic poisoning of the added liquid polyoxyethylene rubber disappeared, and the surface of the molded article was not The surface smoothness of the molded article can be obtained by leaving a gel-like substance.

Here, in the present invention, in order to shorten the aging time necessary for the release film comprising the thermoplastic elastomer 2 component composition, the thermoplastic elastomer 2 component composition may be mixed with a fluorine-containing alcohol compound and a compound of the group consisting of fluorine-containing diols.

The fluorine-containing alcohol-based compound is Rf ₁ (CH ₂ ) _m OH of the formula (A) (wherein Rf ₁ represents a linear or branched perfluoroalkyl group having a carbon number of 3 to 20 or A perfluoroalkyl ether group, m is a compound represented by 1 to 5). Specific examples thereof include C ₆ F ₁₃ CH ₂ OH, C ₇ F ₁₅ CH ₂ OH, C ₈ F ₁₇ CH ₂ OH, C ₈ F ₁₇ CH ₂ CH ₂ OH, and C ₉ F ₁₉ CH ₂ CH. ₂ OH, C ₁₀ F ₂₁ CH ₂ CH ₂ OH, (CF ₃ ) ₂ CF(CF ₂ ) ₈ CH ₂ CH ₂ OH, CF ₃ CF ₂ O(CF ₂ CF ₂ O) _1~5 CF ₂ CH ₂ OH , CF ₃ CF ₂ CF ₂ O (CFCF ₃ CF ₂ O) _1~3 CFCF ₃ CH ₂ OH, and the like. In this case, it is preferred to use C ₆ F ₁₃ CH ₂ OH, C ₇ F ₁₅ CH ₂ OH, C ₈ F ₁₇ CH ₂ OH, C ₈ F ₁₇ CH ₂ CH ₂ containing a linear perfluoroalkyl group. OH, C ₉ F ₁₉ CH ₂ CH ₂ OH, C ₁₀ F ₂₁ CH ₂ CH ₂ OH.

Further, the fluorine-containing diol compound is Rf ₂ (CH ₂ ) _n OCH ₂ CH(OH)CH ₂ OH of the formula (B) (wherein Rf ₂ represents a linear chain having a carbon number of 3 to 20) Or a compound represented by a branched perfluoroalkyl group, n being an integer of 1 or 2. Specific examples include, for example, C ₆ F ₁₃ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₇ F ₁₅ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₈ F ₁₇ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₉ F ₁₉ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₁₀ F ₂₁ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, (CF ₃ ) ₂ CF(CF ₂ ) ₈ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH. In this case, it is preferred to use C ₆ F ₁₃ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₇ F ₁₅ CH ₂ CH ₂ OCH ₂ CH(OH) containing a linear perfluoroalkyl group. CH ₂ OH, C ₈ F ₁₇ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₉ F ₁₉ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH, C ₁₀ F ₂₁ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH.

The fluorine-containing alcohol-based compound and the fluorine-containing diol compound (hereinafter abbreviated as a fluorine-containing alcohol-based compound. diol compound) are reacted with a polyisocyanate which is a raw material of the thermoplastic polyurethane-based elastomer. A polyisocyanate which is a constituent component may remain in the film containing the thermoplastic polyurethane elastomer, and the polyisocyanate may become a catalyzed poison of the addition-form liquid polyoxyethylene rubber to suppress hardening. According to the above situation, if the thermoplastic polyurethane compound is mixed with fluorine-containing alcohol compound. The diol compound reacts with the polyisocyanate to bond the perfluoroalkyl group to the main backbone of the elastomer to eliminate catalogue toxicity. By this action, if the composition of the thermoplastic elastomer 2 is mixed with a fluorine-containing alcohol compound. The film formed by the diol compound can be destroyed by the aging treatment at 40 ° C for more than 3 days, and the curing of the addition-form liquid polyoxyethylene rubber composition does not inhibit hardening. A gel-like adhesive remains on the surface of the molded article. Therefore, in the film for release film containing the thermoplastic elastomer 3 component composition of the present invention, the effect of shortening the aging time, that is, shortening the preparation time, reducing the space necessary for aging, and reducing the energy necessary for aging can be exhibited. cost.

Such a group selected from the group consisting of fluorine-containing alcohol compounds and fluorine-containing diol compounds The compounding amount of one or a plurality of compounds in the group is in the range of 0.05 to 5.0 parts by mass, preferably in the range of 0.1 to 4.0 parts by mass, based on 100 parts by mass of the thermoplastic elastomer 2 component composition. More preferably, it is set within the range of 0.1 to 3.0 parts by mass. If the amount of the mixture is less than 0.05 parts by mass, the effect of mixing cannot be exerted. Further, even if it is more than 5.0 parts by mass, the effect is not increased, and the fluorine-containing alcohol-based compound can be confirmed. The diol compound remains unreacted and overflows on the surface of the film to contaminate the surface of the molded article.

If the above fluorine-containing alcohol compound. When the diol compound is mixed with the thermoplastic elastomer 2 component composition, smoothness is imparted to the surface of the film. Therefore, it is possible to smoothly carry out the transfer of the release film in the molding apparatus and the contact with the mold. When the release film is wrinkled, the peeling property of the polyoxyethylene rubber composition used as the sealing material can be improved.

a compound which can react with the polyisocyanate remaining in the above thermoplastic polyurethane elastomer, in addition to the above-mentioned fluorine-containing alcohol compound. There are many kinds of the diol compound, and examples thereof include a compound having a hydroxyl group in a molecule such as an alcohol compound or a diol compound, or a compound having a carboxylic acid in the molecule. These compounds can replace the fluorine-containing alcohol compounds within the scope of the characteristics of the present invention. A diol compound is used.

In the thermoplastic elastomer 2 component composition and the three component composition (hereinafter collectively referred to as a thermoplastic elastomer composition), other thermoplastic elastomers can be blended without departing from the characteristics of the present invention. Examples of the thermoplastic elastomer include a polyester elastomer, a polyamide-based elastomer, a polyvinyl chloride elastomer, a styrene elastomer, and an olefin elastomer.

In the above thermoplastic elastomer composition, a lubricant such as a polyethylene wax or a guanamine wax, an anti-caking agent such as cerium oxide, a phenol antioxidant, or a phosphorus system may be mixed in a range not degrading the characteristics of the present invention. Antioxidants, etc.

The film for release film comprising the thermoplastic elastomer composition of the present invention can be preferably used in the form of a single layer film, or can be formed with a film comprising a thermoplastic resin or other thermoplastic elastomer, without departing from the characteristics of the present invention. Use as a multilayer film above the layer. In the case of forming a multilayer film, the film comprising the thermoplastic elastomer composition of the present invention may be formed into a release layer in contact with the polyoxyxene rubber. Examples of the thermoplastic resin include polybutylene terephthalate resin, polyethylene terephthalate resin, cyclic polyolefin resin, syndiotactic polystyrene resin, polymethylpentene resin, and polymethylation. A methyl acrylate resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl acetate resin, an acrylonitrile butadiene styrene resin, an acrylonitrile styrene resin, or the like. Examples of the other thermoplastic elastomer include a polyester elastomer, a polyamide-based elastomer, a polyvinyl chloride-based elastomer, a styrene-based elastomer, and an olefin-based elastomer. Moreover, as another material, an ethylene-type copolymer rubber etc. are mentioned, for example. As a method of forming the multilayer film, for example, a conventionally known method such as a co-extrusion method, an extrusion lamination method, or a coating method can be appropriately selected and used.

In the release film of the present invention, the tensile modulus of the film measured in the film longitudinal direction (MD) and film is measured in accordance with JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. The lateral direction (TD) is in the range of 10.0 to 500 N/mm ² . The tensile elastic modulus is preferably in the range of 30.0 to 450 N/mm ² , more preferably in the range of 50.0 to 400 N/mm ² . When the tensile modulus of elasticity is less than 10.0 N/mm ² , it is confirmed that when the release film is taken out from the wound body in the mold forming apparatus, the tension of the film is weak and slack occurs. In the case where the tensile modulus of elasticity exceeds 500 N/mm ² , it is confirmed that the film is not stretched and is not closely adhered to the mold when the release film is suctioned by vacuum in the mold.

In the release film of the present invention, the 50% modulus (50% Mo) of the film measured at a temperature of 23 ° C and a tensile speed of 100 mm / min in accordance with JIS Z 1702 is in the longitudinal direction of the film ( The ratio (MD) / (TD) in the transverse direction (TD) of the film to the film is in the range of 0.90 to 1.20, preferably in the range of 0.95 to 1.20. (MD) / (TD) is not less than 0.90 in the film formed by the extrusion molding method. When it is assumed that (MD)/(TD) exceeds 1.20, it is confirmed that wrinkles are generated in the film when the release film is supplied to the mold in the mold forming apparatus.

In the film for release film of the present invention, 50% modulus (50% Mo) and 100% modulus of the film measured under the conditions of a temperature of 23 ° C and a tensile speed of 100 mm / min in accordance with JIS Z 1702 The ratio of (100% Mo) (100% Mo) / (50% Mo) is in the range of 1.00 to 1.60 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film, preferably in the range of 1.00 to 1.50. Inside. If it is assumed that (100% Mo) / (50% Mo) is less than 1.00, the following problem can be confirmed: since the stress increase accompanying the extension of the film does not occur, the uniform film extension cannot be obtained and is utilized in the mold. Wrinkles are generated when the vacuum is attracted to the film for release. Further, when (100% Mo) / (50% Mo) exceeds 1.60, it is confirmed that the stress increase accompanying the elongation of the film is large, and the film cannot be extended to the extent that the release film is in close contact with the inner surface of the mold. Bad situation.

In the release film of the present invention, the tensile elongation of the film measured in the film longitudinal direction (MD) and the film transverse direction measured in accordance with JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. The direction (TD) is more than 350%. The tensile elongation is preferably 400% or more. When the tensile elongation is less than 350%, it is confirmed that the film is cut at the edge of the mold when the film for suction release is sucked by vacuum in the mold.

The thermoplastic elastomer 2 component composition of the present invention can be produced by the method (1), that is, the thermoplastic polyurethane-based elastomer and the thermoplastic fluororesin are less than the thermoplastic polyurethane-based elastomer. After stirring and mixing at the temperature of the melting point of the body, the mixture is melted and kneaded at a temperature higher than the melting point of the thermoplastic polyurethane elastomer.

Further, as another method, it can be produced by the method (2), that is, a thermoplastic polyurethane elastomer, a thermoplastic fluororesin, and a fluorine-containing alcohol compound. The diol compound is stirred and mixed at a temperature not lower than the melting point of the thermoplastic polyurethane elastomer, and then melt-kneaded at a temperature higher than the melting point of the thermoplastic polyurethane elastomer. As another method, the method can be produced by the method (3), that is, the thermoplastic polyurethane resin is stirred and mixed with the thermoplastic fluororesin, and then the melting point of the thermoplastic polyurethane elastomer is used. Adding a fluorine-containing alcohol compound to the above temperature melting. The diol compound is melted and kneaded. These methods (1), (2), and (3) can be appropriately selected and used.

Further, a thermoplastic polyurethane resin is stirred and mixed with a thermoplastic fluororesin, and a fluorine-containing alcohol compound is added thereto. Mixing and mixing of the diol compound can be carried out using a tumble mixer, a Henschel mixer, and a belt type It is carried out by a known mixer such as a mixer or a universal mixer.

The production of the thermoplastic elastomer 2 component composition of the above (1) and the thermoplastic elastomer 3 component composition of the above (2) are produced by using a single-axis extruder and a double shaft by using the stirring mixture produced by the above method. An extruder such as an extruder is melted and kneaded. The temperature of the extruder in the case of producing the thermoplastic elastomer 2 component composition and the three component composition is not less than the melting point of the thermoplastic polyurethane elastomer, and 240 ° C or less.

Further, in the case of the above (3), the molten mixture of the thermoplastic polyurethane elastomer and the thermoplastic fluororesin is melted in an extruder such as a single-screw extruder or a twin-screw extruder. , adding fluorine-containing alcohol compounds. The diol compound may be melt-kneaded to prepare a thermoplastic elastomer 3 component composition. In the case of producing the thermoplastic elastomer 3 component composition, the temperature of the extruder is not less than the melting point of the polyurethane elastomer, and 240 ° C or less.

When a thermoplastic elastomer composition is produced by using an extruder such as a single-screw extruder or a twin-screw extruder, it may be replaced in the extruder by inert gas replacement as in the case of forming a film as described below. The melt kneading is carried out in an inert gas atmosphere formed by air in a gap between the compositions.

Usually, the thermoplastic elastomer composition is processed into a powder, granule or pellet by a pulverizer or a cutter.

The film for release film containing the above thermoplastic elastomer composition can be formed, for example, by a conventionally known method such as a melt extrusion method or a melt casting method.

In the following examples, a method of forming a release film by a melt extrusion method using a T die is exemplified.

The film for release film obtained by such a method is obtained by using an extruder such as a single-axis extruder or a twin-screw extruder, and is replaced by nitrogen depending on the characteristics of the thermoplastic elastomer composition. The molding material of the thermoplastic elastomer composition is melted and kneaded in an environment of air in the gap between the extruder and the molding material, and the lip portion of the front end of the T die disposed at the front end of the extruder is melted and extruded. The release film is directly clamped between the pressure roller and the cooling roller in the extractor and cooled, or is inserted and cooled by inserting or separating the separator from the pressure roller side and the cooling roller side, and then cooling. The coiler is sequentially taken up to the take-up tube.

Fig. 3 is a view showing a schematic configuration of a film production apparatus for producing a release film by the above method. 4 is a cross-sectional view showing the periphery of a material input funnel of the film manufacturing apparatus shown in FIG. 3. In FIG. 3, the film manufacturing apparatus roughly comprises a material input funnel 2, an extruder 1, a T die 7, a extractor 11, and a coiler 15. The material input funnel 2 is formed by inputting a molding material. As shown in FIG. 4, the material supply funnel 2 is connected to the extruder 1, and the nitrogen gas supply pipe 3 is inserted through the spacer 3a. Further, the nitrogen gas supply pipe 3 is bent so as to extend along the substantially central axis of the material inlet port 1c, and the tip end thereof is extended to the vicinity of the outer circumference of the extrusion screw 1a in the extruder 1. The oxygen contained in the molding material supplied from the material input funnel 2 or the extruder 1 is mixed and stirred by the extrusion screw 1a of the extruder 1 to be supplied to the nitrogen gas supply pipe 3. Replace with nitrogen.

The extruder 1 mixes and stirs the molding material by the extrusion screw 1a, and conveys it in the direction of the arrow B, and is assembled by the electrothermal mechanism (not shown) incorporated in the cylinder 1b of the extruder 1. The forming material is heated and melted. With the above The molding material which is melted and conveyed in this manner is conveyed to the filtering mechanism 5 via the connecting pipe 4 shown in FIG. Then, the unmelted molding material is separated by the filtering mechanism 5, and the molten molding material is sent to the gear pump 6. In the gear pump 6, the molten molding material is extruded into the T-die 7 while increasing the pressure of the molten molding material. In the T die 7, the melt-molded material is extruded under a specific pressure, and a film 8 having a specific thickness and a specific width is formed from the lip portion 7a of the T-die 7. The film 8 formed as described above is taken up to the outer circumferential surface of the cooling roll 10 of the extractor 11, and is adjusted to a specific thickness by the pressure roller 9, and further cooled and solidified, and transported to the roll by the transfer roller pairs 12 and 13. Take the machine 15 inside.

In the coiler 15, the film 8 is guided by the guide rolls 15a, 15b, 15c and wound up by the take-up tube 16. Further, a thickness measuring device 14 is disposed between the pair of conveying rollers 12 and 13 and the guide roller 15a, and the circumference of the cooling roller 10 is adjusted and controlled based on the thickness measured by the thickness measuring device 14 so as to have a desired thickness. speed. Thereby, the above-mentioned release film is formed.

The release film may be formed into a surface shape of the film in accordance with the surface shape necessary for the molded article. For example, when the surface of the LED or the like is a mirror surface, the surface of the release film may be formed into a mirror surface. In addition, since fine irregularities are formed on the surface of the IC or the LSI, the surface of the release film may be formed into fine irregularities.

In the case where the surface of the release film is mirror-finished, the surface of the metal cooling roll is previously mirror-finished, and the film for release film in a molten state is pressure-bonded to the cooling roll by a pressure roller. The surface of the release film can be adjusted to a mirror surface. Moreover, in the case of using a separator, a mirror-polished PET (polyethylene terephthalate, polyethylene terephthalate) may be used. A diester) film or an OPP (oriented polypropylene) film is used as a separator and a method of transferring the surface thereof.

When fine irregularities are formed on the surface of the release film, fine irregularities are formed on the outer peripheral surface of the metal cooling roll in advance, and the release film in a molten state is pressure-bonded to the film by a pressure roller. In the case of cooling the rolls, fine irregularities formed on the outer peripheral surface of the cooling roll may be transferred onto the surface of the release film. Further, in the case of using a separator, a method of using a surface-polished PET film or OPP film as a separator and transferring the surface thereof may be employed.

When the surface of the film for release film is formed into a mirror surface, the surface may be appropriately formed in such a manner that the surface roughness thereof is 0.6 mm/sec in accordance with JIS B0601-2001, and the critical value is 0.8. The arithmetic mean roughness Ra measured under the condition of mm and the evaluation length of 8.0 mm was 0.10 or less, and the maximum height roughness Rz was 1.00 or less. When the arithmetic mean roughness Ra is 0.10 or less and the maximum height roughness Rz is 1.00 or less, the surface of the molded article on the surface of the transfer release film becomes smooth.

In the case where the fine unevenness is formed on the surface of the release film, the arithmetic mean roughness Ra measured in the same manner as described above is 0.5 or more, and the maximum height roughness Rz is 5.00 or more. The surface is fine.

The thickness of the release film of the present invention 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 depending on the shape of the mold to be used. When it is assumed that the thickness of the release film is less than 5 μm, it may occur when the film is used to follow the mold, the release film is thinned and broken, or the film is broken due to the pressure of the sealing material. Therefore And not good. In addition, when the thickness of the release film exceeds 500 μm, the thickness thereof is hindered, and the mold having a fine structure cannot be followed, and the complicated shape of the mold is not transferred to the molded article, which is not preferable.

[Examples]

Hereinafter, Examples 1 to 21 of the release film of the present invention will be described with reference to Fig. 5 (Table 1), Fig. 6 (Table 2), and Fig. 7 (Table 3). The materials of the release films of the examples 1 to 21, the physical properties of the release film, and the evaluation are shown in Fig. 5 (Table 1), Fig. 6 (Table 2), and Fig. 7 (Table 3). Further, the film for release film of the present invention is of course not limited to Examples 1 to 21.

Here, the thermoplastic polyurethane elastomer 1, the thermoplastic polyurethane elastomer 2, the thermoplastic fluororesin 1, the thermoplastic fluororesin 2, and the fluorine-containing alcohol shown in Tables 1 to 3 Compound. Diol compound 1 and fluorine-containing alcohol compound. As the diol compound 2, the materials shown below were used. Here, the first and second notes of the above-mentioned materials indicate different types.

(Thermoplastic polyurethane-based elastomer 1)

Miractran E598PNAT: trade name, manufactured by Nippon Polyurethane Industry, JIS A hardness of 98, Vickers softening temperature of 141 ° C

(Thermoplastic polyurethane-based elastomer 2)

Miractran E559PNAT: trade name, manufactured by Nippon Polyurethane Industry, JIS D hardness 59, Vickers softening temperature 143 ° C

(thermoplastic fluororesin 1)

Dyneon THV500GZ: trade name, manufactured by Sumitomo 3M, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, melting point 165 ° C

(thermoplastic fluororesin 2)

Dyneon THV610GZ: trade name, manufactured by Sumitomo 3M, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, melting point 185 ° C

(Fluorinated alcohol compound. diol compound 1)

Eftop MF-100: trade name, manufactured by Mitsubishi Materials, 3-(2-perfluorohexylethoxy)-1,2-dihydroxypropane (C ₆ F ₁₃ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ OH)

(Fluorinated alcohol compound. diol compound 2)

Eftop PDFOH: trade name, manufactured by Mitsubishi Materials, pentafluorooctyl alcohol (C ₇ F ₁₅ CH ₂ OH)

Hereinafter, the production of the release film, the peelability, the heat resistance, the mold shape transfer property, the presence or absence of the gel-like adhesive, the surface smoothness, and the practicability will be described in detail based on Tables 1 to 3. Further, the above contents of Tables 1 to 3 are also applied to Comparative Examples 1 to 7 of Fig. 8 (Table 4).

(production of release film)

Supplying the thermoplastic elastomer composition to 40 mm, L/D=25 single-axis extruder (manufactured by IKG), using a full-thread extrusion screw with a compression ratio of 2.5, melt-kneading at a cylinder temperature of 180 ° C to 210 ° C, The mold was continuously extruded from a T-die having a width of 400 mm at a mold temperature of 210 ° C to 220 ° C. In the extracting machine, the matte-finished PET film is used as a separator from the side of the pressure-bonding roll, and the mirror-polished PET film is supplied as a separator from the cooling roll side to the extruded release film, and the crimping is performed on the crimping film. The roller and the cooling roller are cooled and cooled, and the both ends are cut by a cutter in a coiler, and the release film is taken up to the take-up tube, thereby using the thicknesses shown in Tables 1 to 3. (Thickness (μm) in Tables 1 to 3) A release film having a width of 250 mm and a length of 50 m was produced. The film for detachment was aged in an environment of 40 ° C in the examples (Tables 1 to 3) and Comparative Examples (Table 4). After the completion of the aging, the release film of the separator and the mirror-polished PET film were peeled off, and the release film was re-wound to obtain a release film for evaluation.

(method of evaluation)

In the evaluation, the mold having the lens shape shown in FIG. 1 was used, and the release film was adsorbed on the mold, and the polyoxyethylene rubber composition was added dropwise to perform hot press forming, and the peelability, heat resistance, and mold shape transfer were evaluated. Sex, gel-like adhesive presence and surface smoothness. Further, in Fig. 1, reference numeral 20 denotes a bullet-type LED lens, and reference numerals 21a, 21b denote wires. The diameter of the cannonball type LED lens 20 is set, for example, 6 mm, set the height to 4 mm, for example. 2 shows a die-casting mold (indicated by reference numeral 30 in the drawing), (a) is a plan view, and (b) is a cross-sectional view taken along line AA of (a). A lens forming recess (indicated by symbol 31 in the figure) corresponding to the shape of the bullet-type LED lens is provided on the surface of the mold. The distance between the central axes of the adjacent lens forming recesses is, for example, 8 mm.

In the mold shown in Fig. 2, the release film is placed on the mold side and the mirror surface is on the air side, and the release film is sucked by vacuum to adsorb the release film onto the mold. Then, a polyoxyethylene rubber composition OE-6636 (trade name, manufactured by Dow Corning-Toray Co., Ltd.) was dropped on the release film, and a hard chrome-plated flat mold was placed on the film, and two molds were used. Clamp and perform hot press forming. Evaluation of the release property of the formed release film and the cured polyoxymethylene rubber, the heat resistance of the release film, the mold transfer property to the cured polyoxyethylene rubber, and the gel-like adhesion The presence or absence of the object and the smoothness of the surface. The hot press forming was carried out under the conditions of a temperature of 140 ° C and a pressure of 10 kg / cm ² for 5 minutes.

(peelability)

The evaluation of the peeling property (in the case of the evaluation and the releasability in Tables 1 to 3) is a case where the formed polyoxyxene rubber composition is peeled off without leaving the film for release film, and is referred to as "good". The case where the silicone rubber composition partially broke and remained on the release film was expressed as "NG".

(heat resistance)

Evaluation of heat resistance (in terms of evaluation and heat resistance in Tables 1 to 3), the film for release of the formed polyoxyxene rubber composition was visually observed, and the film shape was maintained without melting or melting. In the case of "Good", the case where the release film is melted or melted is indicated as "NG".

(die shape transferability)

The mold shape transfer property (in terms of evaluation, mold shape transfer property in Tables 1 to 3) was measured by measuring the size of the formed polyoxyethylene rubber composition. The evaluation criteria of the height of the lens are set to be smaller than the thickness of the film for the release of 4 mm from the hole depth of 4 mm, and then the range of 0.1 mm or less, that is, ((the thickness of the film for 4-release film) - 0.1) mm the above. The case where 25 lenses are within the reference is expressed as "Good", and even if one of the shapes that does not satisfy the reference is expressed as "NG".

(The presence or absence of gelatinous adhesives)

The presence or absence of a gel-like adhesive (in Tables 1 to 3, the evaluation, the presence or absence of a gel-like adhesive) is a combination of a silicone rubber formed by a finger touch. The surface of the object and confirm the adhesion. There was no stickiness on the surface of the polyoxymethylene rubber, and the case where no fingerprint was attached when the finger was left was evaluated as "Good", and the surface was sticky, and the fingerprint was attached when the finger left, and it was evaluated as "NG".

(surface smoothness)

Surface smoothness (in Tables 1 to 3, evaluation, surface smoothness) was evaluated by visually observing the surface state of the formed polyoxyethylene rubber composition. The case where no unevenness or wrinkles were formed on the surface of the polyoxymethylene rubber was indicated as "Good", and the case where irregularities or wrinkles were generated was indicated as "NG".

(practical)

The usability was confirmed and evaluated by resin molding using a die-casting apparatus. Specifically, OE-6636 (trade name, manufactured by Dow Corning-Toray Co., Ltd.) was used as the polyoxyxene rubber in the G-LINE manual press (trade name) manufactured by Apic Yamada Co., Ltd. as a molding apparatus. The composition was visually confirmed for practicality.

Evaluation of practicability (in the case of evaluation and practicability in Tables 1 to 3), the following state is indicated as "Good", and the case where any of the cases is defective is indicated as "NG": in the mold forming apparatus When the film for release film is conveyed, the film is not loosely supplied, and wrinkles are not formed on the film during the adsorption, and the peeling property of the release film and the polyoxyethylene rubber composition after the hot press forming is good, and the cured polyoxylized oxygen The surface of the rubber composition has no irregularities or wrinkles, is smooth and has no gel-like adhesive, is not broken or melted on the release film, and remains of the polyoxymethylene rubber composition, and has no dirt on the mold.

According to this result, in Comparative Example 1 (refer to Table 4), thermoplastic elasticity was employed. The blending amount of the thermoplastic fluororesin of the bulk 2 component composition was set to be less than the blending amount of the present invention, and as a result, peeling property could not be obtained, and the practicality was not satisfied. In Comparative Example 2 (see Table 4), the thermoplastic fluororesin of the thermoplastic elastomer 2 component composition was blended in excess of the blending amount of the present invention, and as a result, wrinkles were generated when the film was adsorbed in the mold and transferred onto the surface of the molded article. , surface smoothness cannot be obtained. In Comparative Example 3 (refer to Table 4), the thermoplastic fluororesin composition of the thermoplastic elastomer 3 component composition was mixed with the fluorine-containing alcohol compound. The blending amount of the diol compound was set to be less than the blending amount of the present invention, and as a result, peeling property could not be obtained, and the practicality was not satisfied. In Comparative Example 4 (refer to Table 4), the thermoplastic fluororesin of the thermoplastic elastomer 3 component composition and the fluorine-containing alcoholic compound were mixed in excess of the compounding amount of the present invention. As a result of the diol compound, when the film is adsorbed in the mold, wrinkles are generated and transferred onto the surface of the molded article, surface smoothness cannot be obtained, and the oil overflowing from the release film adheres to the surface of the molded article. on. In Comparative Example 5 (see Table 4), the thickness of the ETFE film Aflex (trade name) manufactured by Asahi Glass Co., Ltd. was 100 μm, and the mold shape transfer property was inferior, and practicality could not be obtained. In Comparative Example 6 (see Table 4), the thickness of the ETFE film Aflex (trade name) manufactured by Asahi Glass Co., Ltd. was 25 μm, and as a result of comparison, when the film was adsorbed in the mold, the film was broken and practicability was not obtained. In Comparative Example 7 (refer to Table 4), Hytrel 5577 (trade name) manufactured by DuPont-Toray Co., Ltd., a polyester-polyether copolymer, and a thermoplastic elastomer having a D hardness of 55 and a Vickers softening temperature of 192 ° C were contained. A release film having a thickness of 50 μm was used as a comparison object. Wrinkles are formed on the surface of the molded article comprising the polyoxyethylene rubber composition, and the surface smoothness is poor, and gelatinous adhesive is also present. Unable to get practicality.

On the other hand, it is understood that the release film of Examples 1 to 21 (Tables 1 to 3) of the present invention can obtain not only peelability but also heat resistance, and excellent mold form transferability, and no gel-like adhesion remains. The surface is smoothed and imparted with practicality. According to the above, according to the present invention, it is possible to obtain a film for release film which is excellent in peelability from a molded article obtained by molding a sealing material, and which can obtain a molded article excellent in shape and surface properties.

The present invention has been described above using the embodiments, but the technical scope of the present invention is of course not limited to the scope described in the above embodiments. Those skilled in the art will recognize that various modifications or improvements can be made to the above-described embodiments. Further, it is understood that such changes or improvements can be included in the technical scope of the present invention.

1‧‧‧Extrusion machine

2‧‧‧Material input funnel

3‧‧‧Nitrogen supply pipe

4‧‧‧Connecting tube

5‧‧‧Filter

6‧‧‧ Gear pump

7‧‧‧T mode

7a‧‧‧Lip

8‧‧‧ film

9‧‧‧Crimp roller

10‧‧‧Cooling roller

11‧‧‧ extractor

12, 13‧‧‧Transport roller pair

14‧‧‧ Thickness measuring device

16‧‧‧Winding tube

17a, 17b‧‧‧Send rolls

18a, 18b‧‧‧ dividers

20‧‧‧ cannonball type LED lens

21a, 21b‧‧‧ wires

30‧‧‧Mold casting mould

31‧‧‧ lens forming recess

Fig. 1 is a side view of a bullet-type LED lens according to an embodiment of the present invention.

Fig. 2 is a plan view showing a mold of a cannonball type LED lens according to an embodiment of the present invention. (b) A cross-sectional view taken along line A-A of Fig. 2(a) of a mold for a bullet-type LED lens according to an embodiment of the present invention.

Fig. 3 is a view showing a schematic configuration of a film production apparatus for a release film according to an embodiment of the present invention.

Fig. 4 is a cross-sectional view showing the vicinity of a material input funnel of the film production apparatus shown in Fig. 3 according to an embodiment of the present invention.

Fig. 5 is a view showing Table 1 showing an embodiment of the present invention, and shows Examples 1 to 7, and their physical properties and evaluation.

Figure 6 is a table 2 showing an embodiment of the present invention, and shows Example 8 To 14, and its physical properties, evaluation map.

Fig. 7 is a view showing Table 3 showing an embodiment of the present invention, and shows Examples 15 to 21, and their physical properties and evaluation.

Fig. 8 is a view showing Table 4 showing a comparative example of the present invention, and shows Comparative Examples 1 to 7, and their physical properties and evaluation.

Claims (10)

A release film comprising 100 parts by mass of a thermoplastic polyurethane elastomer having a hardness of 70 or more and a Vickers softening temperature of 100 to 180 ° C, in an amount of from 1 to 400 parts by mass. The thermoplastic elastomer 2 component composition containing a thermoplastic fluororesin is included in the range. The release film according to claim 1, wherein the thermoplastic fluororesin is a thermoplastic tetrafluoroethylene copolymer having a melting point of 140 ° C or more and 240 ° C or less. The release film according to claim 1 or 2, which comprises, in an amount of 0.05 to 5.0 parts by mass, based on 100 parts by mass of the thermoplastic elastomer 2 component composition, containing a fluorine-containing alcohol compound and fluorine A thermoplastic elastomer 3 component composition of one or a plurality of compounds of a group consisting of diol compounds. The release film according to claim 2 or 3, wherein the fluorine-containing alcohol compound is a compound represented by the formula (A), and the fluorine-containing diol compound is a compound represented by the formula (B), Rf ₁ (CH ₂ ) _m OH (...) (wherein Rf ₁ represents a linear or branched perfluoroalkyl group or a perfluoroalkyl ether group having a carbon number of 3 to 20, and m is 1~ An integer of 5) Rf ₂ (CH ₂ ) _n OCH ₂ CH(OH)CH ₂ OH (...) (wherein Rf ₂ represents a linear or branched perfluoroalkane having a carbon number of 3 to 20 Base, n is an integer of 1 or 2.) The film for release film according to any one of claims 1, 2, 3, and 4, wherein the thermoplastic elastomer 2 component composition and the three component composition further comprise a lubricant, an anti-caking agent, a phenolic antioxidant, One of phosphorus antioxidants Or a plurality of additives. The film for release film according to any one of claims 1 to 5, wherein the tensile modulus of the film is in the range of 10 to 500 N/mm ² in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. Inside. The film for release film according to any one of claims 1 to 6, wherein a ratio of a 50% modulus (50% Mo) of the film in a longitudinal direction (MD) of the film to a transverse direction (TD) of the film (MD) / ( TD) is in the range of 0.9 to 1.2. The release film according to any one of claims 1 to 7, wherein a ratio of a 50% modulus (50% Mo) of the film to a 100% modulus (100% Mo) (100% Mo) / (50% Mo It is in the range of 1.0 to 1.6 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. The release film according to any one of claims 1 to 8, wherein the tensile elongation of the film exceeds 350% in both the longitudinal direction (MD) and the transverse direction (TD) of the film. The release film according to any one of claims 1 to 9, which comprises a multilayer film comprising a film comprising a thermoplastic resin or a film of a thermoplastic elastomer other than the thermoplastic polyurethane-based elastomer. Composition.