KR20120111959A - Mold release film - Google Patents

Abstract

PURPOSE: A releasing film is provided to have excellent detachability from a mold or molded product, to have excellent shape transcription and surface flatness, and to have excellent heat durability at 140 °C. CONSTITUTION: A releasing comprises a thermoplastic elastomer composition which has a polyurethane-based elastomer with a JIS A hardness of 70 or over, Vicat softening temperature of 100-180 °C. The thermoplastic elastomer compostion comprises 0.05-5.0 parts by weight of a fluorine-based surfactant based on 100.0 parts by weight of the polyurethane-based elastomer. The modulus of tensile elasticity of the film along a machine direction and a transverse direction are all within 10-500 N/mm^2.

Description

Release film {MOLD RELEASE FILM}

This invention relates to the film for mold release used at the time of resin mold shaping | molding of an optical semiconductor element or a semiconductor element, especially at the time of resin mold shaping | molding of an LED lens.

For example, optical semiconductor elements such as LEDs, photoisolators, phototransistors, photodiodes, CCDs, CMOS, and semiconductor elements such as transistors, ICs, LSIs, and ultra-LSIs may be formed of a silicone resin composition or an epoxy resin composition as a sealing material. It is sealed by resin mold molding.

A mold shaping | molding apparatus is used for sealing the above-mentioned optical semiconductor element and a semiconductor element, and the sealing material containing a silicone resin composition or an epoxy resin composition is injected into a mold metal mold | die, and shape | molded.

As a method of releasing a mold metal mold | die and a molded article, the method of interposing the film for mold release between a mold metal mold and mold resin, for example is utilized (for example, refer patent document 1). The release film is supplied to a roll-to-roll in a mold molding apparatus, enters a mold mold temperature controlled at a molding process temperature, is sucked under vacuum, and adhered to the mold mold, and then the mold resin is filled. When the mold die is opened at a time when the mold resin is cured after a certain time, the molded article is released from the release mold film in a state where the mold release film is attracted to the mold die. As the release film, for example, a single layer film containing an ethylene tetrafluoride-ethylene copolymer resin (ETFE resin) of a thermoplastic fluororesin or an tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP resin) is used (for example, , Patent Document 2).

However, when such a release film is used for molding an LED lens having a silicone resin composition as a mold resin, the release film is vacuumed for a shell-shaped lens shape having a bottom surface of about 6 mm and a height of about 4 mm, for example. There is a problem that it may not be stretched even if it is attracted, and even if it is stretched, it does not come into close contact with the mold mold and there is a problem that the LED lens according to the design dimensions cannot be obtained. In addition, when the thickness of the release film is reduced to improve elongation, there is a problem that the release film is broken at the edge of the mold die when suctioned by vacuum.

Moreover, the method of using the film containing the resin composition containing crystalline aromatic polyester containing butylene terephthalate as a crystal component is known as a film for mold release (for example, refer patent document 3).

However, as shown in patent document 3 as a film for mold release, when the film containing the resin composition containing crystalline aromatic polyester containing butylene terephthalate is used for shaping | molding of an LED lens, if the film for mold release is attracted by vacuum, Although closely adhered to the mold, since the film is stretched beyond the yield point, there is a problem that the release film is partially thinned, and irregularities and wrinkles occur on the surface of the molded LED lens. Therefore, there is no film which can be used suitably as a film for mold release in the resin mold shaping | molding of LED lens.

Japanese Patent Laid-Open No. 8-142105 Japanese Patent Laid-Open No. 2001-310336 Japanese Patent Publication No. 2007-224311

This invention is made | formed in view of the above, It is excellent in peelability with a mold metal mold | die and a molded article, It is excellent in the mold-transfer property which the shape of a mold metal mold | die is transferred to a molded article according to a design dimension, and the surface smoothness of a molded article is obtained, Furthermore, it aims at providing the film for mold release which also has heat resistance in the use temperature of about 140 degreeC.

This object is achieved by the present invention of the following (1) to (11).

(1) A release film comprising a thermoplastic elastomer composition containing, as a main component, a polyurethane-based elastomer having a JIS A hardness of 70 or more and a vicat softening temperature of 100 to 180 ° C. alone or a polyurethane-based elastomer.

(2) The film for release according to (1), wherein the polyurethane-based elastomer is a thermoplastic polyurethane-based elastomer obtained by reaction of three components of a polyisocyanate, a polyol, and a chain extender.

(3) In the above (2), the polyol has a number average molecular weight of 500 to 10000 belonging to the group consisting of polyester polyol, polyesteramide polyol, polycarbonate polyol, polyether polyol, polyether ester polyol and polyolefin polyol Release film, characterized in that one or plural selected from phosphorus polymer polyol.

(4) The film for release according to (2) or (3), wherein the chain extender is selected from active hydrogen-containing compounds having a number average molecular weight of less than 500 belonging to low molecular polyols, low molecular polyamines, and low molecular amino alcohols.

(5) The film for release according to any one of (1) to (4), wherein the thermoplastic elastomer composition is a composition containing a fluorine-based surfactant in the range of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the polyurethane elastomer. .

(6) The release film according to (5), wherein the fluorine-based surfactant is a perfluoroalkylsulfonic acid derivative compound having a decomposition temperature of 300 ° C or higher at a melting point of 250 ° C or lower.

(7) The release film according to any one of (1) to (6), wherein the thermoplastic elastomer composition further includes one or a plurality of additives belonging to a lubricant, an antiblocking agent, an antioxidant, and a phosphorus antioxidant. .

(8) The film has any one of (1) to (7), wherein the tensile modulus of the film is in the range of 10 to 500 N / mm ² in both the film longitudinal direction (MD) and the film transverse direction (TD). Release film.

(9) The ratio (MD) / (TD) of the film longitudinal direction (MD) to the film transverse direction (TD) at 50% modulus (50% Mo) of the film according to any one of the above (1) to (8). ) Is in the range of 0.9 to 1.2, the release film.

(10) The ratio (100% Mo) / (50% Mo) of 50% Modulus (50% Mo) to 100% Modulus (100% Mo) of the film according to any one of (1) to (9) above is Release film, characterized in that both the film longitudinal direction (MD) and the film transverse direction (TD) is in the range of 1.0 to 1.6.

(11) The film for release according to any one of (1) to (10), wherein the tensile elongation of the film exceeds 350% in both the film longitudinal direction (MD) and the film transverse direction (TD).

According to the release film of this invention, it is excellent in peelability with a mold metal mold | die and a molded article, the mold transfer property which transfers the shape of a metal mold mold to a molded article according to a design dimension, and the surface smoothness of a molded article is obtained, May also have heat resistance.

1 is a side view of a shell type LED lens according to an embodiment of the present invention.
(A) It is a top view of the mold metal mold | die of the shell type LED lens which concerns on embodiment of this invention, (b) In FIG. 2 (a) of the mold metal mold | die of the shell type LED lens which concerns on embodiment of this invention. AA arrow cross section.
It is a figure which shows schematic structure of the film manufacturing apparatus for mold release which concerns on embodiment of this invention.
FIG. 4 is a cross-sectional view showing the periphery of the material injection hopper of the film production apparatus shown in FIG. 2 according to the embodiment of the present invention. FIG.

The inventors of the present invention conducted various studies to achieve the above object. Among the polyurethane-based elastomers, the polyurethane-based elastomer alone having JIS A hardness of 70 or more, specific gravity of 1.05 to 1.30, and vicat softening temperature of 100 to 180 ° C, or The release film containing the thermoplastic elastomer composition containing the polyurethane-based elastomer as a main component is excellent in peelability with a mold die or a molded article, and has excellent mold transfer property in which the shape of the mold die is transferred to the molded article according to design dimensions. It was clarified that the surface smoothness of the molded article can be obtained, and furthermore, the heat resistance can be provided.

Moreover, as a result of examination, by making a thermoplastic elastomer composition into the composition which contains a fluorine-type surfactant in the range of 0.05-5.0 mass part with respect to 100 mass parts of polyurethane-type elastomers, it discovered that it was more effective and came to complete this invention.

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

As the above-mentioned polyisocyanate, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'- Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylether 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, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Aromatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, and dodecane diisocyanate Aliphatic diisocyanates such as cyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogen Alicyclic diisocyanates such as added diphenylmethane diisocyanate, tetramethylxylene diisocyanate, norbornane diisocyanate methyl, biuret, dimer, trimer, dimer, trimer, carbodiimide, The adduct body etc. which are obtained by reaction of a uretonimine body, a bifunctional or more than polyfunctional, etc. and the said isocyanate are mentioned. Moreover, polyisocyanate which stabilized a part of isocyanate group by the block agent which has one active hydrogen in a molecule | numerator, such as methanol, n-butanol, benzyl alcohol, acetoacetate, ethyl (epsilon) -caprolactam, methyl ethyl ketone oxime, phenol, and cresol, also has Can be mentioned. These can be used 1 type or in mixture of 2 or more types.

The above-mentioned polyols are polymer polyols having a number average molecular weight of 500 to 10,000, and these include polyester polyols, polyesteramide polyols, polycarbonate polyols, polyether polyols, polyether ester polyols, and polyolefin polyols. These polymeric polyols can be used 1 type or in mixture of 2 or more types.

As polyester polyol and polyesteramide polyol, what is obtained by condensation reaction can be mentioned from polycarboxylic acid and a polyol, using a diamine or an amino alcohol in some cases.

Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid, phthalic acid alkyl esters, trimellitic acid, maleic acid, fumaric acid and itaconic acid. Moreover, what is obtained by ring-opening polymerization of cyclic esters, such as butyrolactone, a valerolactone, and a caprolactone, is also mentioned.

Examples of the polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 2 -Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 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-ethylene glycol, 2-n-eichoic acid-1,2-ethylene glycol, 2-n-octacoic acid-1 Ethylene oxide or propylene oxide adduct of ,, 2-ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol or bisphenol A, hydrogenated bisphenol A, 3-hydroxy-2,2-dimethylpropyl Low molecular polyols, such as 3-hydroxy-2, 2- dimethyl propionate, a trimethylol propane, glycerin, and pentaerythritol, are mentioned. As a diamine or an amino alcohol, low-molecular amino alcohols, such as low molecular polyamines, such as ethylenediamine, hexamethylenediamine, xylylenediamine, and isophoronediamine, monoethanolamine, diethanolamine, and triethanolamine, are mentioned, for example. . Furthermore, the lactone polyester polyol obtained by ring-opening polymerization of cyclic ester (lactone) monomers, such as (epsilon) -caprolactone and (gamma) -valerolactone, is mentioned as a low molecular polyol, a low molecular polyamine, and a low molecular amino alcohol as an initiator.

Examples of the polycarbonate polyol include low alcohol polyols used in the synthesis of the above-described polyester polyols, dealcoholization reactions such as diethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate, and dephenols. The thing obtained by reaction etc. are mentioned.

Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc. as an initiator with low molecular polyols, low molecular polyamines and low molecular amino alcohols used in the above polyester polyols. The ether glycol etc. and the polyether polyol which copolymerized these, Furthermore, the polyester ether polyol which used the above-mentioned polyester polyol and polycarbonate polyol as an initiator is mentioned.

As a polyether ester polyol, what is obtained by carrying out similarly to polyester polyol except for using a polyether for one part or all part of the polyol used for the condensation reaction at the time of obtaining the said polyester polyol is mentioned.

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

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

For the production of polyurethane-based elastomers, known production methods such as one shot method, prepolymer method, batch reaction method, continuous reaction method, kneader method, extruder method and the like can be used. .

As for the hardness of the polyurethane-type elastomer used for this invention, JISA hardness measured by the test method of JISK7111 is 70 or more. In addition, when it is 100 or more in JIS A hardness, D hardness is applied and it is preferable to make 70 or less of D hardness an upper limit. This JIS A hardness is preferably 80 or more, more preferably 90 or more. When JIS A hardness is less than 60, since rubber property becomes strong, when the conveyance of the film for mold release in a mold shaping | molding apparatus, there exists a problem that a film for mold release is extended and conveyance is not stabilized. On the other hand, when D hardness exceeds 70, there exists a problem that the gel derived from the three components of a polyisocyanate, a polyol, and a chain extender which are raw materials at the time of extrusion molding generate | occur | produces.

Vicat softening temperature of the polyurethane-type elastomer used for this invention is measured by the test method of JISK7206, and is the range of 100-180 degreeC. This vicat softening temperature becomes like this. Preferably it is 110-180 degreeC, More preferably, it is 120-180 degreeC, More preferably, it is the range of 130-180 degreeC. If the vicat softening temperature is less than 100 ° C., there is a problem of melting at the time of use. That is, heat resistance is not obtained. On the other hand, although the upper limit of the bicat softening temperature is 180 degreeC, the polyurethane-type elastomer which has a bicat softening temperature exceeding 180 degreeC was not obtained.

The fluorine-based surfactant in the present invention is a perfluoroalkylsulfonic acid derivative. Specific examples of the perfluoroalkyl sulfonic acid derivatives include potassium trifluoro methanesulfonic acid (CF ₃ SO ₃ K), sodium trifluoro methanesulfonic acid (CF ₃ SO ₃ Na), and trifluoro methanesulfonic acid lithium (CF ₃ SO ₃ Li). ), Potassium pentafluoroethane sulfonate (C ₂ F ₅ SO ₃ K), sodium pentafluoroethane sulfonate (C ₂ F ₅ SO ₃ Na), lithium pentafluoroethane sulfonate (C ₂ F ₅ SO ₃ Li), Heptafluoropropanesulfonic acid potassium (C ₃ F ₇ SO ₃ K), heptafluoropropanesulfonic acid sodium (C ₃ F ₇ SO ₃ Na), heptafluoropropanesulfonic acid lithium (C ₃ F ₇ SO ₃ Li), nonafluoro Perfluoro such as potassium robutane sulfonate (C ₄ F ₉ SO ₃ K), sodium nonafluorobutane sulfonate (C ₄ F ₉ SO ₃ Na), and lithium nonafluorobutane sulfonate (C ₄ F ₉ SO ₃ Li) Alkyl sulfonate is mentioned.

Further, bis (trifluoro methanesulfonyl) imide potassium salt ((CF ₃ SO ₂ ) ₂ NK), bis (trifluoro methanesulfonyl) imide sodium salt ((CF ₃ SO ₂ ) ₂ NNa), Bis (trifluoro methanesulfonyl) imideammonium salt ((CF ₃ SO ₂ ) ₂ NNH ₄ ), bis (trifluoro methanesulfonyl) imide lithium salt ((CF ₃ SO ₂ ) ₂ NLi), bis ( Pentafluoro ethanesulfonyl) imide potassium salt ((C ₂ F ₅ SO ₂ ) ₂ NK), bis (pentafluoro ethanesulfonyl) imide sodium salt ((C ₂ F ₅ SO ₂ ) ₂ NNa), Bis (pentafluoro ethanesulfonyl) imide ammonium salt ((C ₂ F ₅ SO ₂ ) ₂ NNH ₄ ), Bis (pentafluoro ethanesulfonyl) imide lithium salt ((C ₂ F ₅ SO ₂ ) ₂ NLi ), Bis (heptafluoro propanesulfonyl) imide potassium salt ((C ₃ F ₇ SO ₂ ) ₂ NK), bis (heptafluoro propanesulfonyl) imide sodium salt ((C ₃ F ₇ SO ₂ ) ₂ NNa), bis (nonafluorobutyl butane sulfonyl) imide potassium salt _{((C 4 F 9 SO 2} ) 2 NK), bis (nonafluorobutyl butane sulfonyl) is Sodium salt de _{((C 4 F 9 SO 2} ) 2 NNa), cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium _{(CF 2 (CF 2 SO 2} ) 2 NK), a cycloalkyl And perfluoroalkylsulfonimide salts such as -hexafluoropropane-1,3-bis (sulfonyl) imide sodium salt (CF ₂ (CF ₂ SO ₂ ) ₂ NNa).

Moreover, the ionic liquid which uses perfluoroalkyl sulfonic acid as an anionic species, the ionic liquid which uses bis (perfluoroalkylsulfonyl) imide as an anionic species, and the ionic liquid which uses bis (fluorosulfonyl) imide as an anionic species And ionic liquids using cyclohexafluoropropane-1,3-bis (sulfonyl) imide as an anionic species.

Among the above-mentioned perfluoroalkylsulfonic acid derivatives, compounds having a decomposition temperature of 300 ° C or higher at a melting point of 250 ° C or lower can be preferably used. Specific examples of these include potassium trifluoromethanesulfonate (CF ₃ SO ₃ K) and bis (trifluoro methanesulfonyl) imide potassium salt ((CF ₃ SO ₂ ) ₂ NK).

The fluorine-based surfactant is mixed with the polyurethane-based elastomer for the purpose of imparting lubricity to the release film. Since the lubricity is imparted to the film surface by the mixing of the fluorine-based surfactant, the conveyance of the release film in the mold forming apparatus is smoothed, the effect of preventing wrinkles of the release film when contacting the mold mold, and used as the mold resin. The effect of improving peelability with the silicone resin composition to be obtained is obtained. The mixing amount is in the range of 0.05 to 5.0 parts by mass of the fluorine-based surfactant based on 100 parts by mass of the polyurethane elastomer. When the amount of the mixture is less than 0.05 part by mass, the mixed effect is not expressed. On the other hand, even if it mixes exceeding 5.0 mass parts, an effect does not increase, and there exists a problem that a fluorine-type surfactant bleeds out and blooms out on the film surface, and contaminates the surface of a molded article.

The thermoplastic elastomer composition of the present invention can be mixed with other thermoplastic elastomers within a range that does not impair the characteristics of the present invention. Examples of the thermoplastic elastomers include polyester elastomers, polyamide elastomers, polyvinyl chloride elastomers, styrene elastomers, olefin elastomers, and the like. By co-extruding such another thermoplastic elastomer, it can also be set as an adhesive laminated film.

In the thermoplastic elastomer composition of the present invention, lubricants such as amide waxes, antiblocking agents such as silica, phenolic antioxidants, phosphorus antioxidants and the like can be mixed within a range that does not impair the properties of the present invention.

According to JIS Z 1702, the tensile modulus of the film measured at a temperature of 23 ° C. and a tensile speed of 100 mm / min was 10.0 to 500 N / in both the film longitudinal direction (MD) and the film transverse direction (TD) according to JIS Z 1702. It is in the range of mm ² . This tensile modulus is preferably in the range of 20.0 to 400 N / mm ² , more preferably in the range of 30.0 to 300 N / mm ² . If the tensile modulus is less than 10.0 N / mm ² , there is a problem in that the pulling of the film is weak and relaxation occurs when the release film is taken out from the wound body in the mold forming apparatus. On the other hand, when the tensile modulus exceeds 500 N / mm ² , there is a problem that the film does not stretch and does not adhere to the mold mold when the release film is sucked by vacuum in the mold mold.

The film for mold release in this invention is a film longitudinal direction (MD) and a film transverse direction (TD) in 50% modulus (50% Mo) of the film measured by the temperature of 23 degreeC, and tensile speed 100mm / min based on JISZ1702. ) Ratio (MD) / (TD) is in the range of 0.90 to 1.20. This (MD) / (TD) becomes like this. Preferably it is the range of 0.95-1.20. (MD) / (TD) does not become less than 0.90 in the film shape | molded by the extrusion molding method. On the other hand, when (MD) / (TD) exceeds 1.20, there exists a problem that wrinkles generate | occur | produce in a film when a film for release is supplied to a mold mold in a mold shaping | molding apparatus.

The film for mold release in this invention is the ratio (100%) of 50% modulus (50% Mo) and 100% modulus (100% Mo) of the film measured by the temperature of 23 degreeC, and tensile velocity 100mm / min based on JISZ1702. Mo) / (50% Mo) is both in the range of 1.00 to 1.60 with respect to the film longitudinal direction (MD) and the film transverse direction (TD). This (100% Mo) / (50% Mo) becomes like this. Preferably it is the range of 1.00-1.50. If (100% Mo) / (50% Mo) is less than 1.00, no increase in stress due to an increase in film elongation occurs, so that no elongation of the uniform film is obtained, and the release film is sucked in a mold in a vacuum. When wrinkles occur there is a problem. On the other hand, when (100% Mo) / (50% Mo) exceeds 1.60, there is a large increase in stress due to an increase in film elongation, and the problem that the film is not sufficiently stretched until the release film is in close contact with the mold mold inner surface. have.

According to JIS Z 1702, the tensile elongation of the film measured by the temperature of 23 degreeC and a tensile velocity of 100 mm / min is 350% or more in both a film longitudinal direction (MD) and a film horizontal direction (TD) based on JISZ1702. This tensile elongation becomes like this. Preferably it is 400% or more. If the tensile elongation is less than 350%, there is a problem that the film for releasing is broken at the edge of the mold die when the film for suction is drawn by vacuum in the mold die.

The release film containing the thermoplastic elastomer composition mentioned above can be shape | molded by a conventionally well-known method, such as a melt extrusion method and a melt casting method, for example. In the following examples, the method of shape | molding the film for mold release by the melt-extrusion method using T dice | dies is mentioned as an example.

The release film obtained by the above method uses a extruder such as a single screw extruder or a twin screw extruder as the molding material of the thermoplastic elastomer composition, and in accordance with the characteristics of the thermoplastic elastomer composition, air in the extruder and the gap between the molding materials is replaced with nitrogen gas. Melt kneading in an atmosphere, and the film for release release melt-extruded from the lip portion of the T-die tip disposed at the tip of the extruder is directly inserted between the compression roll and the cooling roll in the take-in machine, or the separator from both or one of the compression roll side and the cooling roll side. It is obtained by inserting and inserting and cooling, and then winding up to a winding pipe sequentially with a winding machine.

It is a block diagram which shows the outline of the film manufacturing apparatus which manufactures the film for mold release by the method mentioned above. 4 is sectional drawing of the periphery of the material input hopper of the film manufacturing apparatus shown in FIG. In FIG. 3, the film manufacturing apparatus is comprised substantially including the material input hopper 2, the extruder 1, the T dice | dies 7, the take-out machine 11, and the winding machine 15. In FIG. The material input hopper 2 is configured to inject the molding material, and as shown in FIG. 4, the nitrogen gas supply pipe 3 is connected to the spacer 3a while being connected to the extruder 1 of the material input hopper 2. It is inserted through. In addition, the pipe 3 for nitrogen gas supply is bent so that it may follow the substantially central axis of the material inlet 1c, The front end extends to the outer periphery vicinity of the extrusion screw 1a in the extruder 1, and is installed. Oxygen contained in the extruder 1 or in the molding material fed from the material input hopper 2 is the nitrogen gas supply pipe 3 when the molding material is mixed and stirred in the extruder screw 1a of the extruder 1. It is replaced by the nitrogen gas supplied to).

The extruder 1 conveys a molding material in the arrow B direction, mixing and stirring it with the extrusion screw 1a, and heats and melts a molding material by the heat transfer means inserted in the cylinder 1b of the extruder 1. As shown in FIG. The molding material melted and conveyed in this way is fed to the filter means 5 via the connection pipe 4 shown in FIG. In addition, the shaping | molding material melt | dissolved by the filter means 5 is isolate | separated, and the molten molding material is supplied to the gear pump 6. In the gear pump 6, the molten molding material is extruded 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 the film 8 having a predetermined thickness and a predetermined width is formed from the lip portion 7a of the T die 7. The film 8 thus formed is adjusted to a predetermined thickness with the pressing roll 9 while being drawn on the outer circumferential surface of the cooling roll 10 of the take-out machine 11, and cooled and solidified to convey the pair of conveying rolls 12, ( 13 is conveyed to the winder 15.

In the winding machine 15, the film 8 is guided by the guide rolls 15a, 15b, and 15c and wound up by the winding pipe 16. As shown in FIG. Moreover, the thickness measuring machine 14 is arrange | positioned between the conveying roll pair 12, 13, and the guide roll 15a, and based on the thickness measured by the thickness measuring machine 14 so that it may become desired thickness, the cooling roll 10 It is to adjust and control the main speed of. Thus, the release film is formed.

The film for mold release can form the surface shape of a film according to the surface shape which a molded article requires. For example, when the surface becomes a mirror surface in LED etc., the release film which made the surface of the release film a mirror surface is used. In addition, since IC, LSI, etc. form fine unevenness | corrugation on the surface, the release film which formed the fine unevenness | corrugation on the surface of the release film is used.

As a method of forming the surface shape of the film for release, when making a surface into a mirror surface, let the surface of the metal cooling roll mentioned above be a mirror surface, and the film for release in a molten state is crimped | bonded by the said compression roll with a compression roll, There is a method of front-facing the surface to a mirror surface. Moreover, when using a separator, there exists a method of transferring the surface using the mirror-finished PET film or OPP film as a separator.

In FIG. 3, the separator 18a is supplied to the crimping roll 9 side of the film 8 from the delivery roll 17a in the arrow direction, and from the delivery roll 17b to the cooling roll 10 side of the film 8 in FIG. By supplying the separator 18b in the direction of the arrow, the surface shape of the film 8 can be transferred from the separator. The film 8 which laminated | stacked the separator 18a, 18b on both surfaces was once wound up, and after peeling the separator 18a, 18b and winding up the film 8, the release film which has a predetermined surface shape You can get it.

In the case of forming fine unevenness on the surface of the film for release, when forming the fine unevenness on the outer circumferential surface of the cooling roll made of metal described above and pressing the film for release in a molten state with the compression roll, There exists a method of transferring the formed fine unevenness | corrugation to the film surface for release. Moreover, when using a separator, there exists a method of transferring the surface using PET film or OPP film which matted the surface as a separator.

When making the surface of the release film into a mirror surface, the arithmetic mean roughness Ra measured by the speed 0.6mm / sec, the cutoff value 0.8mm, and the evaluation length 8.0mm based on JIS B0601-2001 is 0.10 or less, and maximum height roughness The surface can be appropriately formed so that Rz is 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 to which the surface of the film for release is transferred is smoothed.

When fine unevenness | corrugation is formed in the surface of a release film, a surface can be suitably formed so that arithmetic mean roughness Ra of the surface roughness measured similarly to the above may be 0.5 or more, and maximum height roughness Rz is 5.00 or more.

The film for mold release of this invention is the range of 5 micrometers-500 micrometers, Preferably it is the range of 10 micrometers-400 micrometers, It can select suitably according to the shape of the mold metal mold | die used. When the thickness of a release film is less than 5 micrometers, it is unpreferable since there exists a problem that a release film is extended | stretched, becomes thin and tears, or is torn by the pressure of a mold resin when following a mold metal mold | die at the time of use. Moreover, when it exceeds 500 micrometers, since the thickness of a mold release film becomes an obstacle, it cannot become following a mold metal mold | die which has a fine structure, and since there exists a problem that a complicated shape of a mold metal mold | die is not transferred to a molded article, it is preferable. Not.

[Example]

Hereinafter, the Example of the release film of this invention is demonstrated using Tables 1 and 2.

In addition, the film for mold release which concerns on this invention is not limited by Examples 1-8.

Here, the materials shown below are used for the urethane-based elastomer 1, the fluorine-based surfactant 1, and the fluorine-based surfactant 2 shown in Tables 1 and 2.

(Urethane-based elastomer 1)

Miralacran E598PNAT: A brand name, the Nippon Polyurethane high school company make, JIS A hardness 98, Vicat softening temperature 141 degrees Celsius

(Fluorinated Surfactant 1)

F-top EF-N112: Brand name, Mitsubishi Materia Co., Ltd., bis (trifluoro methanesulfonyl) imide potassium salt ((CF ₃ SO ₂ ) ₂ NK), melting point 200 ℃

(Fluorinated Surfactant 2)

F top EF-12: trade name, manufactured by Mitsubishi mate rial, methanesulfonic acid and potassium trifluoroacetate (CF ₃ SO ₃ K), melting point 233 ℃

Hereinafter, preparation, release property, heat resistance, mold size transfer property, surface smoothness, and practical useability of the film for release are demonstrated based on Tables 1 and 2. In addition, the same applies to Comparative Examples 1 to 3 in Table 3.

(Production of release film)

The thermoplastic elastomer composition was supplied to a single-screw extruder (manufactured by IK K. D.) having a diameter of 40 mm and L / D = 25, and melt kneaded under the conditions of a cylinder temperature of 180 to 210 ° C using a full-flight extrusion screw with a compression ratio of 2.5. Then, it extruded continuously on the conditions of the die temperature of 210 degreeC-220 degreeC from T dice | dies of 400 mm in width. This extruded mold release film is made into a separator from the press roll side in a take-out machine, and a mirror processed PET film is supplied as a separator from a cooling roll side, these are sandwiched between a press roll cooling roll, and it cools, Both ends were cut with a slit blade, and the release film of 250 mm in width and 50 m in length was manufactured by the thickness shown in Tables 1-3 by winding the film for mold release into a winding tube. These films for release were left to stand for 24 hours in an atmosphere of 80 ° C to perform aging. After the end of aging, the release film was wound again while peeling off the mat-processed PET film and the mirror-finished PET film of the separator to obtain a release film for evaluation.

(Method of evaluation)

Evaluation was carried out by adsorbing the mold release film to the mold die 30 using the mold die 30 having the configuration shown in Figs. 2 (a) and (b) having the lens shape shown in Fig. The resin composition was dripped and hot-press-molded, and peelability, heat resistance, mold size transfer property, and surface smoothness were evaluated, respectively.

Specifically, the mold release film is provided so that the mat surface of the release film is on the mold mold 30 side and the mirror surface is on the air side, and the film for release is sucked by vacuum to adsorb the release film onto the mold mold 30. I was. Subsequently, the silicone resin composition RHODORSIL RTV141 (made by BLUESTAR SILICONES) was dripped on the film for mold release, and the flat metal mold | die with which the surface was hard-chromium-plated was pressed to these, and it pinched with two metal mold | die. And hot press molding. Mold dimensional transferability and surface smoothness were evaluated about the peelability of the release film of the molded laminated product and the cured silicone resin, the heat resistance of the release film, and the cured silicone resin. Hot press molding was performed under conditions of a temperature of 140 ° C. and a pressure of 10 kg / cm ² for 5 minutes.

(Peelability)

Evaluation of peelability was shown as "x" when the cured silicone resin composition could be peeled off without leaving on the film for mold release, and "x" when the silicone resin composition partially broke and remained on the film for mold release.

(Heat resistance)

Evaluation of heat resistance observed by visual observation of the release film which peeled the hardened silicone resin composition, and when it maintains a film shape without melt | melt and melting, "x", and when the release film has melt | dissolution and melting, it is "x." ".

(Dimensional Transferability)

Mold size transferability measured and evaluated the dimension of the hardened silicone resin composition. The evaluation criteria of the lens height were within a range of -0.1 mm, that is, ((thickness of 4-release film) -0.1) mm or more from the dimension of the hole depth 4 mm minus the thickness of the film for release. All of the 25 lenses were indicated as "(circle)" in the case of within the standard, and "x" in the case where there was a shape that did not satisfy the standard even in the case of one lens.

(Surface smoothness)

Surface smoothness evaluated visually the surface state of the hardened silicone resin composition. In the case where no irregularities or wrinkles are generated on the surface of the silicone resin, "○" is indicated.

(Usability)

About usability, it confirmed and evaluated by resin-molding with the mold shaping | molding apparatus. Specifically, it is practical usability using Rhodosil RTV141 (made by Bluestar Silicones) as a silicone resin composition in the molding apparatus G-LINE manual press (brand name) by Apic Yamada Co., Ltd. as a molding apparatus. It was confirmed by visual observation.

Evaluation of the practical usability is that the film is supplied without being relaxed when the release film is conveyed in the mold forming apparatus, there is no wrinkles in the film at the time of adsorption, and the peelability of the release film and the silicone resin composition after hot press molding. The surface of this good and cured silicone resin composition is smooth without irregularities or wrinkles, and there is no tearing or melting in the release film, no residue of the silicone resin composition, and no contamination in the mold die. When there is a problem, it is indicated as "x".

As shown in Table 3, in Comparative Example 1, the thickness of the ETFE film manufactured by Asahi Glass Co., Ltd. and Aprex (trade name) was 100 µm, but the mold size transferability was deteriorated, and no practical use was obtained. In Comparative Example 2, the thickness of the ETFE film manufactured by Asahi Glass Co., Ltd. and Aprex (trade name) was 25 μm, but the film was torn when adsorbed in the mold die, and practical use was not obtained. In Comparative Example 3, a mold release film having a thickness of 50 µm containing Hytrel 5577 (trade name) manufactured by Toray DuPont, a polyester polyether copolymer, a D hardness of 55, and a thermoplastic elastomer composition having a bicat softening temperature of 192 ° C was prepared. Comparison was made. Wrinkles generate | occur | produced on the surface of the molded article containing a silicone resin composition, surface smoothness deteriorated, and practical usability was not obtained.

On the contrary, as shown in Tables 1 and 2, the release films of the examples according to the present invention not only obtain peelability but also have heat resistance, are excellent in mold dimensional transferability and surface smoothness, and are provided with practical use. It became clear. From this, according to this invention, the film for mold release which can obtain the molded article excellent in peelability with the molded article obtained by shape | molding mold resin, and excellent in shape and surface property can be obtained.

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 changes or improvements can be made to the above embodiments. Moreover, it is clear from description of a claim that the form which added such a change or improvement can also be included in the technical scope of this invention.

1: extruder
2: material input hopper
3: pipe for nitrogen gas supply
4: connector
5: filter
6: gear pump
7: T dice
7a: ribs
8: film
9: crimping roll
10: cooling roll
11: drawer
12, 13: conveying roll pair
14: thickness meter
16: winding tube
17a, 17b: delivery roll
18a, 18b: separator
20: shell type LED lens
21a, 21b: lead wire
30: mold mold
31: lens molding recess

Claims (11)

A release film comprising a thermoplastic elastomer composition having a JIS A hardness of 70 or more and a polyurethane-based elastomer having a bicat softening temperature of 100 to 180 ° C. alone or a polyurethane-based elastomer as a main component. The release film according to claim 1, wherein the polyurethane-based elastomer is a thermoplastic polyurethane-based elastomer obtained by reaction of three components of a polyisocyanate, a polyol, and a chain extender. The polyol according to claim 2, wherein the polyol has a number average molecular weight of 500 to 10000 belonging to the group consisting of polyester polyol, polyesteramide polyol, polycarbonate polyol, polyether polyol, polyether ester polyol and polyolefin polyol. Release film, characterized in that one or plural selected from. The release film according to claim 2 or 3, wherein the chain extender is selected from active hydrogen-containing compounds having a number average molecular weight of less than 500 belonging to low molecular polyols, low molecular polyamines, and low molecular amino alcohols. The release film according to any one of claims 1 to 4, wherein the thermoplastic elastomer composition contains a fluorine-based surfactant in the range of 0.05 to 5.0 parts by mass based on 100 parts by mass of the polyurethane-based elastomer. The release film according to claim 5, wherein the fluorine-based surfactant is a perfluoroalkylsulfonic acid derivative compound having a decomposition temperature of 300 ° C or higher at a melting point of 250 ° C or lower. The release film according to any one of claims 1 to 6, wherein the thermoplastic elastomer composition further comprises one or a plurality of additives belonging to a lubricant, an antiblocking agent, an antioxidant, and a phosphorus antioxidant. The release film according to any one of claims 1 to 7, wherein the tensile modulus of the film is in the range of 10 to 500 N / mm ² in both the film longitudinal direction (MD) and the film transverse direction (TD). The ratio (MD) / (TD) of the film longitudinal direction (MD) and the film transverse direction (TD) of any one of claims 1 to 8 at 50% modulus (50% Mo) of the film is 0.9. Release film, characterized in that the range of 1.2 to 1.2. The ratio (100% Mo) / (50% Mo) of 50% modulus (50% Mo) to 100% modulus (100% Mo) of the film is in the longitudinal direction of the film. Both the (MD) and the film transverse directions (TD) are in the range of 1.0 to 1.6, wherein the release film. The release film according to any one of claims 1 to 10, wherein the tensile elongation of the film exceeds 350% in both the film longitudinal direction (MD) and the film transverse direction (TD).

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