TWI527856B - Mold release film - Google Patents
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- TWI527856B TWI527856B TW101109944A TW101109944A TWI527856B TW I527856 B TWI527856 B TW I527856B TW 101109944 A TW101109944 A TW 101109944A TW 101109944 A TW101109944 A TW 101109944A TW I527856 B TWI527856 B TW I527856B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/68—Release sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明係關於一種光半導體元件或半導體元件之樹脂鑄模成形時,尤其是LED(Light Emitting Diode,發光二極體)透鏡之樹脂鑄模成形時所使用之離型用膜。The present invention relates to a release film used in resin molding of an optical semiconductor element or a semiconductor element, in particular, a resin mold for forming an LED (Light Emitting Diode) lens.
例如,LED、光電耦合器(Photoisolator)、光電晶體(Phototransistor)、光電二極體(Photodiode)、CCD(Charge Coupled Device,電荷耦合器件)、CMOS(Complementary Metal Oxide Semiconductor,互補金屬氧化物半導體)等光半導體元件、或電晶體(Transistor)、IC(Integrated Circuit,集成電路)、LSI(Large Scale Integration,大型積體電路)、超LSI等半導體元件係以聚矽氧樹脂組合物或環氧樹脂組合物為密封材料,藉由樹脂鑄模成形而密封。For example, LED, Photoisolator, Phototransistor, Photodiode, CCD (Charge Coupled Device), CMOS (Complementary Metal Oxide Semiconductor), etc. A semiconductor element such as an optical semiconductor element, a transistor, an IC (Integrated Circuit), an LSI (Large Scale Integration), or a super LSI is a polyoxyxylene resin composition or an epoxy resin combination. The material is a sealing material and is sealed by resin molding.
上述光半導體元件或半導體元件之密封係使用鑄模成形裝置,將包含聚矽氧樹脂組合物或環氧樹脂組合物之密封材料作為鑄模樹脂注入至鑄模模具中而成形。The sealing of the optical semiconductor element or the semiconductor element is carried out by injecting a sealing material containing a polyoxyxylene resin composition or an epoxy resin composition into a mold as a mold resin using a mold forming apparatus.
作為對鑄模模具與成形品進行離型之方法,例如已實用化有於鑄模模具與鑄模樹脂之間插入離型用膜之方法(例如參照專利文獻1)。離型用膜係於鑄模成形裝置內藉由連續捲繞(Roll to Roll)而供給,送入調溫至成形加工溫度之鑄模模具中,以真空吸引而密接於鑄模模具上,其後,填充鑄模樹脂。於一定時間後鑄模樹脂硬化後打開鑄模模具,於離型用膜吸附於鑄模模具之狀態下,直接將成形品自離型用膜剝離。該離型用膜係使用例如包含熱塑性氟樹脂之四氟乙烯-乙烯共聚合樹脂(ETFE(Ethylene Tetrafluoroethylene)樹脂)或四氟乙烯-六氟丙烯共聚合樹脂(FEP(Fluorinated Ethylene Propylene)樹脂)之單層之膜(例如參照專利文獻2)。As a method of releasing the mold and the molded article, for example, a method of inserting a release film between the mold and the mold resin has been put to practical use (for example, see Patent Document 1). The release film is supplied by a roll to roll in a mold forming apparatus, and is fed into a mold of a mold which is tempered to a forming temperature, and is vacuum-sucked and adhered to the mold, and then filled. Mold resin. After a certain period of time, the mold resin is cured, and the mold is opened, and the molded product is directly peeled off from the release film while the release film is adsorbed to the mold. The film for release film is, for example, a tetrafluoroethylene-ethylene copolymer resin (ETFE (Ethylene Tetrafluoroethylene) resin) or a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP (Fluorinated Ethylene Propylene) resin) containing a thermoplastic fluororesin. A film of a single layer (for example, refer to Patent Document 2).
然而,若將此種離型用膜用於以聚矽氧樹脂組合物為鑄模樹脂之LED透鏡之成形,則例如對於底面為Φ6 mm左右、高度為4 mm左右之砲彈型透鏡形狀,即便以真空吸引離型用膜亦存在並不延伸之現象,而且存在即便延伸亦不密接於鑄模模具上,從而無法獲得按照設計尺寸之LED透鏡之異常。又,若使離型用膜之厚度變薄而改善延伸,則於以真空吸引時存在於鑄模模具之邊緣離型用膜破裂之異常。However, when such a film for release film is used for the formation of an LED lens in which a polyoxyxylene resin composition is a mold resin, for example, a bullet-shaped lens shape having a bottom surface of about Φ 6 mm and a height of about 4 mm, even There is also a phenomenon in which the film for vacuum suction release does not extend, and there is an advantage that the LED lens of the design size cannot be obtained even if it is not adhered to the mold. In addition, when the thickness of the release film is made thinner and the elongation is improved, the film for release film which is present at the edge of the mold is broken during vacuum suction.
又,已知有使用包含含有結晶性芳香族聚酯(所述結晶性芳香族聚酯於結晶成分中含有對苯二甲酸丁二酯)之樹脂組合物的膜作為離型用膜之方法(例如參照專利文獻3)。Moreover, it is known to use a film containing a resin composition containing a crystalline aromatic polyester (the crystalline aromatic polyester containing a butylene terephthalate in a crystal component) as a film for release film ( For example, refer to Patent Document 3).
然而,作為離型用膜,如專利文獻3所示那樣,若將包含含有結晶性芳香族聚酯(所述結晶性芳香族聚酯包含對苯二甲酸丁二酯)之樹脂組合物的膜用於LED透鏡之成形,則若以真空吸引離型用膜則密接於鑄模模具上,但由於是超過斷裂點而延伸,因此存在離型用膜部分性變薄,於成形之LED透鏡表面產生凹凸或褶皺之異常。因此,實際情況是於LED透鏡之樹脂鑄模成形中,尚無可較佳地用作離型用膜之膜。However, as a film for release film, as shown in Patent Document 3, a film containing a resin composition containing a crystalline aromatic polyester (the crystalline aromatic polyester containing butylene terephthalate) is contained. In the case of forming a LED lens, if the film for vacuum release is adhered to the mold, but it extends beyond the break point, the release film is partially thinned and is formed on the surface of the formed LED lens. Abnormalities in bumps or wrinkles. Therefore, the actual situation is that in the resin molding of the LED lens, there is no film which can be preferably used as a film for release film.
[專利文獻1]日本專利特開平8-142105號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-142105
[專利文獻2]日本專利特開2001-310336號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-310336
[專利文獻3]日本專利特開2007-224311號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-224311
本發明係鑒於上述而成者,其目的在於提供一種與鑄模模具或成形品之剝離性優異,並且,將鑄模模具之形狀按照設計尺寸轉印至成形品之模具形狀轉印性優異,並且獲得成形品之表面平滑性,進而亦具有140℃左右之使用溫度下之耐熱性之離型用膜。The present invention has been made in view of the above-mentioned advantages, and it is an object of the present invention to provide a mold which is excellent in peelability from a mold or a molded article, and which has a mold shape which is transferred to a molded article in accordance with a design size. The surface smoothness of the molded article further includes a release film having heat resistance at a use temperature of about 140 °C.
此種目的係藉由下述(1)~(11)之發明而達成。Such an object is achieved by the inventions of the following (1) to (11).
(1) 一種離型用膜,其特徵在於:其單獨包含JIS(Japanese Industrial Standards,日本工業標準)A硬度為70以上且維卡軟化溫度為100~180℃之聚胺基甲酸酯系彈性體或者包含以該聚胺基甲酸酯系彈性體為主成分之熱塑性彈性體組合物。(1) A release film comprising JIS (Japanese Industrial Standards) A having a hardness of 70 or more and a Vicat softening temperature of 100 to 180 ° C. The body or a thermoplastic elastomer composition containing the polyurethane-based elastomer as a main component.
(2) 如(1)之離型用膜,其中,聚胺基甲酸酯系彈性體係藉由聚異氰酸酯、多元醇及鏈延長劑這3種成分之反應而獲得之熱塑性聚胺基甲酸酯系彈性體。(2) The release film according to (1), wherein the polyurethane-based elastic system is obtained by reacting three components of a polyisocyanate, a polyol, and a chain extender to obtain a thermoplastic polycarbamic acid. Ester-based elastomer.
(3) 如(2)之離型用膜,其中,多元醇係選自屬於由聚酯多元醇、聚酯醯胺多元醇、聚碳酸酯多元醇、聚醚多元醇、聚醚酯多元醇、及聚烯烴多元醇所組成之群之數量平均分子量為500~10000之高分子多元醇中的1種或複數種。(3) The release film according to (2), wherein the polyol is selected from the group consisting of polyester polyols, polyester decylamine polyols, polycarbonate polyols, polyether polyols, polyether ester polyols And one or more of the polymer polyols having a number average molecular weight of 500 to 10,000, which are composed of a polyolefin polyol.
(4) 如(2)或(3)之離型用膜,其中,鏈延長劑係選自屬於低分子多元醇類、低分子多元胺類、及低分子胺基醇類之數量平均分子量未達500之含活性氫之化合物。(4) The release film according to (2) or (3), wherein the chain extender is selected from the group consisting of low molecular weight polyols, low molecular weight amines, and low molecular weight amines. Up to 500 compounds containing active hydrogen.
(5) 如(1)至(4)中任一項之離型用膜,其中,熱塑性彈性體組合物係相對於聚胺基甲酸酯系彈性體100質量份而含有0.05~5.0質量份之範圍的氟系界面活性劑之組合物。(5) The release film according to any one of (1) to (4), wherein the thermoplastic elastomer composition contains 0.05 to 5.0 parts by mass based on 100 parts by mass of the polyurethane elastomer. A composition of a fluorine-based surfactant in the range.
(6) 如(5)之離型用膜,其中,氟系界面活性劑係熔點為250℃以下且分解溫度為300℃以上之全氟烷基磺酸衍生物化合物。(6) The release film according to (5), wherein the fluorine-based surfactant is a perfluoroalkylsulfonic acid derivative compound having a melting point of 250 ° C or lower and a decomposition temperature of 300 ° C or higher.
(7) 如(1)至(6)中任一項之剝離膜,其中,熱塑性彈性體組合物進而包含1種或複數種屬於潤滑劑、抗結塊劑、抗氧化劑、及磷系抗氧化劑之添加劑。(7) The release film according to any one of (1) to (6), wherein the thermoplastic elastomer composition further comprises one or more of a lubricant, an anti-caking agent, an antioxidant, and a phosphorus-based antioxidant. Additives.
(8) 如(1)至(7)中任一項之離型用膜,其中,膜之拉伸彈性模數於膜縱方向(MD,Machine Direction)及膜橫方向(TD,Transverse Direction)上均為10~500 N/mm2之範圍。(8) The release film according to any one of (1) to (7), 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) Both are in the range of 10~500 N/mm 2 .
(9) 如(1)至(8)中任一項之離型用膜,其中,膜之50%模數(50%Mo)之膜縱方向(MD)與膜橫方向(TD)之比(MD)/(TD)為0.9~1.2之範圍。(9) The film for release film according to any one of (1) to (8), wherein a ratio of a film longitudinal direction (MD) to a film transverse direction (TD) of a 50% modulus (50% Mo) of the film (MD) / (TD) is in the range of 0.9 to 1.2.
(10) 如(1)至(9)中任一項之離型用膜,其中,膜之50%模數(50%Mo)與100%模數(100%Mo)之比(100%Mo)/(50%Mo)於膜縱方向(MD)及膜橫方向(TD)上均為1.0~1.6之範圍。(10) The release film according to any one of (1) to (9), 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.
(11) 如(1)至(10)中任一項之離型用膜,其中,膜之拉伸伸長率於膜縱方向(MD)及膜橫方向(TD)上均超過350%。(11) The release film according to any one of (1) to (10), wherein the tensile elongation of the film exceeds 350% in both the longitudinal direction (MD) and the transverse direction (TD) of the film.
根據本發明之離型用膜,與鑄模模具或成形品之剝離性優異,並且,將鑄模模具之形狀按照設計尺寸轉印至成形品之模具形狀轉印性優異,並且獲得成形品之表面平滑性,進而亦具有耐熱性。According to the film for release film of the present invention, it 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 shape is excellent in transferability, and the surface of the molded article is smoothed. It also has heat resistance.
本發明者等人為達成上述目的而進行各種研究,結果查明單獨包含於聚胺基甲酸酯系彈性體中JIS A硬度為70以上、比重為1.05~1.30及維卡軟化溫度為100~180℃之聚胺基甲酸酯系彈性體或包含以該聚胺基甲酸酯系彈性體為主成分之熱塑性彈性體組合物之離型用膜可與鑄模模具或成形品之剝離性優異,並且,將鑄模模具之形狀按照設計尺寸轉印至成形品之模具形狀轉印性優異,並且獲得成形品之表面平滑性,進而亦具有耐熱性。The inventors of the present invention conducted various studies to achieve the above object, and as a result, found that the JIS A hardness is 70 or more, the specific gravity is 1.05 to 1.30, and the Vicat softening temperature is 100 to 180 in the polyurethane-based elastomer alone. The release film of the polyurethane elastomer of °C or the thermoplastic elastomer composition containing the polyurethane elastomer as a main component is excellent in peelability from a mold or a molded article. Further, the shape of the mold is transferred to the molded article in accordance with the design size, and the shape is excellent in transferability, and the surface smoothness of the molded article is obtained, and further, heat resistance is obtained.
進一步進行研究,結果查明藉由將熱塑性彈性體組合物設為相對於聚胺基甲酸酯系彈性體100質量份而含有0.05~5.0質量份之範圍之氟系界面活性劑之組合物,變得更有效果,從而完成本發明。Further, it has been found that the thermoplastic elastomer composition is a composition containing a fluorine-based surfactant in a range of 0.05 to 5.0 parts by mass based on 100 parts by mass of the polyurethane elastomer. It has become more effective to complete the present invention.
本發明中之聚胺基甲酸酯系彈性體係藉由聚異氰酸酯、多元醇及鏈延長劑這3種成分之反應而獲得之熱塑性聚胺基甲酸酯系彈性體。The polyurethane-based elastic system 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.
作為上述聚異氰酸酯,例如可列舉:2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、二甲苯-1,4-二異氰酸酯、二甲苯-1,3-二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4'-二苯基甲烷二異氰酸酯、2,2'-二苯基甲烷二異氰酸酯、4,4'-二苯醚二異氰酸酯、2-硝基二苯基-4,4'-二異氰酸酯、2,2'-二苯基丙烷-4,4'-二異氰酸酯、3,3'-二甲基二苯基甲烷-4,4'-二異氰酸酯、4,4'-二苯基丙烷二異氰酸酯、間苯二異氰酸酯、對苯二異氰酸酯、伸萘基-1,4-二異氰酸酯、伸萘基-1,5-二異氰酸酯、3,3'-二甲氧基苯基-4,4'-二異氰酸酯等芳香族二異氰酸酯類;四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十二烷基二異氰酸酯、三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯等脂肪族二異氰酸酯類;環己烷二異氰酸酯、二環己基甲烷二異氰酸酯、異佛爾酮二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、氫化二苯基甲烷二異氰酸酯、四甲基二甲苯二異氰酸酯、降冰片烷二異氰酸甲酯等酯環族二異氰酸酯類;上述異氰酸酯之縮二脲體、二聚物體、三聚物體、二聚物-三聚物體、碳二醯亞胺體、脲酮亞胺體、由2官能以上之多元醇等與上述異氰酸酯之反應獲得之加合物體等。又,亦可列舉:利用甲醇、正丁醇、苯甲醇、乙醯乙酸乙酯、ε-己內醯胺、甲基乙基酮肟、苯酚、甲酚等分子內具有1個活性氫之封端劑使異氰酸酯基之一部分穩定化而成之聚異氰酸酯。該等可使用1種或將2種以上混合使用。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, s-naphthyl-1,4-diisocyanate, naphthyl-1,5-diisocyanate, 3,3'-dimethoxy An aromatic diisocyanate such as phenyl-4,4'-diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, dodecyl diisocyanate, trimethyl hexamethylene diisocyanate, or amine Aliphatic diisocyanates such as acid diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated dimethyl An ester cyclic diisocyanate such as phenyl diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylene diisocyanate or norbornane diisocyanate; biuret, dimer, and trisole of the above isocyanate A polymer body, a dimer-trimer, a carbodiimide body, a uretonimine body, an adduct obtained by a reaction of a difunctional or higher polyhydric alcohol with the above isocyanate, or the like. Further, a seal having one active hydrogen in a molecule such as methanol, n-butanol, benzyl alcohol, ethyl acetate, ε-caprolactam, methyl ethyl ketone oxime, phenol or cresol may be mentioned. A polyisocyanate in which a terminal agent stabilizes a portion of an isocyanate group. These may be used alone or in combination of two or more.
上述多元醇係數量平均分子量為500~10000之高分子多元醇,該等中存在有聚酯多元醇、聚酯醯胺多元醇、聚碳酸酯多元醇、聚醚多元醇、聚醚酯多元醇、聚烯烴多元醇等。該等高分子多元醇可使用1種或將2種以上混合使用。The above polymer polyol having a polyol molecular weight average molecular weight of 500 to 10,000, wherein polyester polyol, polyester decylamine polyol, polycarbonate polyol, polyether polyol, polyether ester polyol are present , polyolefin polyols, and the like. These polymer polyols may be used alone or in combination of two or more.
作為聚酯多元醇、聚酯醯胺多元醇,可列舉:由多羧酸與多元醇,視情況併用二胺或胺基醇,藉由縮合反應而獲得者。Examples of the polyester polyol and the polyester decylamine polyol include those obtained by a condensation reaction using a polycarboxylic acid and a polyhydric alcohol, and optionally a diamine or an amino alcohol.
作為該多羧酸,例如有:琥珀酸、己二酸、癸二酸、二聚酸、氫化二聚酸、鄰苯二甲酸、鄰苯二甲酸烷基酯類、偏苯三甲酸、順丁烯二酸、反丁烯二酸、衣康酸等。又,亦可列舉:藉由丁內酯、戊內酯、己內酯等環狀酯類之開環聚合而獲得者。Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid, alkyl phthalate, trimellitic acid, and cis. Aenedioic acid, fumaric acid, itaconic acid, and the like. Further, it is also obtained by ring-opening polymerization of a cyclic ester such as butyrolactone, valerolactone or caprolactone.
作為該多元醇,例如可列舉:乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、2-甲基-1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊二醇、1,8-辛二醇、1,9-壬二醇、2,2-二乙基-1,3-丙二醇、2-正丁基-2-乙基-1,3-丙二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2-正十六烷-1,2-乙二醇、2-正二十烷-1,2-乙二醇、2-正二十八烷-1,2-乙二醇、二乙二醇、二丙二醇、1,4-環己烷二甲醇、或雙酚A之環氧乙烷或環氧丙烷加成物、氫化雙酚A、3-羥基-2,2-二甲基丙基-3-羥基-2,2-二甲基丙酸酯、三羥甲基丙烷、甘油、季戊四醇等低分子多元醇類。作為二胺或胺基醇,例如可列舉:乙二胺、己二胺、苯二甲胺、異佛爾酮二胺等低分子多元胺類,單乙醇胺、二乙醇胺、三乙醇胺等低分子胺基醇類。又,可列舉:以低分子多元醇、低分子多元胺、低分子胺基醇為起始劑,藉由ε-己內酯、γ-戊內酯等環狀酯(內酯)單體之開環聚合而獲得之內酯系聚酯多元醇。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 the amino alcohol include low molecular polyamines such as ethylenediamine, hexamethylenediamine, xylylenediamine, and isophorone diamine, and low molecular amines such as monoethanolamine, diethanolamine, and triethanolamine. Alcohols. Further, examples thereof include a low molecular weight polyol, a low molecular weight polyamine, and a low molecular weight amino alcohol as a starting agent, and a cyclic ester (lactone) monomer such as ε-caprolactone or γ-valerolactone A lactone-based polyester polyol obtained by ring-opening polymerization.
作為聚碳酸酯多元醇,可列舉:藉由上述聚酯多元醇之合成所使用之低分子多元醇、與碳酸二乙二酯、碳酸二甲酯、碳酸二乙酯、碳酸二苯酯等之脫醇反應、脫酚反應等而獲得者。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 a dealcoholization reaction, a dephenolization reaction, and the like.
作為聚醚多元醇,可列舉:以上述聚酯多元醇所使用之低分子多元醇、低分子多元胺、低分子胺基醇為起始劑,使環氧乙烷、環氧丙烷、四氫呋喃等進行開環聚合而成之聚乙二醇、聚丙二醇、聚四氫呋喃等、及使該等進行共聚合而成之聚醚多元醇、進而以上述聚酯多元醇、聚碳酸酯多元醇為起始劑之聚酯醚多元醇。Examples of the polyether polyol include a low molecular polyol, a low molecular weight polyamine, and a low molecular weight amino alcohol used in the above polyester polyol as an initiator, and ethylene oxide, propylene oxide, tetrahydrofuran, etc. Polyethylene glycol, polypropylene glycol, polytetrahydrofuran, etc., which are obtained by ring-opening polymerization, and a polyether polyol obtained by copolymerizing the same, and further starting from the above polyester polyol or polycarbonate polyol A polyester ether polyol.
作為聚醚酯多元醇,可列舉:除於獲得上述聚酯多元醇時之縮合反應中所使用的多元醇之一部分或全部中使用聚醚以外,以與聚酯多元醇相同之方式而獲得者。The polyether ester polyol is obtained by the same method as the polyester polyol except that a polyether is used in part or all of the polyol used in the condensation reaction in obtaining the above polyester polyol. .
作為聚烯烴多元醇,可列舉:含羥基之聚丁二烯、經氫化之含羥基之聚丁二烯、含羥基之聚異戊二烯、經氫化之含羥基之聚異戊二烯、含羥基之氯化聚丙烯、含羥基之氯化聚乙烯等。The polyolefin polyol may, for example, be a hydroxyl group-containing polybutadiene, a hydrogenated hydroxyl group-containing polybutadiene, a hydroxyl group-containing polyisoprene, a hydrogenated hydroxyl group-containing polyisoprene, or the like. Chlorinated polypropylene of hydroxyl group, chlorinated polyethylene containing hydroxyl group, and the like.
上述鏈延長劑係數量平均分子量未達500之含活性氫之化合物,例如可列舉:上述低分子多元醇類、上述低分子多元胺類、上述低分子胺基醇類等。Examples of the active hydrogen-containing compound having a chain extender coefficient and an average molecular weight of less than 500 include, for example, the above-mentioned low molecular polyols, the above-described low molecular polyamines, and the above low molecular weight amino alcohols.
聚胺基甲酸酯系彈性體之製造可採用公知之製造方法,例如:單觸發法、預聚物法、分批反應法、連續反應法、利用捏合機之方法、利用擠出機之方法等方法。The production of the polyurethane elastomer may be carried out by a known production method, for example, a single trigger method, a prepolymer method, a batch reaction method, a continuous reaction method, a method using a kneader, and a method using an extruder. And other methods.
本發明所使用之聚胺基甲酸酯系彈性體之硬度係藉由JIS K 7311之試驗法測定之JIS A硬度為70以上。進而,於JIS A硬度為100以上之情形時,較佳為應用D硬度,以D硬度之70以下為上限。該JIS A硬度較佳為80以上,更佳為90以上。若JIS A硬度未達60,則橡膠性變強,因此於鑄模成形裝置內之離型用膜之傳送時,存在離型用膜延伸而傳送不穩定之異常。另一方面,於D硬度超過70之情形時,於擠出成形時存在產生源自原料聚異氰酸酯、多元醇及鏈延長劑這3種成分之凝膠之異常。The hardness of the polyurethane-based elastomer used in the present invention is JIS A hardness of 70 or more as measured by the test method of JIS K 7311. Further, when the JIS A hardness is 100 or more, it is preferable to apply D hardness, and the D hardness is 70 or less as an upper limit. The JIS A hardness is preferably 80 or more, more preferably 90 or more. When the JIS A hardness is less than 60, the rubber property is increased. Therefore, when the release film is conveyed in the mold forming apparatus, the film for release film is stretched and the conveyance is unstable. On the other hand, when the D hardness exceeds 70, there is an abnormality in the gel generated from the three components of the raw material polyisocyanate, the polyol, and the chain extender at the time of extrusion molding.
本發明所使用之聚胺基甲酸酯系彈性體之維卡軟化溫度係藉由JIS K 7206之試驗法測定,為100~180℃之範圍。該維卡軟化溫度較佳為110~180℃,更佳為120~180℃,進而較佳為130~180℃之範圍。若維卡軟化溫度未達100℃,則存在於使用時熔融之異常。亦即,無法獲得耐熱性。另一方面,維卡軟化溫度之上限為180℃,但尚未獲得具有超過180℃之維卡軟化溫度之聚胺基甲酸酯系彈性體。The Vicat softening temperature of the polyurethane-based elastomer used in the present invention is measured by the test method of JIS K 7206 and is in the range of 100 to 180 °C. The Vicat softening temperature is preferably from 110 to 180 ° C, more preferably from 120 to 180 ° C, and still more preferably from 130 to 180 ° C. If the Vicat softening temperature is less than 100 ° C, there is an abnormality in melting at the time of use. That is, heat resistance cannot be obtained. On the other hand, the upper limit of the Vicat softening temperature is 180 ° C, but a polyurethane-based elastomer having a Vicat softening temperature exceeding 180 ° C has not been obtained.
本發明中之所謂氟系界面活性劑係指全氟烷基磺酸衍生物。作為全氟烷基磺酸衍生物之具體例,可列舉:三氟甲基磺酸鉀(CF3SO3K)、三氟甲基磺酸鈉(CF3SO3Na)、三氟甲基磺酸鋰(CF3SO3Li)、五氟乙基磺酸鉀(C2F5SO3K)、五氟乙基磺酸鈉(C2F5SO3Na)、五氟乙基磺酸鋰(C2F5SO3Li)、七氟丙基磺酸鉀(C3F7SO3K)、七氟丙基磺酸鈉(C3F7SO3Na)、七氟丙基磺酸鋰(C3F7SO3Li)、九氟丁基磺酸鉀(C4F9SO3K)、九氟丁基磺酸鈉(C4F9SO3Na)、九氟丁基磺酸鋰(C4F9SO3Li)等全氟烷基磺酸鹽。The fluorine-based surfactant in the present invention means a perfluoroalkylsulfonic acid derivative. Specific examples of the perfluoroalkylsulfonic acid derivative include potassium trifluoromethanesulfonate (CF 3 SO 3 K), sodium trifluoromethanesulfonate (CF 3 SO 3 Na), and trifluoromethyl group. Lithium sulfonate (CF 3 SO 3 Li), potassium pentafluoroethyl sulfonate (C 2 F 5 SO 3 K), sodium pentafluoroethyl sulfonate (C 2 F 5 SO 3 Na), pentafluoroethyl sulfonate Lithium acid (C 2 F 5 SO 3 Li), potassium heptafluoropropyl sulfonate (C 3 F 7 SO 3 K), sodium heptafluoropropyl sulfonate (C 3 F 7 SO 3 Na), heptafluoropropyl Lithium sulfonate (C 3 F 7 SO 3 Li), potassium nonafluorobutyl sulfonate (C 4 F 9 SO 3 K), sodium nonafluorobutyl sulfonate (C 4 F 9 SO 3 Na), nonafluorobutane A perfluoroalkyl sulfonate such as lithium sulfonate (C 4 F 9 SO 3 Li).
又,可列舉:雙(三氟甲基磺醯基)醯亞胺鉀鹽((CF3SO2)2NK)、雙(三氟甲基磺醯基)醯亞胺鈉鹽((CF3SO2)2NNa)、雙(三氟甲基磺醯基)醯亞胺銨鹽((CF3SO2)2NNH4)、雙(三氟甲基磺醯基)醯亞胺鋰鹽((CF3SO2)2NLi)、雙(五氟乙基磺醯基)醯亞胺鉀鹽((C2F5SO2)2NK)、雙(五氟乙基磺醯基)醯亞胺鈉鹽((C2F5SO2)2NNa)、雙(五氟乙基磺醯基)醯亞胺銨鹽((C2F5SO2)2NNH4)、雙(五氟乙基磺醯基)醯亞胺鋰鹽((C2F5SO2)2NLi)、雙(七氟丙基磺醯基)醯亞胺鉀鹽((C3F7SO2)2NK)、雙(七氟丙基磺醯基)醯亞胺鈉鹽((C3F7SO2)2NNa)、雙(九氟丁基磺醯基)醯亞胺鉀鹽((C4F9SO2)2NK)、雙(九氟丁基磺醯基)醯亞胺鈉鹽((C4F9SO2)2NNa)、環-六氟丙烷-1,3-雙(磺醯基)醯亞胺鉀鹽(CF2(CF2SO2)2NK)、環-六氟丙烷-1,3-雙(磺醯基)醯亞胺鈉鹽(CF2(CF2SO2)2NNa)等全氟烷基磺醯亞胺鹽。Further, a bis(trifluoromethylsulfonyl) sulfinium imide potassium salt ((CF 3 SO 2 ) 2 NK) or a bis(trifluoromethylsulfonyl) sulfinium imide sodium salt ((CF 3 ) SO 2 ) 2 NNa), bis(trifluoromethylsulfonyl) sulfoximine ammonium salt ((CF 3 SO 2 ) 2 NNH 4 ), bis(trifluoromethylsulfonyl) quinone imide lithium salt ( (CF 3 SO 2 ) 2 NLi), bis(pentafluoroethylsulfonyl) quinone imide potassium salt ((C 2 F 5 SO 2 ) 2 NK), bis(pentafluoroethylsulfonyl)pyrene Amine sodium salt ((C 2 F 5 SO 2 ) 2 NNa), bis(pentafluoroethylsulfonyl) sulfoximine ammonium salt ((C 2 F 5 SO 2 ) 2 NNH 4 ), bis (pentafluoroethylene) Lithium sulfonyl) sulfonium imide lithium salt ((C 2 F 5 SO 2 ) 2 NLi), bis(heptafluoropropylsulfonyl) quinone imide potassium salt ((C 3 F 7 SO 2 ) 2 NK) , bis(heptafluoropropylsulfonyl) sulfanilide sodium salt ((C 3 F 7 SO 2 ) 2 NNa), bis(nonafluorobutoxysulfonyl) quinone imide potassium salt ((C 4 F 9 SO 2 ) 2 NK), bis(nonafluorobutylsulfonyl) sulfinium imide ((C 4 F 9 SO 2 ) 2 NNa), cyclo-hexafluoropropane-1,3-bis(sulfonyl)醯imine potassium salt (CF 2 (CF 2 SO 2 ) 2 NK), cyclo-hexafluoropropane-1,3-bis(sulfonyl) sulfinium imide sodium salt (CF 2 (CF 2 SO 2 ) 2 NNa) and other perfluoroalkylsulfonimide salts.
進而,亦可列舉:以全氟烷基磺酸為陰離子種之離子液體、以雙(全氟烷基磺醯基)醯亞胺為陰離子種之離子液體、以雙(氟磺醯基)醯亞胺為陰離子種之離子液體、以環六氟丙烷-1,3-雙(磺醯基)醯亞胺為陰離子種之離子液體等。Further, an ionic liquid in which perfluoroalkyl sulfonic acid is an anionic species, an ionic liquid in which bis(perfluoroalkylsulfonyl) quinone imine is an anionic species, and bis(fluorosulfonyl)fluorene are also mentioned. The imine is an ionic liquid of an anionic species, an ionic liquid having an anion species of cyclohexafluoropropane-1,3-bis(sulfonyl) quinone imine, and the like.
於上述全氟烷基磺酸衍生物中亦可較佳地使用熔點為250℃以下且分解溫度為300℃以上之化合物。作為該等之具體例,可列舉:三氟甲基磺酸鉀(CF3SO3K)或雙(三氟甲基磺醯基)醯亞胺鉀鹽((CF3SO2)2NK)。A compound having a melting point of 250 ° C or lower and a decomposition temperature of 300 ° C or higher can be preferably used in the above perfluoroalkylsulfonic acid derivative. Specific examples of the above include potassium trifluoromethanesulfonate (CF 3 SO 3 K) or bis(trifluoromethylsulfonyl) sulfinium imide ((CF 3 SO 2 ) 2 NK). .
氟系界面活性劑係以賦予離型用膜滑性為目的而混合於聚胺基甲酸酯系彈性體中。藉由氟系界面活性劑之混合而賦予膜表面滑性,因此可獲得如下效果:使鑄模成形裝置內之離型用膜之傳送變得順利之效果、於與鑄模模具相接觸時防止離型用膜之褶皺之效果、提高與用作鑄模樹脂之聚矽氧系樹脂組合物之剝離性之效果。其混合量係相對於聚胺基甲酸酯系彈性體100質量份而言,將氟系界面活性劑設為0.05~5.0質量份之範圍。若混合量未達0.05質量份,則不會展現混合之效果。另一方面,即便超過5.0質量份而混合,效果亦不會增大,又,存在如下之異常:氟系界面活性劑滲出至膜表面或於膜表面起霜,於使用時污染成形品之表面。The fluorine-based surfactant is mixed in the polyurethane elastomer for the purpose of imparting film slip properties for release. By blending the fluorine-based surfactant to impart smoothness to the surface of the film, it is possible to obtain an effect of smoothing the transfer of the release film in the mold forming apparatus, and preventing the release when it comes into contact with the mold. The effect of the wrinkles of the film is used to improve the peeling property of the polyoxynenoid resin composition used as the mold resin. The amount of the fluorine-based surfactant is in the range of 0.05 to 5.0 parts by mass based on 100 parts by mass of the polyurethane elastomer. If the amount of the mixture is less than 0.05 parts by mass, the effect of mixing will not be exhibited. On the other hand, even if it exceeds 5.0 parts by mass, the effect does not increase, and there is an abnormality that the fluorine-based surfactant oozes to the surface of the film or blooms on the surface of the film, and the surface of the molded article is contaminated during use. .
於本發明之熱塑性彈性體組合物中,可於不損及本發明之特性的範圍內混合其他熱塑性彈性體。作為熱塑性彈性體,例如可列舉:聚酯系彈性體、聚醯胺系彈性體、聚氯乙烯系彈性體、苯乙烯系彈性體及烯烴系彈性體等。亦可藉由對此種其他熱塑性彈性體進行共擠壓而製成接著積層膜。In the thermoplastic elastomer composition of the present invention, other thermoplastic elastomers may be blended in a range that does not impair 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. It is also possible to form a subsequent laminated film by co-extruding such other thermoplastic elastomers.
本發明之熱塑性彈性體組合物中,可於不損及本發明之特性的範圍內混合例如醯胺系蠟等潤滑劑、矽石等抗結塊劑、酚系抗氧化劑、磷系抗氧化劑等。In the thermoplastic elastomer composition of the present invention, a lubricant such as a guanamine-based wax, an anti-caking agent such as vermiculite, a phenol-based antioxidant, a phosphorus-based antioxidant, or the like may be mixed in a range that does not impair the characteristics of the present invention. .
本發明中之離型用膜係依據JIS Z 1702,於溫度為23℃、拉伸速度為100 mm/min下測定之膜之拉伸彈性模數於膜縱方向(MD)及膜橫方向(TD)上均為10.0~500 N/mm2之範圍。該拉伸彈性模數較佳為20.0~400 N/mm2之範圍,更佳為30.0~300 N/mm2之範圍。若拉伸彈性模數未達10.0 N/mm2,則存在如下之異常:於在鑄模成形裝置內將離型用膜自捲繞體抽出時,膜之張力較弱而產生鬆弛。另一方面,於拉伸彈性模數超過500 N/mm2之情形時,存在如下之異常:於在鑄模模具內以真空吸引離型用膜時,膜不延伸而不密接於鑄模模具。The release film according to the present invention is a tensile modulus of the film measured in the longitudinal direction (MD) of the film and the transverse direction of the film in accordance with JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. TD) is in the range of 10.0~500 N/mm 2 . The tensile elastic 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 . When the tensile modulus of elasticity is less than 10.0 N/mm 2 , there is an abnormality in 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. On the other hand, when the tensile elastic modulus exceeds 500 N/mm 2 , there is an abnormality in that when the release film is suctioned by vacuum in the mold, the film does not extend without being in close contact with the mold.
本發明中之離型用膜係依據JIS Z 1702,於溫度為23℃、拉伸速度為100 mm/min下測定之膜之50%模數(50%Mo)之膜縱方向(MD)與膜橫方向(TD)之比(MD)/(TD)為0.90~1.20之範圍。該(MD)/(TD)較佳為0.95~1.20之範圍。若為藉由擠出成形法而成形之膜,則無(MD)/(TD)成為未達0.90之現象。另一方面,於(MD)/(TD)超過1.20之情形時,存在如下之異常:於在鑄模成形裝置內將離型用膜向鑄模模具供給時,膜產生褶皺。The film for release film according to the present invention is a film longitudinal direction (MD) of 50% modulus (50% Mo) of a film measured at a temperature of 23 ° C and a tensile speed of 100 mm/min in accordance with JIS Z 1702. The ratio (MD) / (TD) of the film transverse direction (TD) is in the range of 0.90 to 1.20. The (MD) / (TD) is preferably in the range of 0.95 to 1.20. In the case of a film formed by an extrusion molding method, no (MD)/(TD) is less than 0.90. On the other hand, when (MD)/(TD) exceeds 1.20, there is an abnormality in that wrinkles are generated when the release film is supplied to the mold in the mold forming apparatus.
本發明中之離型用膜係依據JIS Z 1702,於溫度為23℃、拉伸速度為100 mm/min下測定之膜之50%模數(50%Mo)與100%模數(100%Mo)之比(100%Mo)/(50%Mo)於膜縱方向(MD)及膜橫方向(TD)上均為1.00~1.60之範圍。該(100%Mo)/(50%Mo)較佳為1.00~1.50之範圍。若(100%Mo)/(50%Mo)未達1.00,則存在如下之異常:不會隨著膜之延伸之增加而產生応力之增加,因此無法獲得均勻的膜之延伸,於在鑄模模具內以真空吸引離型用膜時產生褶皺。另一方面,於(100%Mo)/(50%Mo)超過1.60之情形時,存在如下之異常:隨著膜之延伸之增加的応力之增加較大,膜不能完全延伸至使離型用膜密接於鑄模模具內表面。The film for release film according to the present invention is a 50% modulus (50% Mo) and a 100% modulus (100%) of a film measured at a temperature of 23 ° C and a tensile speed of 100 mm / min in accordance with JIS Z 1702. The ratio of 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. The (100% Mo) / (50% Mo) is preferably in the range of 1.00 to 1.50. If (100%Mo)/(50%Mo) does not reach 1.00, there is an abnormality that the increase in the force does not occur as the elongation of the film increases, so that a uniform film extension cannot be obtained in the mold. Wrinkles are generated when the film for release film is suctioned by vacuum. On the other hand, in the case where (100%Mo) / (50%Mo) exceeds 1.60, there is an abnormality that the film does not extend completely to the release type as the increase in the tensile force of the film is increased. The film is intimately attached to the inner surface of the mold.
本發明之離型用膜係依據JIS Z 1702,於溫度為23℃、拉伸速度為100 mm/min下測定之膜之拉伸伸長率於膜縱方向(MD)及膜橫方向(TD)上均為350%以上。該拉伸伸長率較佳為400%以上。若拉伸伸長率未達350%,則存在如下之異常:於在鑄模模具內以真空吸引離型用膜時,於鑄模模具之邊緣破裂。The release film of the present invention is obtained by measuring the tensile elongation of the film in the film longitudinal direction (MD) and the film transverse direction (TD) according to JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. Both are above 350%. The tensile elongation is preferably 400% or more. If the tensile elongation is less than 350%, there is an abnormality in that the film is broken at the edge of the mold when the film for release is vacuum-drawn in the mold.
上述包含熱塑性彈性體組合物之離型用膜可藉由例如熔融擠出法或熔融澆鑄法等先前公知之方法而成形。於以下例中,列舉藉由使用T模之熔融擠出法而成形離型用膜之方法。The film for release film containing the thermoplastic elastomer composition described above can be formed 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.
利用此種方法獲得之離型用膜係藉由如下步驟而獲得:使用單軸擠出機或雙軸擠出機等擠出機,根據熱塑性彈性體組合物之特性,於以氮氣置換存在於擠出機內及成形材料間之間隙之空氣的氣體環境下,對熱塑性彈性體組合物之成形材料進行熔融混練,將自配置於擠出機前端之T模前端之模唇部熔融擠出的離型用膜直接夾於牽拉機內之壓接輥與冷卻輥之間進行冷卻,或自壓接輥側與冷卻輥側之兩側或一側插入分隔件來夾持而進行冷卻,繼而利用捲取機依序捲取於捲取管。The film for release film obtained by this method is obtained by using an extruder such as a single-axis extruder or a twin-screw extruder, and is substituted with nitrogen according to the characteristics of the thermoplastic elastomer composition. The molding material of the thermoplastic elastomer composition is melt-kneaded in a gas atmosphere of air in a gap between the extruder and the molding material, and the lip portion of the tip end of the T-die disposed at the tip of the extruder is melt-extruded. The release film is directly sandwiched between the pressure roller and the cooling roller in the stretching machine, or is inserted into the separator on both sides or one side of the pressure roller side and the cooling roller side to be cooled, and then cooled. The coiler is sequentially taken up by the coiler.
圖3係表示利用上述方法製造離型用膜之膜製造裝置之概略之構成圖。又,圖4係圖3所示之膜製造裝置之材料投入料斗之周邊之剖面圖。於圖3中,膜製造裝置係大致包括材料投入料斗2、擠出機1、T模7、牽拉機11、捲取機15而構成。材料投入料斗2係用以投入成形材料,如圖4所示,於材料投入料斗2與擠出機1連接之途中經由間隔物3a插入有氮氣供給用導管3。又,氮氣供給用導管3係以沿材料投入口1c之大致中心軸之方式彎曲,其前端係延設至擠出機1內之擠出螺桿1a之外周附近。自材料投入料斗2投入之成形材料中或擠出機1內所含之氧氣係於利用擠出機1之擠出螺桿1a對成形材料進行混合、攪拌時,由供給至氮氣供給用導管3之氮氣所置換。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 of the periphery of the material input hopper of the film manufacturing apparatus shown in FIG. 3. In FIG. 3, the film manufacturing apparatus basically comprises a material input hopper 2, an extruder 1, a T die 7, a pulling machine 11, and a coiler 15. The material input hopper 2 is for inserting a molding material, and as shown in FIG. 4, the nitrogen supply conduit 3 is inserted through the spacer 3a while the material input hopper 2 is connected to the extruder 1. Further, the nitrogen supply conduit 3 is bent so as to extend along the substantially central axis of the material inlet 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 hopper 2 or the extruder 1 is supplied to the nitrogen supply conduit 3 when the molding material is mixed and stirred by the extrusion screw 1a of the extruder 1. Replaced by nitrogen.
擠出機1係一面藉由擠出螺桿1a對成形材料進行混合、攪拌,一面向箭頭B方向傳送,並藉由內裝於擠出機1之料缸1b內之電熱機構,對成形材料進行加熱、熔融。以此種方式熔融而傳送之成形材料係經由如圖3所示之連接管4送給至過濾機構5。繼而,藉由過濾機構5,將未熔融之成形材料分離,將熔融之成形材料送給至齒輪泵6。於齒輪泵6中,一面提高熔融之成形材料之壓力,一面向T模7擠出熔融成形材料。於T模7中,以特定壓力擠出熔融成形材料,自T模7之模唇部7a成形特定厚度、特定寬度之膜8。以此種方式成形之膜8係一面捲繞於牽拉機11之冷卻輥10之外周面上,一面利用壓接輥9調整為特定厚度,進而進行冷卻、固化,利用傳送輥對12、13而傳送至捲取機15。The extruder 1 is configured by mixing and stirring the molding material by the extrusion screw 1a, and conveying it in the direction of the arrow B, and performing the molding material by the electric heating mechanism built in the cylinder 1b of the extruder 1. Heat and melt. The molding material which is melted and conveyed in this manner is supplied to the filtering mechanism 5 via the connecting pipe 4 as shown in FIG. Then, the unmelted molding material is separated by the filtering mechanism 5, and the molten molding material is supplied to the gear pump 6. In the gear pump 6, the pressure of the molten molding material is increased, and the molten molding material is extruded toward the T-die 7. In the T die 7, the melt-molded material is extruded at a specific pressure, and the 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 in this manner is wound around the outer circumferential surface of the cooling roll 10 of the stretching machine 11, and is adjusted to a specific thickness by the pressure roller 9, and further cooled and solidified by the conveying roller pair 12, 13 It is transferred to the winder 15.
於捲取機15中,膜8係由引導輥15a、15b、15c引導並藉由捲取管16捲取。再者,於傳送輥對12、13與引導輥15a之間配設有厚度測定器14,根據由厚度測定器14測定之厚度,調整、控制冷卻輥10之圓周速度以使其成為所需之厚度。藉此形成上述離型用膜。In the coiler 15, the film 8 is guided by the guide rolls 15a, 15b, 15c and taken 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 circumferential speed of the cooling roller 10 is adjusted and controlled so as to be required according to the thickness measured by the thickness measuring device 14. thickness. Thereby, the film for release film described above is formed.
離型用膜只要係根據成形品所必需之表面形狀而形成膜之表面形狀即可。例如,於LED等其表面成為鏡面之情形時,使用使離型用膜之表面為鏡面之離型用膜。又,IC或LSI等係使其表面形成有微細之凹凸,因此使用於離型用膜之表面形有微細之凹凸之離型用膜。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, in the case where the surface of the LED or the like is a mirror surface, a film for leaving the surface of the film for release film is used as a mirror surface. In addition, since the IC or the LSI is formed with fine irregularities on its surface, it is used for a release film having fine irregularities on the surface of the release film.
作為形成離型用膜之表面形狀之方法,於使表面為鏡面之情形時,存在有預先使上述之金屬製冷卻輥之表面為鏡面,以壓接輥將處於熔融狀態之離型用膜壓接於該冷卻輥上,將離型用膜之表面調整為鏡面之方法。又,於使用分隔件之情形時,存在有使用鏡面拋光之PET(polyethylene terephthalate,聚對苯二甲酸乙二酯)膜或OPP(Oriented polypropylene,定向聚丙烯)膜作為分隔件,而轉印其表面之方法。As a method of forming the surface shape of the film for release film, when the surface is mirror-finished, there is a film surface in which the surface of the metal cooling roll is previously mirror-shaped, and the film for release film in a molten state is pressed by the pressure roller. The method of adjusting the surface of the release film to the mirror surface is carried out on the cooling roll. Further, in the case of using a separator, there is a PET (polyethylene terephthalate) film or an OPP (Oriented polypropylene) film as a separator, and transfer thereof The method of the surface.
於圖3中,於膜8之壓接輥9之側,自送出輥17a將分隔件18a向箭頭之方向供給,於膜8之冷卻輥10之側,自送出輥17b將分隔件18b向箭頭之方向供給,藉此可由分隔件而轉印膜8之表面形狀。於雙面積層有分隔件18a、18b之膜8暫時捲取後,將分隔件18a、18b剝離而捲取膜8,藉此可獲得具有特定表面形狀之離型膜。In Fig. 3, on the side of the pressure roller 9 of the film 8, the separator 18a is supplied from the delivery roller 17a in the direction of the arrow, on the side of the cooling roller 10 of the film 8, and the separator 18b is directed to the arrow from the delivery roller 17b. The direction is supplied, whereby the surface shape of the film 8 can be transferred by the spacer. After the film 8 having the separators 18a and 18b in the double-area layer is temporarily wound up, the separators 18a and 18b are peeled off and the film 8 is taken up, whereby a release film having a specific surface shape can be obtained.
於在離型用膜之表面形成微細之凹凸之情形時,存在有如下方法:預先於上述之金屬製冷卻輥之外周面形成微細之凹凸,以壓接輥將處於熔融狀態之離型用膜壓接於該冷卻輥上時,使形成於冷卻輥之外周面之微細之凹凸轉印至離型用膜表面。又,於使用分隔件之情形時,存在有使用對表面進行了消光加工之PET膜或OPP膜作為分隔件,而轉印其表面之方法。In the case where fine irregularities are formed on the surface of the release film, there is a method in which fine irregularities are formed on the outer peripheral surface of the above-mentioned metal cooling roll, and the release film is melted by a pressure roller. When the pressure roller is pressed against the cooling roll, the fine unevenness formed on the outer peripheral surface of the cooling roll is transferred to the surface of the release film. Further, in the case of using a separator, there is a method of transferring a surface thereof by using a PET film or an OPP film which has been matted on the surface as a separator.
於使離型用膜之表面為鏡面之情形時,只要以其表面粗度係依據JIS B0601-2001,於速度為0.6 mm/秒、截斷值為0.8 mm、評價長度為8.0 mm下測定之輪廓算術平均偏差Ra為0.10以下,最大高度粗糙度Rz成為1.00以下之方式,適當地形成表面即可。若輪廓算術平均偏差Ra為0.10以下及最大高度粗糙度Rz為1.00以下,則轉印有離型用膜之表面的成形品之表面變得平滑。When the surface of the release film is mirror-finished, the surface roughness is determined according to JIS B0601-2001 at a speed of 0.6 mm/sec, a cutoff value of 0.8 mm, and an evaluation length of 8.0 mm. The arithmetic mean deviation Ra may be 0.10 or less, and the maximum height roughness Rz may be 1.00 or less, and the surface may be appropriately formed. When the contour arithmetic mean deviation 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 release film is transferred is smooth.
於在離型用膜之表面形成微細之凹凸之情形時,只要以其表面粗度係與上述同樣地測定之輪廓算術平均偏差Ra為0.5以上,最大高度粗糙度Rz成為5.00以上之方式,適當地形成表面即可。When the fine unevenness is formed on the surface of the release film, the arithmetic mean deviation Ra of the profile 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 can be formed on the ground.
本發明之離型用膜之厚度為5 μm~500 μm之範圍,較佳為10 μm~400 μm之範圍,只要根據所使用之鑄模模具之形狀適當地選擇即可。於將離型用膜之厚度設為未達5 μm之情形時,於在使用時追從鑄模模具時,存在離型用膜延伸變薄而斷裂,或因鑄模樹脂之壓力而破損之異常,因此欠佳。又,於超過500 μm之情形時,離型用膜之厚度成為障礙,從而存在變得無法追從具有微細之構造之鑄模模具之異常,或者變得無法將鑄模模具之複雜的形狀轉印至成形品之異常,因此欠佳。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 for use. When the thickness of the film for release film is less than 5 μm, when the mold is used in the mold, the film for release film is thinned and broken, or the film is broken due to the pressure of the mold resin. Therefore, it is not good. In addition, when the thickness exceeds 500 μm, the thickness of the release film becomes an obstacle, and there is an abnormality that the mold of the mold having a fine structure cannot be traced, or the complicated shape of the mold cannot be transferred to The abnormality of the molded article is therefore not good.
[實施例][Examples]
以下,使用表1、2對本發明之離型用膜之實施例加以說明。Hereinafter, examples of the release film of the present invention will be described using Tables 1 and 2.
再者,本發明之離型用膜不限定於實施例1~8。Further, the release film of the present invention is not limited to Examples 1 to 8.
此處,表1、2所示之胺基甲酸酯系彈性體1、氟系界面活性劑1及氟系界面活性劑2係使用如下所示之材料。Here, the urethane-based elastomer 1, the fluorine-based surfactant 1 and the fluorine-based surfactant 2 shown in Tables 1 and 2 are the materials shown below.
(胺基甲酸酯系彈性體1)(urethane-based elastomer 1)
Miractran E598PNAT:商品名,日本聚胺酯工業公司製造,JIS A硬度為98,維卡軟化溫度為141℃Miractran E598PNAT: trade name, manufactured by Japan Polyurethane Industry Co., Ltd., JIS A hardness is 98, Vicat softening temperature is 141 °C
(氟系界面活性劑1)(Fluorine surfactant 1)
Eftop EF-N112:商品名,三菱綜合材料公司製造,雙(三氟甲基磺醯基)醯亞胺鉀鹽((CF3SO2)2NK),熔點為200℃Eftop EF-N112: trade name, manufactured by Mitsubishi Materials Corporation, bis(trifluoromethylsulfonyl) quinone imide potassium salt ((CF 3 SO 2 ) 2 NK), melting point 200 ° C
(氟系界面活性劑2)(Fluorine surfactant 2)
Eftop EF-12:商品名,三菱綜合材料公司製造,三氟甲基磺酸鉀(CF3SO3K),熔點為233℃Eftop EF-12: trade name, manufactured by Mitsubishi Materials Corporation, potassium trifluoromethanesulfonate (CF 3 SO 3 K), melting point 233 ° C
以下,基於表1、2,對離型用膜之製作、剝離性、耐熱性、模具尺寸轉印性、表面平滑性及實際使用性加以詳述。再者,該等成為於表3之比較例1~3中亦同樣地適用之內容。Hereinafter, the production, release property, heat resistance, mold size transferability, surface smoothness, and practical use of the film for release film will be described in detail based on Tables 1 and 2. In addition, these are similarly applied to the comparative examples 1 to 3 of Table 3.
(離型用膜之製作)(production of release film)
將熱塑性彈性體組合物供給至Φ40 mm、L/D=25之單軸擠出機(IKG公司製造),使用壓縮比為2.5之全螺紋擠出螺桿,於料缸溫度為180℃~210℃之條件下,進行熔融混練,於鑄模溫度為210℃~220℃之條件下自寬度為400 mm之T模連續地擠出。該擠出之離型用膜係於牽拉機內,自壓接輥側使消光加工PET膜為分隔件,自冷卻輥側使鏡面加工PET膜為分隔件而供給,將該等夾於壓接輥冷卻輥之間進行冷卻,於捲取機內利用切刀將兩端部裁斷,將離型用膜捲取至捲取管上,藉此製造表1~3中記載之厚度、且寬度為250 mm、長度為50 m之離型用膜。將該等離型用膜於80℃之氣體環境下放置24小時進行熟化。於熟化結束後,一面將分隔件之消光加工PET膜及鏡面加工PET膜剝離,一面重新捲繞離型膜,獲得評價用離型膜。The thermoplastic elastomer composition was supplied to a single-axis extruder (manufactured by IKG Corporation) of Φ40 mm and L/D=25, and a full-thread extrusion screw with a compression ratio of 2.5 was used at a cylinder temperature of 180 ° C to 210 ° C. Under the conditions, melt-kneading was carried out, and the T-die having a width of 400 mm was continuously extruded at a mold temperature of 210 ° C to 220 ° C. The film for extrusion release is attached to a pulling machine, and the matte-processed PET film is used as a separator from the side of the pressure-bonding roll, and the mirror-finished PET film is supplied as a separator from the side of the cooling roll, and the film is sandwiched by the pressure. Cooling is performed between the cooling rolls of the rolls, 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 manufacturing the thickness and width described in Tables 1 to 3. A release film of 250 mm and a length of 50 m. The film for detachment was allowed to stand in a gas atmosphere at 80 ° C for 24 hours for aging. After the completion of the aging, the matte film of the matte film and the mirror-finished PET film were peeled off, and the release film was re-wound to obtain a release film for evaluation.
(評價之方法)(method of evaluation)
評價係使用具備圖1所示之透鏡形狀之圖2(a)、(b)所示之構成之鑄模模具30,使離型用膜吸附於鑄模模具30後,滴加聚矽氧樹脂組合物而進行熱壓成形,分別對剝離性、耐熱性、模具尺寸轉印性、表面平滑性進行評價。In the evaluation, the mold 30 having the configuration shown in FIGS. 2(a) and 2(b) having the lens shape shown in FIG. 1 is used, and the release film is adsorbed to the mold 30, and the polyoxymethylene resin composition is added dropwise. Further, hot press forming was performed to evaluate peelability, heat resistance, mold size transferability, and surface smoothness.
具體而言,以於鑄模模具30中離型用膜之消光面成為鑄模模具30側,鏡面成為空氣側之方式張設離型用膜,以真空吸引而使離型用膜吸附於鑄模模具30。繼而,於離型用膜上滴加聚矽氧樹脂組合物RHODORSIL RTV141(BLUESTAR SILICONES公司製造),於該等上貼壓表面經硬鉻電鍍之平板模具,由兩個模具夾持進行熱壓成形。對成形之積層品的離型用膜與硬化之聚矽氧樹脂之剝離性、離型用膜之耐熱性、硬化之聚矽氧樹脂進行模具尺寸轉印性與表面平滑性評價。熱壓成形係於溫度為140℃、壓力為10 kg/cm2、5分鐘之條件下實施。Specifically, the matte surface of the release film in the mold 30 is placed on the side of the mold 30, and the release film is placed on the air side, and the release film is adsorbed to the mold 30 by vacuum suction. . Then, a polyoxyphthalocene resin composition RHODORSIL RTV141 (manufactured by BLUESTAR SILICONES Co., Ltd.) was dropped on the release film, and the flat plate mold which was subjected to hard chrome plating on the surface was subjected to hot press forming by sandwiching the two molds. . The mold release property and the surface smoothness were evaluated for the release property of the formed release product from the cured release resin, the heat resistance of the release film, and the cured polyoxymethylene resin. 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.
(剝離性)(peelability)
剝離性之評價係將硬化之聚矽氧樹脂組合物可不殘留於離型用膜上地剝離之情形表示為「○」,將聚矽氧樹脂組合物部分性地破斷而殘存於離型用膜上之情形表示為「×」。The peeling property is evaluated as "○" in the case where the cured polyoxyxene resin composition is peeled off without leaving the release film, and the polyoxyxylene resin composition is partially broken and remains in the release type. The condition on the film is expressed as "x".
(耐熱性)(heat resistance)
耐熱性之評價係以目視觀察剝離了硬化之聚矽氧樹脂組合物之離型用膜,將無熔融、熔化地保持膜形狀之情形表示為「○」,將離型用膜存在熔融、熔化之情形表示為「×」。In the evaluation of the heat resistance, the film for release of the cured polyfluorene resin composition was peeled off by visual observation, and the film shape was maintained as "○" without melting or melting, and the release film was melted and melted. The situation is expressed as "X".
(模具尺寸轉印性)(mold size transferability)
模具尺寸轉印性係測定硬化之聚矽氧樹脂組合物之尺寸而進行評價。將透鏡高度之評價基準設為自孔深4 mm減去離型用膜之厚度而得之尺寸進一步-0.1 mm以內之範圍,亦即,設為((4-離型用膜之厚度)-0.1)mm以上。將25個透鏡全部於基準以內之情形表示為「○」,將即便存在1個未滿足基準之形狀之情形表示為「×」。The mold size transferability was evaluated by measuring the size of the hardened polyoxyxene resin composition. The evaluation criterion of the height of the lens is set to be within a range of -0.1 mm or less from the thickness of the film for the release of 4 mm from the hole depth, that is, ((the thickness of the film for 4-release film) - 0.1) or more. The case where all of the 25 lenses are within the reference is expressed as "○", and the case where there is one shape that does not satisfy the reference is indicated as "x".
(表面平滑性)(surface smoothness)
表面平滑性係以目視對硬化之聚矽氧樹脂組合物之表面狀態進行評價。將聚矽氧樹脂之表面未產生凹凸或褶皺之情形表示為「○」,將產生凹凸或褶皺之情形表示為「×」。The surface smoothness was evaluated by visually observing the surface state of the hardened polyoxyxene resin composition. The case where no unevenness or wrinkles were formed on the surface of the polyoxymethylene resin was indicated as "○", and the case where irregularities or wrinkles were generated was indicated as "x".
(實際使用性)(actual usability)
關於實際使用性,係藉由於鑄模成形裝置內進行樹脂鑄模成形而進行確認、評價。具體而言,於作為模塑裝置的APIC YAMADA公司製造之鑄模成形裝置G-LINE manual press(商品名)中,使用RHODORSIL RTV141(BLUESTAR SILICONES公司製造)作為聚矽氧樹脂組合物,藉由目視確認實際使用性。The actual usability was confirmed and evaluated by resin molding in a mold forming apparatus. Specifically, RHODORSIL RTV141 (manufactured by BLUESTAR SILICONES Co., Ltd.) was used as a polyoxyxylene resin composition in a mold forming apparatus G-LINE manual press (trade name) manufactured by APIC YAMADA Co., Ltd., which is a molding apparatus, and visually confirmed. Practical use.
實際使用性之評價係將如下狀態設為「○」:於在鑄模成形裝置內傳送離型用膜時於不使膜鬆弛之狀態下供給,於吸附時膜不產生褶皺,熱壓成形後,離型用膜與聚矽氧樹脂組合物之剝離性良好,且硬化之聚矽氧樹脂組合物之表面無凹凸或褶皺而平滑,離型用膜無破損或熔斷,無聚矽氧樹脂組合物之殘留,鑄模模具無污垢;將或多或少存在異常之情形表示為「×」。In the evaluation of the practical use, the following state is set to "○": when the release film is conveyed in the mold forming apparatus, the film is supplied without being loosened, and the film does not wrinkle during the adsorption, and after hot press forming, The release film and the polyoxymethylene resin composition have good peelability, and the surface of the cured polyoxymethylene resin composition is smooth without unevenness or wrinkles, and the release film is not broken or melted, and the polyoxymethylene resin composition is not provided. The residue of the mold is free from dirt; the case where there is more or less abnormality is expressed as "x".
如表3所示,於比較例1中,以旭硝子公司製造之ETFE膜、Aflex(商品名)之厚度100 μm者為比較對象,模具尺寸轉印性較差,未能獲得實際使用性。於比較例2中,以旭硝子公司製造之ETFE膜、Aflex(商品名)之厚度25 μm者為比較對象,於吸附至鑄模模具內時膜破損,未能獲得實際使用性。於比較例3中,以Toray-DuPont公司製造之Hytre 15577(商品名),亦即包含聚酯-聚醚共聚物,D硬度為55,維卡軟化溫度為192℃之熱塑性彈性體組合物的厚度為50 μm之離型用膜為比較對象。於包含聚矽氧樹脂組合物之成形品之表面產生褶皺,表面平滑性較差,未能獲得實際使用性。As shown in Table 3, in Comparative Example 1, the ETFE film manufactured by Asahi Glass Co., Ltd. and the Aflex (trade name) having a thickness of 100 μm were compared, and the mold size transferability was poor, and practical use was not obtained. In Comparative Example 2, the ETFE film manufactured by Asahi Glass Co., Ltd. and the Aflex (trade name) having a thickness of 25 μm were compared, and when the film was adsorbed into the mold, the film was broken, and practical use was not obtained. In Comparative Example 3, Hytre 15577 (trade name) manufactured by Toray-DuPont Co., Ltd., that is, a thermoplastic elastomer composition comprising a polyester-polyether copolymer having a D hardness of 55 and a Vicat softening temperature of 192 ° C was used. A release film having a thickness of 50 μm was used as a comparison object. Wrinkles were formed on the surface of the molded article containing the polyoxyxene resin composition, and the surface smoothness was poor, and practical use was not obtained.
相對於此,如表1、2所示,可明確本發明之各實施例之離型用膜,除了獲得剝離性以外,亦具有耐熱性,且模具尺寸轉印性與表面平滑性優異,進而賦予有實際使用性。由此可知:藉由本發明可獲得具有如下性質之離型用膜:與對鑄模樹脂進行成形加工而獲得之成形品之剝離性優異,並且可獲得形狀與表面性優異之成形品。On the other hand, as shown in Tables 1 and 2, it is possible to clarify that the release film of each of the examples of the present invention has heat resistance and is excellent in mold size transferability and surface smoothness, in addition to the release property. Give practical use. According to the present invention, it is possible to obtain a release film having the following properties, which is excellent in peelability from a molded article obtained by molding a mold resin, and a molded article excellent in shape and surface properties can be obtained.
以上,使用實施形態對本發明進行了說明,本發明之技術範圍當然並不限定於上述實施形態所記載之範圍。業者應明白可對上述實施形態加以多種變更或改良。又,由申請專利範圍之記載可明確加以此種變更或改良之形態亦可包含於本發明之技術範圍內。The present invention has been described above using the embodiments, and the technical scope of the present invention is of course not limited to the scope described in the above embodiments. The skilled person will appreciate that various modifications or improvements can be made to the above-described embodiments. Further, it is to be understood that such changes or modifications can be made without departing from the scope of the invention.
1...擠出機1. . . Extruder
2...材料投入料斗2. . . Material input hopper
3...氮氣供給用導管3. . . Nitrogen supply conduit
4...連接管4. . . Connecting pipe
5...過濾器5. . . filter
6...齒輪泵6. . . Gear pump
7...T模7. . . T mode
7a...模唇部7a. . . Lip lip
8...膜8. . . membrane
9...壓接輥9. . . Crimp roller
10...冷卻輥10. . . Cooling roller
11...牽拉機11. . . Pulling machine
12、13...傳送輥對12, 13. . . Conveyor roller pair
14...厚度測定器14. . . Thickness measuring device
16...捲取管16. . . Take-up tube
17a、17b...送出輥17a, 17b. . . Feed roller
18a、18b...分隔件18a, 18b. . . Separator
20...砲彈型LED透鏡20. . . Cannonball type LED lens
21a、21b...導線21a, 21b. . . wire
30...鑄模模具30. . . Molding mold
31...透鏡成形凹部31. . . Lens forming recess
圖1係本發明之實施形態之砲彈型LED透鏡之側視圖。Fig. 1 is a side view of a bullet-type LED lens according to an embodiment of the present invention.
圖2(a)係本發明之實施形態之砲彈型LED透鏡之鑄模模具的俯視圖。圖2(b)係本發明之實施形態之砲彈型LED透鏡之鑄模模具的圖2(a)之A-A箭頭方向指向剖面圖。Fig. 2 (a) is a plan view showing a mold of a cannonball type LED lens according to an embodiment of the present invention. Fig. 2 (b) is a cross-sectional view taken along the line A-A of Fig. 2 (a) of the casting mold of the bullet-type LED lens according to the embodiment of the present invention.
圖3係表示本發明之實施形態之離型用膜膜製造裝置之概略構成的圖。Fig. 3 is a view showing a schematic configuration of a film forming apparatus for release film according to an embodiment of the present invention.
圖4係表示本發明之實施形態的圖2所示之膜製造裝置之材料投入料斗之周邊的剖面圖。Fig. 4 is a cross-sectional view showing the vicinity of a material input hopper of the film production apparatus shown in Fig. 2 according to an embodiment of the present invention.
20...砲彈型LED透鏡20. . . Cannonball type LED lens
21a、21b...導線21a, 21b. . . wire
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JP5541468B2 (en) * | 2012-02-20 | 2014-07-09 | 信越ポリマー株式会社 | Release film |
CN107541053A (en) * | 2017-09-04 | 2018-01-05 | 瑞安市鸿日塑胶有限公司 | Ameliorative TUP films |
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JP4849595B2 (en) * | 2005-11-11 | 2012-01-11 | 信越ポリマー株式会社 | Holding jig |
JP4910413B2 (en) * | 2006-02-02 | 2012-04-04 | 三菱化学株式会社 | Releaseable resin composition, molded product and laminate thereof |
KR101446928B1 (en) * | 2007-12-26 | 2014-10-06 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Multi-layer transparent sheet having electrostatic dissipative properties |
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2011
- 2011-03-30 JP JP2011076089A patent/JP5288422B2/en not_active Expired - Fee Related
-
2012
- 2012-01-11 KR KR1020120003257A patent/KR20120111959A/en not_active Application Discontinuation
- 2012-03-22 TW TW101109944A patent/TWI527856B/en not_active IP Right Cessation
- 2012-03-27 CN CN2012100844557A patent/CN102729369A/en active Pending
Also Published As
Publication number | Publication date |
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KR20120111959A (en) | 2012-10-11 |
TW201239032A (en) | 2012-10-01 |
JP2012206490A (en) | 2012-10-25 |
JP5288422B2 (en) | 2013-09-11 |
CN102729369A (en) | 2012-10-17 |
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