TWI492829B - Release film - Google Patents

Release film Download PDF

Info

Publication number
TWI492829B
TWI492829B TW101138135A TW101138135A TWI492829B TW I492829 B TWI492829 B TW I492829B TW 101138135 A TW101138135 A TW 101138135A TW 101138135 A TW101138135 A TW 101138135A TW I492829 B TWI492829 B TW I492829B
Authority
TW
Taiwan
Prior art keywords
film
release film
thermoplastic
elastomer
mold
Prior art date
Application number
TW101138135A
Other languages
Chinese (zh)
Other versions
TW201334938A (en
Inventor
Michimasa Ote
Norimasa Shinada
Takashi Nogami
Original Assignee
Shinetsu Polymer Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shinetsu Polymer Co filed Critical Shinetsu Polymer Co
Publication of TW201334938A publication Critical patent/TW201334938A/en
Application granted granted Critical
Publication of TWI492829B publication Critical patent/TWI492829B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/56Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68Release sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/12Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/22Thermoplastic resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (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

離型用膜Release film

本發明係關於一種離型用膜,例如係關於一種光半導體元件或半導體元件之模鑄成形時所使用,尤其是LED(light-emitting diode,發光二極體)透鏡之模鑄成形時所使用之離型用膜。The present invention relates to a release film, for example, used in the molding of an optical semiconductor element or a semiconductor element, particularly in the molding of an LED (light-emitting diode) lens. Release film.

例如包含LED、光隔離器、光電晶體、光二極體、CCD(Charge Coupled Device,電荷耦合元件)、CMOS(Complementary Metal Oxide Semiconductor,互補性金屬氧化半導體)等之光半導體元件、或包含電晶體、IC(Integrated Circuit,積體電路)、LSI(Large Scale Integrated Circuit,大型積體電路)、超LSI等之半導體元件係將聚矽氧橡膠組合物或環氧樹脂組合物作為密封材料,藉由模鑄成形進行密封而構成。For example, an optical semiconductor element including an LED, an optical isolator, a photoelectric crystal, a photodiode, a CCD (Charge Coupled Device), a CMOS (Complementary Metal Oxide Semiconductor), or a transistor, A semiconductor element such as an IC (Integrated Circuit), an LSI (Large Scale Integrated Circuit), or a super LSI uses a polyoxyethylene rubber composition or an epoxy resin composition as a sealing material by a mold. It is formed by casting and sealing.

於此種光半導體元件或半導體元件之密封中使用模鑄成形裝置,於該模鑄成形裝置之模具中填充聚矽氧橡膠組合物或環氧樹脂組合物作為密封材料並成形。A die-casting apparatus is used for sealing such an optical semiconductor element or a semiconductor element, and a polyoxyxylene rubber composition or an epoxy resin composition is filled in a mold of the mold-forming apparatus as a sealing material and molded.

於該情形時,作為使模具與成形品離型之方法,例如使離型用膜介於模具與填充於該模具中之密封材料間之方法已實用化(參照專利文獻1)。離型用膜於模鑄成形裝置內利用輥-輥(Roll to Roll)進行供給,並放入溫度調整為成形加工溫度之模具中,利用真空進行吸引而密接於模具上,其後填充密封材料。於一定時間後打開模具時,在離型用膜 被吸引於模具上之狀態下將成形品自離型用膜剝離。作為該離型用膜,例如使用包含熱塑性氟樹脂之四氟乙烯-乙烯共聚合樹脂(ETFE(ethylene-tetra fluoro ethylene)樹脂)、或四氟乙烯-六氟丙烯共聚合樹脂(FEP(fluorinated ethylene propylene,氟化乙烯丙烯)樹脂)之單層膜(參照專利文獻2)。In this case, as a method of releasing the mold from the molded article, for example, a method in which the release film is interposed between the mold and the sealing material filled in the mold has been put into practical use (see Patent Document 1). The release film is supplied by a roll-to-roll in a die-casting apparatus, and placed in a mold whose temperature is adjusted to a molding temperature, and is suctioned by vacuum to adhere to the mold, and then filled with a sealing material. . When the mold is opened after a certain period of time, the film for release film The molded article is peeled off from the release film in a state of being attracted to the mold. As the film for release film, for example, a tetrafluoroethylene-ethylene copolymer resin (ETFE) containing a thermoplastic fluororesin or a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP (fluorinated ethylene) is used. A single layer film of propylene (fluorinated ethylene propylene) resin (refer to Patent Document 2).

然而,於將此種離型用膜用於以聚矽氧橡膠組合物作為密封材料之LED透鏡之成形的情形時,例如對於底面為6 mm左右且高度為4 mm左右之砲彈型透鏡形狀,存在如下不良情況:離型用膜有時即便利用真空進行吸引亦無法延伸,且即便延伸亦未密接於模具,從而無法獲得按照設計之LED透鏡。又,若使離型用膜之厚度變薄而使其容易延伸,則會產生於利用真空進行吸引時因模具之邊緣而損壞離型用膜之不良情況。However, when such a release film is used for the formation of an LED lens using a polyoxyethylene rubber composition as a sealing material, for example, the bottom surface is A shape of a cannonball lens of about 6 mm and a height of about 4 mm has the following disadvantages: the release film may not be stretched even if it is attracted by vacuum, and even if it is extended, it is not closely adhered to the mold, so that it cannot be obtained according to design. LED lens. Further, when the thickness of the release film is made thin and it is easily stretched, it may cause a problem that the release film is damaged by the edge of the mold when suction is performed by vacuum.

另一方面,作為離型用膜,如下述專利文獻3所示,已知有使用包含如下樹脂組合物之膜之方法,該樹脂組合物含有於結晶成分中包含對苯二甲酸丁二酯之結晶性芳香族聚酯。On the other hand, as a release film, as disclosed in the following Patent Document 3, there is known a method of using a film comprising a resin composition containing butylene terephthalate in a crystal component. Crystalline aromatic polyester.

然而,於將由含有包含對苯二甲酸丁二酯之結晶性芳香族聚酯之樹脂組合物所構成的膜用於LED透鏡之成形之情形時,雖然離型用膜在利用真空進行吸引時密接於模具上,但由於超過降伏點而延伸,故而產生離型用膜局部變薄,於所成形之LED透鏡之表面上形成凹凸或褶皺的不良狀況。又,作為聚矽氧橡膠組合物,使用有加成型液狀聚 矽氧橡膠,但產生如下不良情況:存在於離型用膜中之化合物成為加成型液狀聚矽氧橡膠之觸媒毒而抑制硬化,與離型用膜之接觸面未硬化而殘留凝膠狀黏著物。因此,於使用加成型液狀聚矽氧橡膠之LED透鏡之模鑄成形中,實際情況為尚無可較佳地用作離型用膜之膜。However, when a film composed of a resin composition containing a crystalline aromatic polyester containing butylene terephthalate is used for the formation of an LED lens, the release film is adhered while being sucked by vacuum. On the mold, since it extends beyond the point of undulation, the film for release film is locally thinned, and defects such as irregularities or wrinkles are formed on the surface of the formed LED lens. Moreover, as a polyoxyxene rubber composition, an additive liquid polymerization is used. Oxide rubber, but the following problems occur: the compound present in the film for release molding is a catalytic poison of the addition-form liquid polyoxyethylene rubber, and the hardening is inhibited, and the contact surface with the release film is not hardened and the gel remains. Adhesive. Therefore, in the molding of an LED lens using an additive liquid polyoxyethylene rubber, it is practical that there is no film which can be preferably used as a film for release film.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[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

本發明係鑒於此種情況而完成者,其目的在於提供一種於使用加成型液狀聚矽氧橡膠之LED透鏡之模鑄成形中,與模具或成形品之剝離性優異之離型用膜。The present invention has been made in view of such a situation, and an object of the present invention is to provide a release film which is excellent in peelability from a mold or a molded article in die casting using an LED lens in which a liquid polyoxyethylene rubber is added.

又,本發明之目的在於提供一種將模具之形狀按照設計轉印至成形品上的模形狀轉印性優異之離型用膜。Moreover, an object of the present invention is to provide a release film which is excellent in mold transferability by transferring a shape of a mold to a molded article.

又,本發明之目的在於提供一種於成形品之表面上不殘留凝膠狀黏著物而獲得成形品之表面平滑性之離型用膜。Moreover, an object of the present invention is to provide a release film which does not leave a gel-like adhesive on the surface of a molded article and obtains surface smoothness of the molded article.

進而,本發明之目的在於提供一種具有於140℃前後之使用溫度下之耐熱性的離型用膜。Further, an object of the present invention is to provide a release film having heat resistance at a use temperature of about 140 °C.

為達成此種目的,本發明係於熱塑性聚胺基甲酸酯系彈性體中含有熱塑性氟樹脂而構成,該熱塑性聚胺基甲酸酯 系彈性體之JIS A硬度為70以上,維氏軟化溫度為100~180℃,且上述熱塑性氟樹脂相對於熱塑性聚胺基甲酸酯系彈性體100質量份,含於1~400質量份之範圍內。In order to achieve such an object, the present invention is constituted by a thermoplastic fluororesin contained in a thermoplastic polyurethane elastomer, which is a thermoplastic urethane. The JIS A hardness of the elastomer is 70 or more, the Vickers softening temperature is 100 to 180 ° C, and the thermoplastic fluororesin is contained in an amount of 1 to 400 parts by mass based on 100 parts by mass of the thermoplastic polyurethane elastomer. Within the scope.

本發明可藉由以下構成而理解。The present invention can be understood by the following constitution.

(1)本發明之離型用膜之特徵在於由相對於JIS A硬度為70以上、維氏軟化溫度為100~180℃之熱塑性聚胺基甲酸酯系彈性體100質量份,於1~400質量份之範圍內含有熱塑性氟樹脂之熱塑性彈性體2成分組合物所構成。(1) The film for release film of the present invention is characterized in that it is composed of 100 parts by mass of a thermoplastic polyurethane elastomer having a hardness of 70 or more and a Vickers softening temperature of 100 to 180 ° C with respect to JIS A. A thermoplastic elastomer 2 component composition containing a thermoplastic fluororesin in a range of 400 parts by mass.

(2)如(1)之構成之本發明之離型用膜,其中上述熱塑性氟樹脂為熔點140℃以上、240℃以下之熱塑性四氟乙烯系共聚物。(2) The release film of the present invention, wherein the thermoplastic fluororesin is a thermoplastic tetrafluoroethylene copolymer having a melting point of 140 ° C or more and 240 ° C or less.

(3)如(1)或(2)之構成之本發明之離型用膜,其包含相對於上述熱塑性彈性體2成分組合物100質量份,於0.05~5.0質量份之範圍內含有選自由含氟之醇系化合物與含氟之二醇化合物所組成之群中的一種或複數種化合物之熱塑性彈性體3成分組合物。(3) The film for release film of the present invention having the composition of the thermoplastic elastomer 2 component composition, which is contained in the range of 0.05 to 5.0 parts by mass, selected from the group consisting of (1) or (2) A thermoplastic elastomer 3 component composition of one or a plurality of compounds of a group consisting of a fluorine-containing alcohol compound and a fluorine-containing diol compound.

(4)如(2)或(3)之構成之本發明之離型用膜,其中上述含氟之醇系化合物為通式(A)所示之化合物,上述含氟之二醇化合物為通式(B)所示之化合物,Rf1 (CH2 )m OH………(A)(式中,Rf1 表示碳數為3~20之直鏈狀或支鏈狀之全氟烷基或全氟烷基醚基,m為1~5之整數)Rf2 (CH2 )n OCH2 CH(OH)CH2 OH………(B)(式中,Rf2 表示碳數為3~20之直鏈狀或支鏈狀之全氟烷 基,n表示1或2之整數)。(4) The film for release film of the present invention having the composition of (2) or (3), wherein the fluorine-containing alcohol compound is a compound represented by the formula (A), and the fluorine-containing diol compound is a pass. a compound of the formula (B), Rf 1 (CH 2 ) m OH (...) (wherein Rf 1 represents a linear or branched perfluoroalkyl group having a carbon number of 3 to 20 or Perfluoroalkyl ether group, m is an integer from 1 to 5) Rf 2 (CH 2 ) n OCH 2 CH(OH)CH 2 OH (...) (wherein Rf 2 represents a carbon number of 3 to 20 A linear or branched perfluoroalkyl group, n represents an integer of 1 or 2.

(5)如(1)至(4)之任一構成之本發明之離型用膜,其中上述熱塑性彈性體2成分組合物及3成分組合物更包含屬於潤滑劑、抗結塊劑、酚系抗氧化劑、磷系抗氧化劑中之一種或複數種添加劑。(5) The film for release film of the present invention having any one of (1) to (4), wherein the thermoplastic elastomer 2 component composition and the three component composition further comprise a lubricant, an anti-caking agent, and a phenol. It is one of an antioxidant or a phosphorus antioxidant or a plurality of additives.

(6)如(1)至(5)之任一構成之本發明之離型用膜,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 之範圍內。(6) The release film of the present invention according to any one of (1) to (5), wherein the tensile modulus of the film is in the longitudinal direction of the film (MD, Machine Direction) and the transverse direction of the film (TD, Transverse) Direction) is in the range of 10~500 N/mm 2 .

(7)如(1)至(6)之任一構成之本發明之離型用膜,其中膜之50%模數(50% Mo)於膜縱方向(MD)與膜橫方向(TD)上之比(MD)/(TD)為0.9~1.2之範圍內。(7) The release film of the present invention according to any one of (1) to (6), wherein the film has a 50% modulus (50% Mo) in the film longitudinal direction (MD) and the film transverse direction (TD). The upper ratio (MD) / (TD) is in the range of 0.9 to 1.2.

(8)如(1)至(7)之任一構成之本發明之離型用膜,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之範圍內。(8) The release film of the present invention having any one of (1) to (7), wherein a ratio of a 50% modulus (50% Mo) of the film to a 100% modulus (100% Mo) (100) % Mo) / (50% Mo) is in the range of 1.0 to 1.6 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film.

(9)如(1)至(8)之任一構成之本發明之離型用膜,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%。(9) The release film of the present invention having any one of (1) to (8), wherein the tensile elongation of the film exceeds 350% in both the longitudinal direction (MD) and the transverse direction (TD) of the film. .

(10)如(1)至(9)之任一構成之本發明之離型用膜,其係由含有包含熱塑性樹脂之膜、或包含上述熱塑性聚胺基甲酸酯系彈性體以外之其他熱塑性彈性體之膜的多層膜所構成。(10) The release film of the present invention having any one of (1) to (9), which comprises a film containing a thermoplastic resin or a thermoplastic polyurethane-containing elastomer A multilayer film of a film of a thermoplastic elastomer.

根據本發明之離型用膜,與模具或成形品之剝離性優 異,且將模具之形狀按照設計轉印至成形品之模形狀轉印性優異,並且於成形品之表面上不殘留凝膠狀黏著物而可獲得成形品之表面平滑性,亦可具備耐熱性。The release film according to the present invention has excellent peelability from a mold or a molded article The shape of the mold is excellent in transferability to the shape of the mold to be transferred to the molded article, and the gel-like adhesive does not remain on the surface of the molded article, so that the surface smoothness of the molded article can be obtained, and heat resistance can be obtained. Sex.

本發明者等人為達成上述目的進行了各種研究,結果判明,包含如下熱塑性彈性體2成分組合物之離型用膜與模具或成形品之剝離性優異,且將模具之形狀按照設計轉印至成形品之模形狀轉印性優異,並且於成形品之表面上不殘留凝膠狀黏著物而可獲得成形品之表面平滑性,亦可具備耐熱性,上述熱塑性彈性體2成分組合物相對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及維氏軟化溫度為100~180℃之熱塑性聚胺基甲酸酯系彈性體100質量份,含有熱塑性氟樹脂1~400質量份。The present inventors have conducted various studies to achieve the above object, and as a result, it has been found that the film for release film comprising the thermoplastic elastomer 2 component composition is excellent in peelability from a mold or a molded article, and the shape of the mold is transferred to the design. The molded article has excellent mold shape transferability, and does not leave a gel-like adhesive on the surface of the molded article, thereby obtaining surface smoothness of the molded article, and also having heat resistance, and the thermoplastic elastomer 2 component composition is relative to 100 parts by mass of a thermoplastic polyurethane elastomer having a JIS A hardness of 70 or more, a specific gravity of 1.05 to 1.30, and a Vickers softening temperature of 100 to 180 ° C in a polyurethane-based elastomer, and containing thermoplastic fluorine The resin is 1 to 400 parts by mass.

本發明中之熱塑性聚胺基甲酸酯系彈性體係藉由聚異氰酸酯、多元醇及鏈延長劑之3成分之反應而獲得之熱塑性聚胺基甲酸酯系彈性體。The thermoplastic polyurethane-based elastomer of the present invention is a thermoplastic polyurethane-based elastomer obtained by a reaction of three components of a polyisocyanate, a polyol, and a chain extender.

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、萘-1,4-二異氰酸酯、萘-1,5-二 異氰酸酯、3,3'-二甲氧基二苯基-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、降烷二異氰酸甲酯等脂環族二異氰酸酯類,上述異氰酸酯之縮二脲體、二聚物、三聚物、二聚物-三聚物、碳二醯亞胺體、脲酮亞胺體、由二官能以上之多元醇等與上述異氰酸酯之反應而獲得之加成物等。又,可列舉利用甲醇、正丁醇、苄醇、乙醯乙酸乙酯、ε-己內醯胺、甲基乙基酮肟、苯酚、甲酚等在分子內具有一個活性氫之阻斷劑而使異氰酸酯基之一部分穩定化的聚異氰酸酯。該等可使用一種或混合兩種以上而使用。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, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl- Aromatic diisocyanates such as 4,4'-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane diisocyanate, trimethylhexamethylene diisocyanate, leucine diisocyanate, etc. Aliphatic diisocyanates, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate Acid ester, hydrogenated diphenylmethane diisocyanate, tetramethyl xylene diisocyanate, lower An alicyclic diisocyanate such as methyl alkane diisocyanate, a diuret, a dimer, a trimer, a dimer-trimer, a carbodiimide, a uretonimine of the above isocyanate An adduct obtained by reacting a difunctional or higher polyhydric alcohol with the above isocyanate or the like. Further, a blocking agent having an active hydrogen in a molecule such as methanol, n-butanol, benzyl alcohol, ethyl acetate, ε-caprolactam, methyl ethyl ketoxime, phenol or cresol may be mentioned. A polyisocyanate which partially stabilizes one of the isocyanate groups. These may be used alone or in combination of two or more.

上述多元醇係數量平均分子量為500~10000之高分子多元醇,例如可列舉聚酯多元醇、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。該等可使用一種或混合兩種以上而使用。The polymer polyol having a polyhydric alcohol coefficient and an average molecular weight of 500 to 10,000 may, for example, be a polyester polyol, a polyester decylamine polyol, a polycarbonate polyol, a polyether polyol, a polyether ester polyol, or a poly Olefin polyols and the like. These may be used alone or in combination of two or more.

作為上述聚酯多元醇、聚酯醯胺多元醇,例如可列舉由多羧酸與多元醇,或根據需要併用二胺或胺基醇,藉由縮合反應而獲得者。The polyester polyol and the polyester decylamine polyol are, for example, those obtained by a condensation reaction using a polycarboxylic acid and a polyhydric alcohol, or a diamine or an amino alcohol in combination, if necessary.

作為上述多羧酸,例如可列舉: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,例如可列舉藉由丁內酯、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, and alkyl phthalate. Esters, trimellitic acid, maleic acid, fumaric acid, itaconic acid, and the like. Further, for example, those obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone, and caprolactone may be mentioned.

作為上述多元醇,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。作為上述二胺或胺基醇,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,可列舉將低分子多元醇、低分子多胺、低分子胺基醇作為起始劑,利用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 amino alcohol include low molecular polyamines such as ethylenediamine, hexamethylenediamine, xylylenediamine, and isophorone diamine, and low molecular weights such as monoethanolamine, diethanolamine, and triethanolamine. Amino alcohols. Further, a low molecular weight polyol, a low molecular weight polyamine, and a low molecular weight amino alcohol are used as a starting agent, and ring-opening of a cyclic ester (lactone) monomer such as ε-caprolactone or γ-valerolactone is used. A lactone-based polyester polyol obtained by polymerization.

作為上述聚碳酸酯多元醇,可列舉藉由用於上述聚酯多元醇之合成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 alcohol reaction, dephenolization reaction, and the like.

作為上述聚醚多元醇,可列舉將用於上述聚酯多元醇之低分子多元醇、低分子多胺、低分子胺基醇作為起始劑使環氧乙烷、環氧丙烷、四氫呋喃等開環聚合而成之聚乙二醇、聚丙二醇、聚四亞甲基醚二醇等、及使該等共聚合而成之聚醚多元醇,進而可列舉將上述聚酯多元醇、聚碳酸酯多元醇作為起始劑之聚酯醚多元醇。Examples of the polyether polyol include a low molecular polyol, a low molecular polyamine, and a low molecular weight amino alcohol used in the above polyester polyol as an initiator to open ethylene oxide, propylene oxide, tetrahydrofuran, and the like. Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., which are obtained by cyclic polymerization, and polyether polyols obtained by copolymerizing these, and further, the above-mentioned polyester polyol and polycarbonate A polyester ether polyol having a polyol as a starter.

作為上述聚醚酯多元醇,可列舉除於獲得上述聚酯多元醇時之縮合反應所使用的多元醇之一部分或全部使用聚醚以外,以與上述聚酯多元醇相同之方式獲得者。The polyether ester polyol is obtained in the same manner as the above polyester polyol, except that a part or all of the polyol used for the condensation reaction in obtaining the above polyester polyol is used.

作為上述聚烯烴多元醇,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。Examples of the polyolefin polyol include a hydroxyl group-containing polybutadiene, a hydrogenated hydroxyl group-containing polybutadiene, a hydroxyl group-containing polyisoprene, and a hydrogenated hydroxyl group-containing polyisoprene. Hydroxy-containing chlorinated polypropylene, hydroxyl-containing chlorinated polyethylene, and the like.

又,上述鏈延長劑為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、上述低分子多胺類、上述低分子胺基醇類等。Further, the chain extender is a compound containing an active hydrogen having a number average molecular weight of less than 500, and examples thereof include the above low molecular polyols, the above low molecular polyamines, and the above low molecular weight amino alcohols.

於本發明所使用之上述熱塑性聚胺基甲酸酯系彈性體之製造中,可採用公知之製造方法,例如可採用一步法(one-shot method)、預聚物法、分批反應法、連續反應法、利用捏合機之方法、及利用擠出機之方法等方法。In the production of the above thermoplastic polyurethane-based elastomer used in the present invention, a known production method can be employed, and for example, a one-shot method, a prepolymer method, a batch reaction method, or the like can be employed. A continuous reaction method, a method using a kneader, and a method using an extruder.

關於該熱塑性聚胺基甲酸酯系彈性體之硬度,利用JIS K 7311之試驗法而測定之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硬度並將D硬度之80以下設為上限。該JIS A硬度較佳為80以上,更佳 為90以上。於假設JIS A硬度未達70之情形時,可確認到橡膠性變強,於模鑄成形裝置內之離型用膜之搬送時,離型用膜進行延伸而使搬送不穩定的不良情況。又,於D硬度超過80之情形時,可確認到於擠出成形時產生源自於原料之聚異氰酸酯、多元醇及鏈延長劑之3成分之凝膠的不良情況。The hardness of the thermoplastic polyurethane-based elastomer is 70 or more in JIS A hardness measured by the test method of JIS K 7311. Further, when the JIS A hardness is 100 or more, it is preferable to apply the D hardness and set the D hardness to 80 or less as the upper limit. The JIS A hardness is preferably 80 or more, more preferably It is 90 or more. When it is assumed that the JIS A hardness is less than 70, it is confirmed that the rubber property is strong, and when the release film is conveyed in the mold forming apparatus, the release film is stretched to make the conveyance unstable. Moreover, when the D hardness exceeded 80, it was confirmed that the gel derived from the three components of the polyisocyanate, the polyol, and the chain extender of the raw material was generated at the time of extrusion molding.

上述熱塑性聚胺基甲酸酯系彈性體之維氏軟化溫度係藉由JIS K 7206之試驗法而測定,為100~180℃之範圍內。該維氏軟化溫度較佳為110~180℃之範圍內,更佳為120~180℃之範圍內,進而較佳為130~180℃之範圍內。若假設維氏軟化溫度未達100℃,則可確認到於使用時膜熔接於聚矽氧橡膠而使剝離性降低之不良情況。再者,將維氏軟化溫度之上限設為180℃,其原因在於:無法獲取維氏軟化溫度超過180℃之熱塑性聚胺基甲酸酯系彈性體。The Vickers softening temperature of the above thermoplastic polyurethane-based elastomer is measured by the test method of JIS K 7206 and is in the range of 100 to 180 °C. The Vickers softening temperature is preferably in the range of 110 to 180 ° C, more preferably in the range of 120 to 180 ° C, and still more preferably in the range of 130 to 180 ° C. If the Vickers softening temperature is less than 100 ° C, it is confirmed that the film is welded to the polyoxyethylene rubber at the time of use, and the peeling property is lowered. Further, the upper limit of the Vickers softening temperature was set to 180 ° C because the thermoplastic polyurethane elastomer having a Vickers softening temperature of more than 180 ° C could not be obtained.

本發明所使用之熱塑性氟樹脂為熱塑性四氟乙烯系共聚物。作為熱塑性四氟乙烯系共聚物,例如可列舉四氟乙烯及可與四氟乙烯共聚合之共聚合單體之共聚物。作為共聚合單體,例如可列舉:乙烯、丙烯、丁烯等烯烴類,CF2 =CH2 、CF2 =CFCl等氟乙烯類,CF2 =CFCF3 、CF2 =CHCF3 等氟丙烯類,CF3 CF2 CF2 CF2 CH=CH2 、CF3 CF2 CF2 CF2 CF=CH2 等全氟烷基之碳數為4~12之全氟烷基乙烯類,Rf (OCFXCF2 )m OCF=CF2 (式中,Rf 表示碳數1~6之全氟烷基,X表示氟原子或三氟甲基,m表示0~5之整數)等全氟乙烯基醚基等。該等共聚合單體可單獨使用或以兩種以上 之組合而使用。The thermoplastic fluororesin used in the present invention is a thermoplastic tetrafluoroethylene copolymer. Examples of the thermoplastic tetrafluoroethylene copolymer include a copolymer of tetrafluoroethylene and a copolymerizable monomer copolymerizable with tetrafluoroethylene. Examples of the copolymerizable monomer include olefins such as ethylene, propylene, and butylene; fluoroethylenes such as CF 2 =CH 2 and CF 2 =CFCl; and fluoropropenes such as CF 2 =CFCF 3 and CF 2 =CHCF 3 . , CF 3 CF 2 CF 2 CF 2 CH=CH 2 , CF 3 CF 2 CF 2 CF 2 CF=CH 2 and other perfluoroalkyl groups having a carbon number of 4 to 12 perfluoroalkyl vinyls, R f (OCFXCF 2 ) m OCF=CF 2 (wherein, R f represents a perfluoroalkyl group having 1 to 6 carbon atoms, X represents a fluorine atom or a trifluoromethyl group, and m represents an integer of 0 to 5), and the like is a perfluorovinyl ether group. Wait. These copolymerized monomers may be used singly or in combination of two or more.

作為上述熱塑性四氟乙烯系共聚物之具體例,例如可列舉:乙烯-四氟乙烯共聚物、四氟乙烯-六氟丙烯共聚物、四氟乙烯-全氟(丙基乙烯基醚)共聚物、四氟乙烯-偏二氟乙烯共聚物、四氟乙烯-六氟丙烯-偏二氟乙烯共聚物等。該等熱塑性四氟乙烯系共聚物之熔點較佳為設為140℃以上、240℃以下。若假設熔點未達140℃,則可確認到於用作離型用膜時,膜於模具內熔融之不良情況。又,於使用熔點超過240℃之四氟乙烯系共聚物之情形時,可確認到於熱塑性聚胺基甲酸酯系彈性體之成形加工溫度範圍內未熔融而於膜中殘留未熔融物之不良情況。Specific examples of the thermoplastic tetrafluoroethylene copolymer include an ethylene-tetrafluoroethylene copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a tetrafluoroethylene-perfluoro(propyl vinyl ether) copolymer. , a tetrafluoroethylene-vinylidene fluoride copolymer, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, and the like. The melting point of the thermoplastic tetrafluoroethylene copolymer is preferably 140 ° C or higher and 240 ° C or lower. When the melting point is less than 140 ° C, it is confirmed that the film is melted in the mold when it is used as a release film. Further, when a tetrafluoroethylene-based copolymer having a melting point of more than 240 ° C was used, it was confirmed that the unmelted material remained in the film without being melted in the molding processing temperature range of the thermoplastic polyurethane elastomer. Bad situation.

上述熱塑性氟樹脂係為對膜賦予與模具或成形品之剝離性而混合。熱塑性氟樹脂之混合量相對於熱塑性聚胺基甲酸酯系彈性體100質量份為1~400質量份之範圍內,較佳為5~300質量份之範圍內,更佳為10~200質量份之範圍內,進而較佳為10~100質量份之範圍內。假設於混合量未達1質量份之情形時,可確認到未發揮混合之效果而未使剝離性提高之不良情況。又,若混合量超過400質量份,則可確認到如下不良狀況:熱塑性氟樹脂未均勻地分散於熱塑性聚胺基甲酸酯系彈性體中,於膜延伸時,受到熱塑性氟樹脂所具有之拉伸特性中之降伏點之影響而於膜上產生褶皺。The thermoplastic fluororesin is mixed by imparting releasability to a film or a molded article. The blending amount of the thermoplastic fluororesin is in the range of 1 to 400 parts by mass, preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass based on 100 parts by mass of the thermoplastic polyurethane elastomer. Within the range of the portion, it is preferably in the range of 10 to 100 parts by mass. When the amount of the mixture is less than 1 part by mass, it is confirmed that the effect of mixing is not exerted and the peeling property is not improved. In addition, when the amount is more than 400 parts by mass, it is confirmed that the thermoplastic fluororesin is not uniformly dispersed in the thermoplastic polyurethane elastomer, and is formed by the thermoplastic fluororesin when the film is stretched. Wrinkles are formed on the film due to the influence of the drop point in the tensile properties.

包含以上述方式將熱塑性氟樹脂混合於熱塑性聚胺基甲酸酯系彈性體中而成之熱塑性彈性體2成分組合物的離型 用膜不但與模具或成形品之剝離性優異,而且將模具之形狀按照設計尺寸而轉印至成形品之模形狀轉印性優異,亦可具備耐熱性。進而,於進行將製造後之膜於40℃環境下保溫60天以上之熟化處理之情形時,可確認到對加成型液狀聚矽氧橡膠之觸媒毒消失,於成形品之表面上未殘留凝膠狀物質而可獲得成形品之表面平滑性。The release of the thermoplastic elastomer 2 component composition comprising the thermoplastic fluororesin blended in the thermoplastic polyurethane elastomer in the above manner The film is excellent in peelability from a mold or a molded article, and the shape of the mold is transferred to the molded article in accordance with the design size, and the mold shape is excellent in transferability and heat resistance. Further, in the case where the film after the production was kept at 40 ° C for 60 days or more, it was confirmed that the catalytic poisoning of the added liquid polyoxyethylene rubber disappeared, and the surface of the molded article was not The surface smoothness of the molded article can be obtained by leaving a gel-like substance.

此處,於本發明中,為縮短包含熱塑性彈性體2成分組合物之離型用膜所必需之熟化時間,可於該熱塑性彈性體2成分組合物中混合選自由含氟之醇系化合物與含氟之二醇所組成之群中之化合物。Here, in the present invention, in order to shorten the aging time necessary for the release film comprising the thermoplastic elastomer 2 component composition, the thermoplastic elastomer 2 component composition may be mixed with a fluorine-containing alcohol compound and a compound of the group consisting of fluorine-containing diols.

上述含氟之醇系化合物係以通式(A)之Rf1 (CH2 )m OH(式中,Rf1 表示碳數為3~20之直鏈狀或支鏈狀之全氟烷基或全氟烷基醚基,m為1~5)所表示之化合物。作為其具體例,例如可列舉:C6 F13 CH2 OH、C7 F15 CH2 OH、C8 F17 CH2 OH、C8 F17 CH2 CH2 OH、C9 F19 CH2 CH2 OH、C10 F21 CH2 CH2 OH、(CF3 )2 CF(CF2 )8 CH2 CH2 OH、CF3 CF2 O(CF2 CF2 O)1~5 CF2 CH2 OH、CF3 CF2 CF2 O(CFCF3 CF2 O)1~3 CFCF3 CH2 OH等。於該情形時,較佳為使用含有直鏈狀全氟烷基之C6 F13 CH2 OH、C7 F15 CH2 OH、C8 F17 CH2 OH、C8 F17 CH2 CH2 OH、C9 F19 CH2 CH2 OH、C10 F21 CH2 CH2 OH。The fluorine-containing alcohol-based compound is Rf 1 (CH 2 ) m OH of the formula (A) (wherein Rf 1 represents a linear or branched perfluoroalkyl group having a carbon number of 3 to 20 or A perfluoroalkyl ether group, m is a compound represented by 1 to 5). Specific examples thereof include C 6 F 13 CH 2 OH, C 7 F 15 CH 2 OH, C 8 F 17 CH 2 OH, C 8 F 17 CH 2 CH 2 OH, and C 9 F 19 CH 2 CH. 2 OH, C 10 F 21 CH 2 CH 2 OH, (CF 3 ) 2 CF(CF 2 ) 8 CH 2 CH 2 OH, CF 3 CF 2 O(CF 2 CF 2 O) 1~5 CF 2 CH 2 OH , CF 3 CF 2 CF 2 O (CFCF 3 CF 2 O) 1~3 CFCF 3 CH 2 OH, and the like. In this case, it is preferred to use C 6 F 13 CH 2 OH, C 7 F 15 CH 2 OH, C 8 F 17 CH 2 OH, C 8 F 17 CH 2 CH 2 containing a linear perfluoroalkyl group. OH, C 9 F 19 CH 2 CH 2 OH, C 10 F 21 CH 2 CH 2 OH.

又,上述含氟之二醇化合物係以通式(B)之Rf2 (CH2 )n OCH2 CH(OH)CH2 OH(式中,Rf2 表示碳數為3~20之直鏈狀或支鏈狀之全氟烷基,n為1或2之整數)所表示之化合物。作為具體例,例如可列舉:C6 F13 CH2 CH2 OCH2 CH(OH)CH2 OH、 C7 F15 CH2 CH2 OCH2 CH(OH)CH2 OH、C8 F17 CH2 CH2 OCH2 CH(OH)CH2 OH、C9 F19 CH2 CH2 OCH2 CH(OH)CH2 OH、C10 F21 CH2 CH2 OCH2 CH(OH)CH2 OH、(CF3 )2 CF(CF2 )8 CH2 CH2 OCH2 CH(OH)CH2 OH等。於該情形時,較佳為使用含有直鏈狀全氟烷基之C6 F13 CH2 CH2 OCH2 CH(OH)CH2 OH、C7 F15 CH2 CH2 OCH2 CH(OH)CH2 OH、C8 F17 CH2 CH2 OCH2 CH(OH)CH2 OH、C9 F19 CH2 CH2 OCH2 CH(OH)CH2 OH、C10 F21 CH2 CH2 OCH2 CH(OH)CH2 OH。Further, the fluorine-containing diol compound is Rf 2 (CH 2 ) n OCH 2 CH(OH)CH 2 OH of the formula (B) (wherein Rf 2 represents a linear chain having a carbon number of 3 to 20) Or a compound represented by a branched perfluoroalkyl group, n being an integer of 1 or 2. Specific examples include, for example, C 6 F 13 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 7 F 15 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 8 F 17 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 9 F 19 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 10 F 21 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, (CF 3 ) 2 CF(CF 2 ) 8 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH. In this case, it is preferred to use C 6 F 13 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 7 F 15 CH 2 CH 2 OCH 2 CH(OH) containing a linear perfluoroalkyl group. CH 2 OH, C 8 F 17 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 9 F 19 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH, C 10 F 21 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH.

此種含氟之醇系化合物及含氟之二醇化合物(以下簡稱為含氟之醇系化合物.二醇化合物)與作為熱塑性聚胺基甲酸酯系彈性體之原料的聚異氰酸酯反應。於包含熱塑性聚胺基甲酸酯系彈性體之膜中有時殘留作為其構成成分之聚異氰酸酯,且有時該聚異氰酸酯成為加成型液狀聚矽氧橡膠之觸媒毒而抑制硬化。根據上述情況,若於熱塑性聚胺基甲酸酯系彈性體中混合含氟之醇系化合物.二醇化合物,則與聚異氰酸酯反應使全氟烷基鍵結於彈性體之主骨架上而消滅觸媒毒。藉由該作用,若為於熱塑性彈性體2成分組合物中混合含氟之醇系化合物.二醇化合物而成之膜,則可藉由在40℃環境下進行3天以上之熟化處理而消滅觸媒毒,於加成型液狀聚矽氧橡膠組合物之成形中不抑制硬化而不於成形品之表面上殘留凝膠狀黏著物。藉此,於包含本發明之熱塑性彈性體3成分組合物之離型用膜中,可發揮如下效果:可縮短熟化時間即縮短準備時間,削減熟化所必需之空間,並削減熟化所必需之能量成本。The fluorine-containing alcohol-based compound and the fluorine-containing diol compound (hereinafter abbreviated as a fluorine-containing alcohol-based compound. diol compound) are reacted with a polyisocyanate which is a raw material of the thermoplastic polyurethane-based elastomer. A polyisocyanate which is a constituent component may remain in the film containing the thermoplastic polyurethane elastomer, and the polyisocyanate may become a catalyzed poison of the addition-form liquid polyoxyethylene rubber to suppress hardening. According to the above situation, if the thermoplastic polyurethane compound is mixed with fluorine-containing alcohol compound. The diol compound reacts with the polyisocyanate to bond the perfluoroalkyl group to the main backbone of the elastomer to eliminate catalogue toxicity. By this action, if the composition of the thermoplastic elastomer 2 is mixed with a fluorine-containing alcohol compound. The film formed by the diol compound can be destroyed by the aging treatment at 40 ° C for more than 3 days, and the curing of the addition-form liquid polyoxyethylene rubber composition does not inhibit hardening. A gel-like adhesive remains on the surface of the molded article. Therefore, in the film for release film containing the thermoplastic elastomer 3 component composition of the present invention, the effect of shortening the aging time, that is, shortening the preparation time, reducing the space necessary for aging, and reducing the energy necessary for aging can be exhibited. cost.

此種選自由含氟之醇系化合物與含氟之二醇化合物所組 成之群中的一種或複數種化合物之混合量相對於熱塑性彈性體2成分組合物100質量份,為0.05~5.0質量份之範圍內,較佳為設為0.1~4.0質量份之範圍內,更佳為設為0.1~3.0質量份之範圍內。若假設混合量未達0.05質量份,則無法發揮混合之效果。又,即便混合超過5.0質量份,效果亦不會增大,進而可確認到該等含氟之醇系化合物.二醇化合物未反應而殘留,溢出於膜表面而污染成形品之表面的不良情況。Such a group selected from the group consisting of fluorine-containing alcohol compounds and fluorine-containing diol compounds The compounding amount of one or a plurality of compounds in the group is in the range of 0.05 to 5.0 parts by mass, preferably in the range of 0.1 to 4.0 parts by mass, based on 100 parts by mass of the thermoplastic elastomer 2 component composition. More preferably, it is set within the range of 0.1 to 3.0 parts by mass. If the amount of the mixture is less than 0.05 parts by mass, the effect of mixing cannot be exerted. Further, even if it is more than 5.0 parts by mass, the effect is not increased, and the fluorine-containing alcohol-based compound can be confirmed. The diol compound remains unreacted and overflows on the surface of the film to contaminate the surface of the molded article.

若將上述含氟之醇系化合物.二醇化合物混合於熱塑性彈性體2成分組合物中,則亦對膜表面賦予平滑性,故而可附加如下效果:可流暢地進行模鑄成形裝置內之離型用膜之搬送、於接觸於模具時可防止離型用膜之褶皺、可提高與用作密封材料之聚矽氧橡膠組合物之剝離性。If the above fluorine-containing alcohol compound. When the diol compound is mixed with the thermoplastic elastomer 2 component composition, smoothness is imparted to the surface of the film. Therefore, it is possible to smoothly carry out the transfer of the release film in the molding apparatus and the contact with the mold. When the release film is wrinkled, the peeling property of the polyoxyethylene rubber composition used as the sealing material can be improved.

可與上述熱塑性聚胺基甲酸酯系彈性體中殘留之聚異氰酸酯反應之化合物除上述含氟之醇系化合物.二醇化合物以外亦有許多種,此外可列舉:醇系化合物或二醇系化合物等分子內具有羥基之化合物、或於分子內具有羧酸之化合物等。該等化合物可於無損本發明之特性之範圍內代替含氟之醇系化合物.二醇化合物而使用。a compound which can react with the polyisocyanate remaining in the above thermoplastic polyurethane elastomer, in addition to the above-mentioned fluorine-containing alcohol compound. There are many kinds of the diol compound, and examples thereof include a compound having a hydroxyl group in a molecule such as an alcohol compound or a diol compound, or a compound having a carboxylic acid in the molecule. These compounds can replace the fluorine-containing alcohol compounds within the scope of the characteristics of the present invention. A diol compound is used.

於上述熱塑性彈性體2成分組合物及3成分組合物(以下將兩者一併稱為熱塑性彈性體組合物)中,可於無損本發明之特性之範圍內混合其他熱塑性彈性體。作為該熱塑性彈性體,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。In the thermoplastic elastomer 2 component composition and the three component composition (hereinafter collectively referred to as a thermoplastic elastomer composition), other thermoplastic elastomers can be blended without departing from the characteristics of the present invention. Examples of the thermoplastic elastomer include a polyester elastomer, a polyamide-based elastomer, a polyvinyl chloride elastomer, a styrene elastomer, and an olefin elastomer.

於上述熱塑性彈性體組合物中,可於無損本發明之特性之範圍內混合例如聚乙烯系蠟、醯胺系蠟等潤滑劑,二氧化矽等抗結塊劑,酚系抗氧化劑、磷系抗氧化劑等。In the above thermoplastic elastomer composition, a lubricant such as a polyethylene wax or a guanamine wax, an anti-caking agent such as cerium oxide, a phenol antioxidant, or a phosphorus system may be mixed in a range not degrading the characteristics of the present invention. Antioxidants, etc.

本發明之包含熱塑性彈性體組合物之離型用膜可以單層膜之形式較佳地使用,亦可於無損本發明之特性之範圍內與包含熱塑性樹脂或其他熱塑性彈性體等之膜形成兩層以上之多層膜而使用。於製成多層膜之情形時,只要將本發明之包含熱塑性彈性體組合物之膜形成為與聚矽氧橡膠接觸之離型層即可。作為熱塑性樹脂,例如可列舉:聚對苯二甲酸丁二酯樹脂、聚對苯二甲酸乙二酯樹脂、環狀聚烯烴樹脂、間規聚苯乙烯樹脂、聚甲基戊烯樹脂、聚甲基丙烯酸甲酯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚苯乙烯樹脂、聚乙酸乙烯酯樹脂、丙烯腈丁二烯苯乙烯樹脂及丙烯腈苯乙烯樹脂等。作為其他熱塑性彈性體,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。又,作為其他材料,例如亦可列舉乙烯系共聚物橡膠等。作為形成多層膜之方法,例如可適當選擇共擠出法、擠出層壓法、塗佈法等先前公知之方法而使用。The film for release film comprising the thermoplastic elastomer composition of the present invention can be preferably used in the form of a single layer film, or can be formed with a film comprising a thermoplastic resin or other thermoplastic elastomer, without departing from the characteristics of the present invention. Use as a multilayer film above the layer. In the case of forming a multilayer film, the film comprising the thermoplastic elastomer composition of the present invention may be formed into a release layer in contact with the polyoxyxene rubber. Examples of the thermoplastic resin include polybutylene terephthalate resin, polyethylene terephthalate resin, cyclic polyolefin resin, syndiotactic polystyrene resin, polymethylpentene resin, and polymethylation. A methyl acrylate resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl acetate resin, an acrylonitrile butadiene styrene resin, an acrylonitrile styrene resin, or the like. Examples of the other thermoplastic elastomer include a polyester elastomer, a polyamide-based elastomer, a polyvinyl chloride-based elastomer, a styrene-based elastomer, and an olefin-based elastomer. Moreover, as another material, an ethylene-type copolymer rubber etc. are mentioned, for example. As a method of forming the multilayer film, for example, a conventionally known method such as a co-extrusion method, an extrusion lamination method, or a coating method can be appropriately selected and used.

於本發明之離型用膜中,依照JIS Z 1702而於溫度為23℃、拉伸速度為100 mm/min之條件下測定的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 之範圍內。該拉伸彈性模數較佳為30.0~450 N/mm2 之範圍內,更佳為50.0~400 N/mm2 之範圍內。若假設拉伸 彈性模數未達10.0 N/mm2 ,則可確認到於模鑄成形裝置內自捲繞體抽出離型用膜時,膜之張力較弱而產生鬆弛之不良情況。又,於拉伸彈性模數超過500 N/mm2 之情形時,可確認到於模具內利用真空吸引離型用膜時,膜未延伸而未密接於模具上之不良情況。In the release film of the present invention, the tensile modulus of the film measured in the film longitudinal direction (MD) and film is measured in accordance with JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. The lateral direction (TD) is in the range of 10.0 to 500 N/mm 2 . The tensile elastic modulus is preferably in the range of 30.0 to 450 N/mm 2 , more preferably in the range of 50.0 to 400 N/mm 2 . When the tensile modulus of elasticity is less than 10.0 N/mm 2 , it is confirmed that when the release film is taken out from the wound body in the mold forming apparatus, the tension of the film is weak and slack occurs. In the case where the tensile modulus of elasticity exceeds 500 N/mm 2 , it is confirmed that the film is not stretched and is not closely adhered to the mold when the release film is suctioned by vacuum in the mold.

於本發明之離型用膜中,依照JIS Z 1702而於溫度為23℃、拉伸速度為100 mm/min之條件下測定的膜之50%模數(50% Mo)於膜縱方向(MD)與膜橫方向(TD)上之比(MD)/(TD)為0.90~1.20之範圍內,較佳為0.95~1.20之範圍內。(MD)/(TD)於藉由擠出成形法而成形之膜中不會未達0.90。並且於假設(MD)/(TD)超過1.20之情形時,可確認到於模鑄成形裝置內將離型用膜供給於模具時,會於膜上產生褶皺之不良情況。In the release film of the present invention, the 50% modulus (50% Mo) of the film measured at a temperature of 23 ° C and a tensile speed of 100 mm / min in accordance with JIS Z 1702 is in the longitudinal direction of the film ( The ratio (MD) / (TD) in the transverse direction (TD) of the film to the film is in the range of 0.90 to 1.20, preferably in the range of 0.95 to 1.20. (MD) / (TD) is not less than 0.90 in the film formed by the extrusion molding method. When it is assumed that (MD)/(TD) exceeds 1.20, it is confirmed that wrinkles are generated in the film when the release film is supplied to the mold in the mold forming apparatus.

於本發明之離型用膜中,依照JIS Z 1702而於溫度為23℃、拉伸速度為100 mm/min之條件下測定的膜之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之範圍內,較佳為1.00~1.50之範圍內。若假設(100% Mo)/(50% Mo)未達1.00,則可確認到如下不良情況:由於未產生伴隨膜之延伸增加之應力增加,故而無法獲得均勻之膜之延伸,於模具內利用真空吸引離型用膜時產生褶皺。又,於(100% Mo)/(50% Mo)超過1.60之情形時,可確認到伴隨膜之延伸增加之應力增加較大,膜無法延伸至離型用膜密接於模具內面之程度的不良情況。In the film for release film of the present invention, 50% modulus (50% Mo) and 100% modulus of the film measured under the conditions of a temperature of 23 ° C and a tensile speed of 100 mm / min in accordance with JIS Z 1702 The ratio of (100% Mo) (100% Mo) / (50% Mo) is in the range of 1.00 to 1.60 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film, preferably in the range of 1.00 to 1.50. Inside. If it is assumed that (100% Mo) / (50% Mo) is less than 1.00, the following problem can be confirmed: since the stress increase accompanying the extension of the film does not occur, the uniform film extension cannot be obtained and is utilized in the mold. Wrinkles are generated when the vacuum is attracted to the film for release. Further, when (100% Mo) / (50% Mo) exceeds 1.60, it is confirmed that the stress increase accompanying the elongation of the film is large, and the film cannot be extended to the extent that the release film is in close contact with the inner surface of the mold. Bad situation.

於本發明之離型用膜中,依照JIS Z 1702而於溫度為23℃、拉伸速度為100 mm/min之條件下測定的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。若假設拉伸伸長率未達350%,則可確認到於模具內利用真空吸引離型用膜時,於模具之邊緣被切斷的不良情況。In the release film of the present invention, the tensile elongation of the film measured in the film longitudinal direction (MD) and the film transverse direction measured in accordance with JIS Z 1702 at a temperature of 23 ° C and a tensile speed of 100 mm / min. The direction (TD) is more than 350%. The tensile elongation is preferably 400% or more. When the tensile elongation is less than 350%, it is confirmed that the film is cut at the edge of the mold when the film for suction release is sucked by vacuum in the mold.

本發明中之熱塑性彈性體2成分組合物可藉由(1)方法而製作,即,將熱塑性聚胺基甲酸酯系彈性體與熱塑性氟樹脂於未達熱塑性聚胺基甲酸酯系彈性體之熔點之溫度下攪拌混合後,於熱塑性聚胺基甲酸酯系彈性體之熔點以上之溫度下熔融混練。The thermoplastic elastomer 2 component composition of the present invention can be produced by the method (1), that is, the thermoplastic polyurethane-based elastomer and the thermoplastic fluororesin are less than the thermoplastic polyurethane-based elastomer. After stirring and mixing at the temperature of the melting point of the body, the mixture is melted and kneaded at a temperature higher than the melting point of the thermoplastic polyurethane elastomer.

又,作為其他方法,可藉由(2)方法而製作,即,將熱塑性聚胺基甲酸酯系彈性體、熱塑性氟樹脂及含氟之醇系化合物.二醇化合物於未達熱塑性聚胺基甲酸酯系彈性體之熔點之溫度下攪拌混合後,於熱塑性聚胺基甲酸酯系彈性體之熔點以上之溫度下熔融混練。作為另一方法,可藉由(3)方法而製作,即,將熱塑性聚胺基甲酸酯系彈性體與熱塑性氟樹脂攪拌混合後,於以熱塑性聚胺基甲酸酯系彈性體之熔點以上之溫度熔融中添加含氟之醇系化合物.二醇化合物並熔融混練。可適當選擇該等(1)、(2)、(3)之各方法而使用。Further, as another method, it can be produced by the method (2), that is, a thermoplastic polyurethane elastomer, a thermoplastic fluororesin, and a fluorine-containing alcohol compound. The diol compound is stirred and mixed at a temperature not lower than the melting point of the thermoplastic polyurethane elastomer, and then melt-kneaded at a temperature higher than the melting point of the thermoplastic polyurethane elastomer. As another method, the method can be produced by the method (3), that is, the thermoplastic polyurethane resin is stirred and mixed with the thermoplastic fluororesin, and then the melting point of the thermoplastic polyurethane elastomer is used. Adding a fluorine-containing alcohol compound to the above temperature melting. The diol compound is melted and kneaded. These methods (1), (2), and (3) can be appropriately selected and used.

再者,熱塑性聚胺基甲酸酯系彈性體與熱塑性氟樹脂之攪拌混合、及於該等中添加含氟之醇系化合物.二醇化合物之攪拌混合可使用滾筒混合機、亨舍爾混合機、帶型攪 拌機或萬能攪拌混合機等公知之混合機而進行。Further, a thermoplastic polyurethane resin is stirred and mixed with a thermoplastic fluororesin, and a fluorine-containing alcohol compound is added thereto. Mixing and mixing of the diol compound can be carried out using a tumble mixer, a Henschel mixer, and a belt type It is carried out by a known mixer such as a mixer or a universal mixer.

上述(1)之熱塑性彈性體2成分組合物之製作、上述(2)之熱塑性彈性體3成分組合物之製作係藉由將以上述方法所製作之攪拌混合物使用單軸擠出機、雙軸擠出機等擠出機進行熔融混練而進行。製作熱塑性彈性體2成分組合物及3成分組合物之情形的擠出機之溫度為熱塑性聚胺基甲酸酯系彈性體之熔點以上、240℃以下。The production of the thermoplastic elastomer 2 component composition of the above (1) and the thermoplastic elastomer 3 component composition of the above (2) are produced by using a single-axis extruder and a double shaft by using the stirring mixture produced by the above method. An extruder such as an extruder is melted and kneaded. The temperature of the extruder in the case of producing the thermoplastic elastomer 2 component composition and the three component composition is not less than the melting point of the thermoplastic polyurethane elastomer, and 240 ° C or less.

又,於上述(3)之情形時,只要於使熱塑性聚胺基甲酸酯系彈性體與熱塑性氟樹脂之攪拌混合物於單軸擠出機、雙軸擠出機等擠出機中熔融後,添加含氟之醇系化合物.二醇化合物進行熔融混練而製作熱塑性彈性體3成分組合物即可。該製作熱塑性彈性體3成分組合物之情形的擠出機之溫度為聚胺基甲酸酯系彈性體之熔點以上、240℃以下。Further, in the case of the above (3), the molten mixture of the thermoplastic polyurethane elastomer and the thermoplastic fluororesin is melted in an extruder such as a single-screw extruder or a twin-screw extruder. , adding fluorine-containing alcohol compounds. The diol compound may be melt-kneaded to prepare a thermoplastic elastomer 3 component composition. In the case of producing the thermoplastic elastomer 3 component composition, the temperature of the extruder is not less than the melting point of the polyurethane elastomer, and 240 ° C or less.

於使用單軸擠出機或雙軸擠出機等擠出機而製作熱塑性彈性體組合物之情形時,亦可與下述形成膜之情形同樣地於利用惰性氣體置換存在於擠出機內及組合物間之空隙之空氣而成的惰性氣體環境下進行熔融混練。When a thermoplastic elastomer composition is produced by using an extruder such as a single-screw extruder or a twin-screw extruder, it may be replaced in the extruder by inert gas replacement as in the case of forming a film as described below. The melt kneading is carried out in an inert gas atmosphere formed by air in a gap between the compositions.

通常,熱塑性彈性體組合物係利用粉碎機或切割機加工成粉狀、顆粒狀或丸狀而使用。Usually, the thermoplastic elastomer composition is processed into a powder, granule or pellet by a pulverizer or a cutter.

包含上述熱塑性彈性體組合物之離型用膜例如可藉由熔融擠出法或熔融澆鑄法等先前公知之方法而成形。The film for release film containing the above thermoplastic elastomer composition can be formed, for example, by a conventionally known method such as a melt extrusion method or a melt casting method.

於以下例中,列舉藉由使用T模之熔融擠出法而使離型用膜成形之方法。In the following examples, a method of forming a release film by a melt extrusion method using a T die is exemplified.

利用此種方法而獲得之離型用膜係藉由以下方式獲得,即使用單軸擠出機或雙軸擠出機等擠出機,於視熱塑性彈性體組合物之特性而利用氮氣置換存在於擠出機內及成形材料間之間隙中之空氣而成的環境下,將熱塑性彈性體組合物之成形材料熔融混練,將自配置於擠出機前端之T模前端之唇部熔融擠出的離型用膜直接夾持於抽取機內之壓接輥與冷卻輥之間並冷卻,或者自壓接輥側與冷卻輥側兩者或一者插入分隔件而夾持並加以冷卻,繼而利用捲取機依序捲取至捲取管上。The film for release film obtained by such a method is obtained by using an extruder such as a single-axis extruder or a twin-screw extruder, and is replaced by nitrogen depending on the characteristics of the thermoplastic elastomer composition. The molding material of the thermoplastic elastomer composition is melted and kneaded in an environment of air in the gap between the extruder and the molding material, and the lip portion of the front end of the T die disposed at the front end of the extruder is melted and extruded. The release film is directly clamped between the pressure roller and the cooling roller in the extractor and cooled, or is inserted and cooled by inserting or separating the separator from the pressure roller side and the cooling roller side, and then cooling. The coiler is sequentially taken up to the take-up tube.

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的構成圖。又,圖4係圖3所示之膜製造裝置之材料投入漏斗之周邊的剖面圖。於圖3中,膜製造裝置大致包含材料投入漏斗2、擠出機1、T模7、抽取機11、捲取機15而構成。材料投入漏斗2以投入成形材料之方式形成,如圖4所示,於材料投入漏斗2連接於擠出機1之中途,經由間隔件3a而插入氮氣供給用管3。又,氮氣供給用管3以沿著材料投入口1c之大致中心軸之方式彎曲,其前端延設至擠出機1內之擠出螺桿1a之外周附近為止。自材料投入漏斗2所投入之成形材料中或擠出機1內所含之氧氣於利用擠出機1之擠出螺桿1a而混合、攪拌成形材料時,以供給至氮氣供給用管3中之氮氣予以置換。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 showing the periphery of a material input funnel of the film manufacturing apparatus shown in FIG. 3. In FIG. 3, the film manufacturing apparatus roughly comprises a material input funnel 2, an extruder 1, a T die 7, a extractor 11, and a coiler 15. The material input funnel 2 is formed by inputting a molding material. As shown in FIG. 4, the material supply funnel 2 is connected to the extruder 1, and the nitrogen gas supply pipe 3 is inserted through the spacer 3a. Further, the nitrogen gas supply pipe 3 is bent so as to extend along the substantially central axis of the material inlet port 1c, and the tip end thereof is extended to the vicinity of the outer circumference of the extrusion screw 1a in the extruder 1. The oxygen contained in the molding material supplied from the material input funnel 2 or the extruder 1 is mixed and stirred by the extrusion screw 1a of the extruder 1 to be supplied to the nitrogen gas supply pipe 3. Replace with nitrogen.

擠出機1一面將成形材料藉由擠出螺桿1a進行混合、攪拌,一面向箭頭B方向搬送,並藉由組入擠出機1之圓筒1b內之電熱機構(未圖示)而將成形材料加熱、熔融。以上述 方式熔融並搬送之成形材料經由圖3所示之連接管4而輸送至過濾機構5中。然後,藉由過濾機構5分離未熔融之成形材料,將熔融之成形材料輸送至齒輪泵6中。於齒輪泵6中,一面提高熔融之成形材料之壓力,一面將熔融成形材料擠出至T模7中。於T模7中,於特定壓力下擠出熔融成形材料,自T模7之唇部7a形成特定厚度、特定寬度之膜8。將以上述方式形成之膜8一面抽取至抽取機11之冷卻輥10之外周面上,一面利用壓接輥9調整成特定厚度,進而進行冷卻、固化,利用搬送輥對12、13搬送至捲取機15內。The extruder 1 mixes and stirs the molding material by the extrusion screw 1a, and conveys it in the direction of the arrow B, and is assembled by the electrothermal mechanism (not shown) incorporated in the cylinder 1b of the extruder 1. The forming material is heated and melted. With the above The molding material which is melted and conveyed in this manner is conveyed to the filtering mechanism 5 via the connecting pipe 4 shown in FIG. Then, the unmelted molding material is separated by the filtering mechanism 5, and the molten molding material is sent to the gear pump 6. In the gear pump 6, the molten molding material is extruded into the T-die 7 while increasing the pressure of the molten molding material. In the T die 7, the melt-molded material is extruded under a specific pressure, and a film 8 having a specific thickness and a specific width is formed from the lip portion 7a of the T-die 7. The film 8 formed as described above is taken up to the outer circumferential surface of the cooling roll 10 of the extractor 11, and is adjusted to a specific thickness by the pressure roller 9, and further cooled and solidified, and transported to the roll by the transfer roller pairs 12 and 13. Take the machine 15 inside.

於捲取機15中,利用導輥15a、15b、15c引導膜8並藉由捲取管16進行捲取。再者,於搬送輥對12、13與導輥15a之間配設有厚度測定器14,以成為所期望之厚度之方式基於利用厚度測定器14所測定之厚度調整並控制冷卻輥10之周速度。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 wound up by the take-up tube 16. Further, a thickness measuring device 14 is disposed between the pair of conveying rollers 12 and 13 and the guide roller 15a, and the circumference of the cooling roller 10 is adjusted and controlled based on the thickness measured by the thickness measuring device 14 so as to have a desired thickness. speed. Thereby, the above-mentioned release film is formed.

離型用膜只要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等之表面為鏡面之情形時,只要以離型用膜之表面成為鏡面之方式形成即可。又,由於IC或LSI等之表面形成微細之凹凸,故而只要以離型用膜之表面成為微細之凹凸之方式形成即可。The release film may be formed into a surface shape of the film in accordance with the surface shape necessary for the molded article. For example, when the surface of the LED or the like is a mirror surface, the surface of the release film may be formed into a mirror surface. In addition, since fine irregularities are formed on the surface of the IC or the LSI, the surface of the release film may be formed into fine irregularities.

於將離型用膜之表面製成鏡面之情形時,只要預先將上述金屬製之冷卻輥之表面製成鏡面,並利用壓接輥將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成鏡面即可。又,於使用分隔件之情形時,可採用將鏡面拋光之PET(polyethylene terephthalate,聚對苯二甲酸乙 二酯)膜或OPP(oriented polypropylene,延伸聚丙烯)膜用作分隔件並轉印其表面之方法。In the case where the surface of the release film is mirror-finished, the surface of the metal cooling roll is previously mirror-finished, and the film for release film in a molten state is pressure-bonded to the cooling roll by a pressure roller. The surface of the release film can be adjusted to a mirror surface. Moreover, in the case of using a separator, a mirror-polished PET (polyethylene terephthalate, polyethylene terephthalate) may be used. A diester) film or an OPP (oriented polypropylene) film is used as a separator and a method of transferring the surface thereof.

於離型用膜之表面上形成微細之凹凸之情形時,只要預先於上述金屬製之冷卻輥之外周面形成微細之凹凸,於將熔融狀態之離型用膜利用壓接輥壓接於該冷卻輥時,將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上即可。又,於使用分隔件之情形時,可採用將表面經消光加工之PET膜或OPP膜用作分隔件並轉印其表面之方法。When fine irregularities are formed on the surface of the release film, fine irregularities are formed on the outer peripheral surface of the metal cooling roll in advance, and the release film in a molten state is pressure-bonded to the film by a pressure roller. In the case of cooling the rolls, fine irregularities formed on the outer peripheral surface of the cooling roll may be transferred onto the surface of the release film. Further, in the case of using a separator, a method of using a surface-polished PET film or OPP film as a separator and transferring the surface thereof may be employed.

於將離型用膜之表面製成鏡面之情形時,只要以如下方式適當形成表面即可,即其表面粗糙度中,依照JIS B0601-2001,於速度為0.6 mm/秒、臨界值為0.8 mm、評價長度為8.0 mm之條件下測定之算術平均粗糙度Ra為0.10以下,最大高度粗糙度Rz為1.00以下。若算術平均粗糙度Ra為0.10以下及最大高度粗糙度Rz為1.00以下,則轉印離型用膜之表面之成形品之表面變得平滑。When the surface of the film for release film is formed into a mirror surface, the surface may be appropriately formed in such a manner that the surface roughness thereof is 0.6 mm/sec in accordance with JIS B0601-2001, and the critical value is 0.8. The arithmetic mean roughness Ra measured under the condition of mm and the evaluation length of 8.0 mm was 0.10 or less, and the maximum height roughness Rz was 1.00 or less. When the arithmetic mean roughness Ra is 0.10 or less and the maximum height roughness Rz is 1.00 or less, the surface of the molded article on the surface of the transfer release film becomes smooth.

於離型用膜之表面上形成微細之凹凸之情形時,只要以其表面粗糙度中與上述同樣地測定之算術平均粗糙度Ra為0.5以上,最大高度粗糙度Rz為5.00以上之方式適當形成表面即可。In the case where the fine unevenness is formed on the surface of the release film, the arithmetic mean roughness Ra measured in the same manner as described above is 0.5 or more, and the maximum height roughness Rz is 5.00 or more. The surface is fine.

本發明之離型用膜之厚度處於5 μm~500 μm之範圍內,較佳為10 μm~400 μm之範圍內,只要視所使用之模具之形狀適當選擇即可。於假設將離型用膜之厚度設為未達5 μm之情形時,會產生於使用時追隨於模具時,離型用膜延伸變薄而破裂,或因密封材料之壓力而破裂之不良情況,故 而欠佳。又,於離型用膜之厚度超過500 μm之情形時,會產生其厚度成為阻礙,無法追隨具有微細結構之模具,模具之複雜形狀未轉印至成形品的不良情況,故而欠佳。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 to be used. When it is assumed that the thickness of the release film is less than 5 μm, it may occur when the film is used to follow the mold, the release film is thinned and broken, or the film is broken due to the pressure of the sealing material. Therefore And not good. In addition, when the thickness of the release film exceeds 500 μm, the thickness thereof is hindered, and the mold having a fine structure cannot be followed, and the complicated shape of the mold is not transferred to the molded article, which is not preferable.

[實施例][Examples]

以下,使用圖5(表1)、圖6(表2)、圖7(表3)來說明本發明之離型用膜之實施例1~實施例21。於圖5(表1)、圖6(表2)、圖7(表3)中表示實施例1~實施例21之各離型用膜之材料、離型膜物性、及評價。再者,本發明之離型用膜當然並不限定於實施例1~實施例21。Hereinafter, Examples 1 to 21 of the release film of the present invention will be described with reference to Fig. 5 (Table 1), Fig. 6 (Table 2), and Fig. 7 (Table 3). The materials of the release films of the examples 1 to 21, the physical properties of the release film, and the evaluation are shown in Fig. 5 (Table 1), Fig. 6 (Table 2), and Fig. 7 (Table 3). Further, the film for release film of the present invention is of course not limited to Examples 1 to 21.

此處,表1~表3所示之熱塑性聚胺基甲酸酯系彈性體1、熱塑性聚胺基甲酸酯系彈性體2、熱塑性氟樹脂1、熱塑性氟樹脂2、含氟之醇系化合物.二醇化合物1及含氟之醇系化合物.二醇化合物2係使用以下所示之材料。此處,上述材料之最後所附注之1、2係表示種類不同。Here, the thermoplastic polyurethane elastomer 1, the thermoplastic polyurethane elastomer 2, the thermoplastic fluororesin 1, the thermoplastic fluororesin 2, and the fluorine-containing alcohol shown in Tables 1 to 3 Compound. Diol compound 1 and fluorine-containing alcohol compound. As the diol compound 2, the materials shown below were used. Here, the first and second notes of the above-mentioned materials indicate different types.

(熱塑性聚胺基甲酸酯系彈性體1)(Thermoplastic polyurethane-based elastomer 1)

Miractran E598PNAT:商品名,Nippon Polyurethane Industry公司製造,JIS A硬度為98,維氏軟化溫度為141℃Miractran E598PNAT: trade name, manufactured by Nippon Polyurethane Industry, JIS A hardness of 98, Vickers softening temperature of 141 ° C

(熱塑性聚胺基甲酸酯系彈性體2)(Thermoplastic polyurethane-based elastomer 2)

Miractran E559PNAT:商品名,Nippon Polyurethane Industry公司製造,JIS D硬度為59,維氏軟化溫度為143℃Miractran E559PNAT: trade name, manufactured by Nippon Polyurethane Industry, JIS D hardness 59, Vickers softening temperature 143 ° C

(熱塑性氟樹脂1)(thermoplastic fluororesin 1)

Dyneon THV500GZ:商品名,住友3M公司製造,四氟乙烯-六氟丙烯-偏二氟乙烯共聚物,熔點為165℃Dyneon THV500GZ: trade name, manufactured by Sumitomo 3M, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, melting point 165 ° C

(熱塑性氟樹脂2)(thermoplastic fluororesin 2)

Dyneon THV610GZ:商品名,住友3M公司製造,四氟乙烯-六氟丙烯-偏二氟乙烯共聚物,熔點為185℃Dyneon THV610GZ: trade name, manufactured by Sumitomo 3M, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, melting point 185 ° C

(含氟之醇系化合物.二醇化合物1)(Fluorinated alcohol compound. diol compound 1)

Eftop MF-100:商品名,Mitsubishi Materials公司製造,3-(2-全氟己基乙氧基)-1,2-二羥基丙烷(C6 F13 CH2 CH2 OCH2 CH(OH)CH2 OH)Eftop MF-100: trade name, manufactured by Mitsubishi Materials, 3-(2-perfluorohexylethoxy)-1,2-dihydroxypropane (C 6 F 13 CH 2 CH 2 OCH 2 CH(OH)CH 2 OH)

(含氟之醇系化合物.二醇化合物2)(Fluorinated alcohol compound. diol compound 2)

Eftop PDFOH:商品名,Mitsubishi Materials公司製造,十五氟辛醇(C7 F15 CH2 OH)Eftop PDFOH: trade name, manufactured by Mitsubishi Materials, pentafluorooctyl alcohol (C 7 F 15 CH 2 OH)

以下,基於表1~表3,對離型用膜之製作、剝離性、耐熱性、模形狀轉印性、凝膠狀黏著物之有無、表面平滑性及實用性進行詳細闡述。再者,表1~表3之上述內容亦同樣應用於圖8(表4)之比較例1~7中。Hereinafter, the production of the release film, the peelability, the heat resistance, the mold shape transfer property, the presence or absence of the gel-like adhesive, the surface smoothness, and the practicability will be described in detail based on Tables 1 to 3. Further, the above contents of Tables 1 to 3 are also applied to Comparative Examples 1 to 7 of Fig. 8 (Table 4).

(離型用膜之製作)(production of release film)

將熱塑性彈性體組合物供給至40 mm、L/D=25之單軸擠出機(IKG公司製造)中,使用壓縮比為2.5之全螺紋擠出螺桿,於圓筒溫度為180℃~210℃之條件下熔融混練,於模溫度為210℃~220℃之條件下自寬度為400 mm之T模中連續地擠出。於抽取機內,自壓接輥側將消光加工PET膜作為分隔件,自冷卻輥側將鏡面拋光PET膜作為分隔件而供給該擠出之離型用膜,將該等夾持於壓接輥與冷卻輥之間並加以冷卻,於捲取機中利用切割刀切斷兩端部,並將離型用膜捲取至捲取管上,藉此以表1至表3所記載之厚度 (表1至表3中之厚度(μm)項)製造寬度為250 mm、長度為50 m之離型用膜。將該等離型用膜於40℃之環境下以實施例(表1至表3)及比較例(表4)所記載之時間進行熟化。熟化結束後,一面剝離分隔件之消光加工PET膜及鏡面拋光PET膜,一面重新捲取離型用膜,獲得評價用之離型用膜。Supplying the thermoplastic elastomer composition to 40 mm, L/D=25 single-axis extruder (manufactured by IKG), using a full-thread extrusion screw with a compression ratio of 2.5, melt-kneading at a cylinder temperature of 180 ° C to 210 ° C, The mold was continuously extruded from a T-die having a width of 400 mm at a mold temperature of 210 ° C to 220 ° C. In the extracting machine, the matte-finished PET film is used as a separator from the side of the pressure-bonding roll, and the mirror-polished PET film is supplied as a separator from the cooling roll side to the extruded release film, and the crimping is performed on the crimping film. The roller and the cooling roller are cooled and cooled, and the both ends are cut by a cutter in a coiler, and the release film is taken up to the take-up tube, thereby using the thicknesses shown in Tables 1 to 3. (Thickness (μm) in Tables 1 to 3) A release film having a width of 250 mm and a length of 50 m was produced. The film for detachment was aged in an environment of 40 ° C in the examples (Tables 1 to 3) and Comparative Examples (Table 4). After the completion of the aging, the release film of the separator and the mirror-polished PET film were peeled off, and the release film was re-wound to obtain a release film for evaluation.

(評價之方法)(method of evaluation)

評價係使用具備圖1所示之透鏡形狀之模具,使離型用膜吸附於模具上後,滴加聚矽氧橡膠組合物進行熱壓成形,分別評價剝離性、耐熱性、模形狀轉印性、凝膠狀黏著物之有無、及表面平滑性。再者,於圖1中,符號20表示砲彈型LED透鏡,符號21a、21b表示導線。將砲彈型LED透鏡20之直徑例如設為6 mm,將高度例如設為4 mm。又,圖2表示模鑄模具(圖中以符號30表示),(a)為平面圖,(b)為(a)之A-A線下之剖面圖。於模鑄模具之表面設置有5×5個對應於砲彈型LED透鏡之形狀的透鏡成形凹部(圖中以符號31表示)。相鄰接之透鏡成形凹部之中心軸間之距離例如為8 mm。In the evaluation, the mold having the lens shape shown in FIG. 1 was used, and the release film was adsorbed on the mold, and the polyoxyethylene rubber composition was added dropwise to perform hot press forming, and the peelability, heat resistance, and mold shape transfer were evaluated. Sex, gel-like adhesive presence and surface smoothness. Further, in Fig. 1, reference numeral 20 denotes a bullet-type LED lens, and reference numerals 21a, 21b denote wires. The diameter of the cannonball type LED lens 20 is set, for example, 6 mm, set the height to 4 mm, for example. 2 shows a die-casting mold (indicated by reference numeral 30 in the drawing), (a) is a plan view, and (b) is a cross-sectional view taken along line AA of (a). A lens forming recess (indicated by symbol 31 in the figure) corresponding to the shape of the bullet-type LED lens is provided on the surface of the mold. The distance between the central axes of the adjacent lens forming recesses is, for example, 8 mm.

於圖2所示之模具中,以離型用膜之消光面成為模具側、鏡面成為空氣側之方式鋪設離型用膜,利用真空進行吸引而使離型用膜吸附於模具上。繼而,於離型用膜上滴加聚矽氧橡膠組合物OE-6636(商品名,Dow Corning-Toray公司製造),將表面鍍硬鉻之平板模具抵接於該等上,利用兩個模具夾持並進行熱壓成形。評價所成形之積層品的離型用膜與經硬化之聚矽氧橡膠之剝離性、離型用膜之耐 熱性、對經硬化之聚矽氧橡膠之模形狀轉印性、凝膠狀黏著物之有無及表面平滑性。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。In the mold shown in Fig. 2, the release film is placed on the mold side and the mirror surface is on the air side, and the release film is sucked by vacuum to adsorb the release film onto the mold. Then, a polyoxyethylene rubber composition OE-6636 (trade name, manufactured by Dow Corning-Toray Co., Ltd.) was dropped on the release film, and a hard chrome-plated flat mold was placed on the film, and two molds were used. Clamp and perform hot press forming. Evaluation of the release property of the formed release film and the cured polyoxymethylene rubber, the heat resistance of the release film, the mold transfer property to the cured polyoxyethylene rubber, and the gel-like adhesion The presence or absence of the object and the smoothness of the surface. The hot press forming was carried out under the conditions of a temperature of 140 ° C and a pressure of 10 kg / cm 2 for 5 minutes.

(剝離性)(peelability)

剝離性之評價(表1至表3中,評價、剝離性之項)係將所成形之聚矽氧橡膠組合物可不殘留於離型用膜上而剝離之情形表示為「good」,將聚矽氧橡膠組合物部分斷裂而殘留於離型用膜上之情形表示為「NG」。The evaluation of the peeling property (in the case of the evaluation and the releasability in Tables 1 to 3) is a case where the formed polyoxyxene rubber composition is peeled off without leaving the film for release film, and is referred to as "good". The case where the silicone rubber composition partially broke and remained on the release film was expressed as "NG".

(耐熱性)(heat resistance)

耐熱性之評價(表1至表3中,評價、耐熱性之項)係以目視觀察所成形之聚矽氧橡膠組合物經剝離之離型用膜,將無熔融、熔斷而保持膜形狀之情形表示為「Good」,將於離型用膜中有熔融、熔斷之情形表示為「NG」。Evaluation of heat resistance (in terms of evaluation and heat resistance in Tables 1 to 3), the film for release of the formed polyoxyxene rubber composition was visually observed, and the film shape was maintained without melting or melting. In the case of "Good", the case where the release film is melted or melted is indicated as "NG".

(模形狀轉印性)(die shape transferability)

模形狀轉印性(表1至表3中,評價、模形狀轉印性之項)係測定所成形之聚矽氧橡膠組合物之尺寸進行評價。將透鏡高度之評價基準設為自對孔深4 mm減去離型用膜之厚度後之尺寸進而減去0.1 mm以內之範圍,即((4-離型用膜之厚度)-0.1)mm以上。將25個透鏡均為基準以內之情形表示為「Good」,將哪怕有一個未滿足基準之形狀之情形表示為「NG」。The mold shape transfer property (in terms of evaluation, mold shape transfer property in Tables 1 to 3) was measured by measuring the size of the formed polyoxyethylene rubber composition. The evaluation criteria of the height of the lens are set to be smaller than the thickness of the film for the release of 4 mm from the hole depth of 4 mm, and then the range of 0.1 mm or less, that is, ((the thickness of the film for 4-release film) - 0.1) mm the above. The case where 25 lenses are within the reference is expressed as "Good", and even if one of the shapes that does not satisfy the reference is expressed as "NG".

(凝膠狀黏著物之有無)(The presence or absence of gelatinous adhesives)

凝膠狀黏著物之有無(表1至表3中,評價、凝膠狀黏著物之有無之項)係利用手指觸摸所成形之聚矽氧橡膠組合 物之表面並確認黏著感。將於聚矽氧橡膠之表面上無黏著感,且手指離開時無指紋附著之情形評價為「Good」,將表面有黏著感,且手指離開時附著指紋之情形評價為「NG」。The presence or absence of a gel-like adhesive (in Tables 1 to 3, the evaluation, the presence or absence of a gel-like adhesive) is a combination of a silicone rubber formed by a finger touch. The surface of the object and confirm the adhesion. There was no stickiness on the surface of the polyoxymethylene rubber, and the case where no fingerprint was attached when the finger was left was evaluated as "Good", and the surface was sticky, and the fingerprint was attached when the finger left, and it was evaluated as "NG".

(表面平滑性)(surface smoothness)

表面平滑性(表1至表3中,評價、表面平滑性之項)係以目視對所成形之聚矽氧橡膠組合物之表面狀態進行評價。將聚矽氧橡膠之表面上未產生凹凸或褶皺之情形表示為「Good」,將產生凹凸或褶皺之情形表示為「NG」。Surface smoothness (in Tables 1 to 3, evaluation, surface smoothness) was evaluated by visually observing the surface state of the formed polyoxyethylene rubber composition. The case where no unevenness or wrinkles were formed on the surface of the polyoxymethylene rubber was indicated as "Good", and the case where irregularities or wrinkles were generated was indicated as "NG".

(實用性)(practical)

實用性係藉由利用模鑄成形裝置進行樹脂模鑄成形而確認並評價。具體而言,於作為模鑄裝置之Apic Yamada公司製造之模鑄成形裝置G-LINE manual press(商品名)中,使用OE-6636(商品名,Dow Corning-Toray公司製造)作為聚矽氧橡膠組合物,以目視確認實用性。The usability was confirmed and evaluated by resin molding using a die-casting apparatus. Specifically, OE-6636 (trade name, manufactured by Dow Corning-Toray Co., Ltd.) was used as the polyoxyxene rubber in the G-LINE manual press (trade name) manufactured by Apic Yamada Co., Ltd. as a molding apparatus. The composition was visually confirmed for practicality.

實用性之評價(表1至表3中,評價、實用性之項)係將如下狀態表示為「Good」,將任一者有不良情況之情形表示為「NG」:於模鑄成形裝置內搬送離型用膜時膜不鬆弛地供給,於吸附時於膜上未產生褶皺,於熱壓成形後,離型用膜與聚矽氧橡膠組合物之剝離性良好,經硬化之聚矽氧橡膠組合物之表面無凹凸或褶皺,平滑且無凝膠狀黏著物,於離型用膜上無破裂或熔斷、及聚矽氧橡膠組合物之殘留,於模具上無污垢。Evaluation of practicability (in the case of evaluation and practicability in Tables 1 to 3), the following state is indicated as "Good", and the case where any of the cases is defective is indicated as "NG": in the mold forming apparatus When the film for release film is conveyed, the film is not loosely supplied, and wrinkles are not formed on the film during the adsorption, and the peeling property of the release film and the polyoxyethylene rubber composition after the hot press forming is good, and the cured polyoxylized oxygen The surface of the rubber composition has no irregularities or wrinkles, is smooth and has no gel-like adhesive, is not broken or melted on the release film, and remains of the polyoxymethylene rubber composition, and has no dirt on the mold.

根據此種結果,於比較例1(參照表4)中,將熱塑性彈性 體2成分組合物之熱塑性氟樹脂之混合量設為未達本發明之混合量,結果無法獲得剝離性,而未滿足實用性。於比較例2(參照表4)中,超過本發明之混合量而混合熱塑性彈性體2成分組合物之熱塑性氟樹脂,結果於膜吸附於模具內時產生褶皺並轉印至成形品之表面上,無法獲得表面平滑性。於比較例3(參照表4)中,將熱塑性彈性體3成分組合物之熱塑性氟樹脂之混合量與含氟之醇系化合物.二醇化合物之混合量設為未達本發明之混合量,結果無法獲得剝離性,未滿足實用性。於比較例4(參照表4)中,超過本發明之混合量而混合熱塑性彈性體3成分組合物之熱塑性氟樹脂與含氟之醇系化合物.二醇化合物,結果有如下不良情況:於膜吸附於模具內時產生褶皺而轉印至成形品之表面上,無法獲得表面平滑性,而且自離型用膜溢出之油附著於成形品之表面上。於比較例5(參照表4)中,將旭硝子公司製造之ETFE膜Aflex(商品名)之厚度為100 μm者作為比較對象,結果模形狀轉印性較差,無法獲得實用性。於比較例6(參照表4)中,將旭硝子公司製造之ETFE膜Aflex(商品名)之厚度為25 μm者作為比較對象,結果於吸附於模具內時膜破裂而無法獲得實用性。於比較例7(參照表4)中,將包含DuPont-Toray公司製造之Hytrel 5577(商品名)、聚酯-聚醚共聚物、及D硬度為55、維氏軟化溫度為192℃之熱塑性彈性體組合物的厚度為50 μm之離型用膜作為比較對象。於包含聚矽氧橡膠組合物之成形品之表面上產生褶皺,且表面平滑性較差,又,亦有凝膠狀黏著物, 無法獲得實用性。According to this result, in Comparative Example 1 (refer to Table 4), thermoplastic elasticity was employed. The blending amount of the thermoplastic fluororesin of the bulk 2 component composition was set to be less than the blending amount of the present invention, and as a result, peeling property could not be obtained, and the practicality was not satisfied. In Comparative Example 2 (see Table 4), the thermoplastic fluororesin of the thermoplastic elastomer 2 component composition was blended in excess of the blending amount of the present invention, and as a result, wrinkles were generated when the film was adsorbed in the mold and transferred onto the surface of the molded article. , surface smoothness cannot be obtained. In Comparative Example 3 (refer to Table 4), the thermoplastic fluororesin composition of the thermoplastic elastomer 3 component composition was mixed with the fluorine-containing alcohol compound. The blending amount of the diol compound was set to be less than the blending amount of the present invention, and as a result, peeling property could not be obtained, and the practicality was not satisfied. In Comparative Example 4 (refer to Table 4), the thermoplastic fluororesin of the thermoplastic elastomer 3 component composition and the fluorine-containing alcoholic compound were mixed in excess of the compounding amount of the present invention. As a result of the diol compound, when the film is adsorbed in the mold, wrinkles are generated and transferred onto the surface of the molded article, surface smoothness cannot be obtained, and the oil overflowing from the release film adheres to the surface of the molded article. on. In Comparative Example 5 (see Table 4), the thickness of the ETFE film Aflex (trade name) manufactured by Asahi Glass Co., Ltd. was 100 μm, and the mold shape transfer property was inferior, and practicality could not be obtained. In Comparative Example 6 (see Table 4), the thickness of the ETFE film Aflex (trade name) manufactured by Asahi Glass Co., Ltd. was 25 μm, and as a result of comparison, when the film was adsorbed in the mold, the film was broken and practicability was not obtained. In Comparative Example 7 (refer to Table 4), Hytrel 5577 (trade name) manufactured by DuPont-Toray Co., Ltd., a polyester-polyether copolymer, and a thermoplastic elastomer having a D hardness of 55 and a Vickers softening temperature of 192 ° C were contained. A release film having a thickness of 50 μm was used as a comparison object. Wrinkles are formed on the surface of the molded article comprising the polyoxyethylene rubber composition, and the surface smoothness is poor, and gelatinous adhesive is also present. Unable to get practicality.

相對於此,可知本發明之實施例1至21(表1至表3)之離型用膜不僅可獲得剝離性,而且具有耐熱性,且模形狀轉印性優異,可不殘留凝膠狀黏著物而獲得表面平滑性,賦予有實用性。根據上述情況,藉由本發明可獲得如下離型用膜:與將密封材料成形加工而獲得之成形品的剝離性優異,並且可獲得形狀與表面性優異之成形品。On the other hand, it is understood that the release film of Examples 1 to 21 (Tables 1 to 3) of the present invention can obtain not only peelability but also heat resistance, and excellent mold form transferability, and no gel-like adhesion remains. The surface is smoothed and imparted with practicality. According to the above, according to the present invention, it is possible to obtain a film for release film which is excellent in peelability from a molded article obtained by molding a sealing material, and which can obtain a molded article excellent in shape and surface properties.

以上,使用實施形態對本發明進行了說明,但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內。業者應知曉可對上述實施形態進行多種變更或改良。又,根據申請專利範圍之記載可知進行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, but the technical scope of the present invention is of course not limited to the scope described in the above embodiments. Those skilled in the art will recognize that various modifications or improvements can be made to the above-described embodiments. Further, it is understood that such changes or improvements can be included in the technical scope of the present invention.

1‧‧‧擠出機1‧‧‧Extrusion machine

2‧‧‧材料投入漏斗2‧‧‧Material input funnel

3‧‧‧氮氣供給用管3‧‧‧Nitrogen supply pipe

4‧‧‧連接管4‧‧‧Connecting tube

5‧‧‧過濾器5‧‧‧Filter

6‧‧‧齒輪泵6‧‧‧ Gear pump

7‧‧‧T模7‧‧‧T mode

7a‧‧‧唇部7a‧‧‧Lip

8‧‧‧膜8‧‧‧ film

9‧‧‧壓接輥9‧‧‧Crimp roller

10‧‧‧冷卻輥10‧‧‧Cooling roller

11‧‧‧抽取機11‧‧‧ extractor

12、13‧‧‧搬送輥對12, 13‧‧‧Transport roller pair

14‧‧‧厚度測定器14‧‧‧ Thickness measuring device

16‧‧‧捲取管16‧‧‧Winding tube

17a、17b‧‧‧送出輥17a, 17b‧‧‧Send rolls

18a、18b‧‧‧分隔件18a, 18b‧‧‧ dividers

20‧‧‧砲彈型LED透鏡20‧‧‧ cannonball type LED lens

21a、21b‧‧‧導線21a, 21b‧‧‧ wires

30‧‧‧模鑄模具30‧‧‧Mold casting mould

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係(a)本發明之實施形態之砲彈型LED透鏡之模具之俯視圖。(b)係本發明之實施形態之砲彈型LED透鏡之模具的圖2(a)之A-A箭頭剖面圖。Fig. 2 is a plan view showing a mold of a cannonball type LED lens according to an embodiment of the present invention. (b) A cross-sectional view taken along line A-A of Fig. 2(a) of a mold for a bullet-type LED lens according to an embodiment of the present invention.

圖3係表示本發明之實施形態之離型用膜的膜製造裝置之概略構成之圖。Fig. 3 is a view showing a schematic configuration of a film production apparatus for a release film according to an embodiment of the present invention.

圖4係表示本發明之實施形態之圖3所示膜製造裝置之材料投入漏斗之周邊的剖面圖。Fig. 4 is a cross-sectional view showing the vicinity of a material input funnel of the film production apparatus shown in Fig. 3 according to an embodiment of the present invention.

圖5係包含表示本發明之實施例之表1,且表示實施例1至7、以及其物性、評價之圖。Fig. 5 is a view showing Table 1 showing an embodiment of the present invention, and shows Examples 1 to 7, and their physical properties and evaluation.

圖6係包含表示本發明之實施例之表2,且表示實施例8 至14、以及其物性、評價之圖。Figure 6 is a table 2 showing an embodiment of the present invention, and shows Example 8 To 14, and its physical properties, evaluation map.

圖7係包含表示本發明之實施例之表3,且表示實施例15至21、以及其物性、評價之圖。Fig. 7 is a view showing Table 3 showing an embodiment of the present invention, and shows Examples 15 to 21, and their physical properties and evaluation.

圖8係包含表示本發明之比較例之表4,且表示比較例1至7、以及其物性、評價之圖。Fig. 8 is a view showing Table 4 showing a comparative example of the present invention, and shows Comparative Examples 1 to 7, and their physical properties and evaluation.

Claims (10)

一種離型用膜,其特徵在於由相對於JIS A硬度為70以上、維卡軟化溫度(Vicat Softening Temperature)為100~180℃之熱塑性聚胺基甲酸酯系彈性體100質量份,於1~400質量份之範圍內含有熱塑性氟樹脂之熱塑性彈性體2成分組合物所構成。 A film for release film characterized by comprising 100 parts by mass of a thermoplastic polyurethane elastomer having a hardness of 70 or more and a Vicat Softening Temperature of 100 to 180 ° C with respect to JIS A; It is composed of a thermoplastic elastomer 2 component composition containing a thermoplastic fluororesin in a range of up to 400 parts by mass. 如請求項1之離型用膜,其中上述熱塑性氟樹脂係熔點為140℃以上、240℃以下之熱塑性四氟乙烯系共聚物。 The release film according to claim 1, wherein the thermoplastic fluororesin is a thermoplastic tetrafluoroethylene copolymer having a melting point of 140 ° C or more and 240 ° C or less. 如請求項1之離型用膜,其包含相對於上述熱塑性彈性體2成分組合物100質量份,於0.05~5.0質量份之範圍內含有選自由含氟之醇系化合物與含氟之二醇化合物所組成之群中的一種或複數種化合物之熱塑性彈性體3成分組合物。 The film for release film of claim 1, which comprises, in a range of 0.05 to 5.0 parts by mass, based on 100 parts by mass of the thermoplastic elastomer 2 component composition, a diol selected from the group consisting of a fluorine-containing alcohol compound and a fluorine-containing diol. A thermoplastic elastomer 3 component composition of one or a plurality of compounds of the group consisting of the compounds. 如請求項3之離型用膜,其中上述含氟之醇系化合物為通式(A)所表示之化合物,上述含氟之二醇化合物為通式(B)所表示之化合物,Rf1 (CH2 )m OH…(A)(式中,Rf1 表示碳數3~20之直鏈狀或支鏈狀之全氟烷基或全氟烷基醚基,m為1~5之整數)Rf2 (CH2 )n OCH2 CH(OH)CH2 OH…(B)(式中,Rf2 表示碳數3~20之直鏈狀或支鏈狀之全氟烷基,n為1或2之整數)。The release film according to claim 3, wherein the fluorine-containing alcohol compound is a compound represented by the formula (A), and the fluorine-containing diol compound is a compound represented by the formula (B), Rf 1 ( CH 2 ) m OH (A) (wherein Rf 1 represents a linear or branched perfluoroalkyl or perfluoroalkyl ether group having a carbon number of 3 to 20, and m is an integer of 1 to 5) Rf 2 (CH 2 ) n OCH 2 CH(OH)CH 2 OH (B) (wherein Rf 2 represents a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, and n is 1 or 2 integer). 如請求項1至4中任一項之離型用膜,其中上述熱塑性彈性體2成分組合物及3成分組合物更包含屬於潤滑劑、抗 結塊劑、酚系抗氧化劑、磷系抗氧化劑中之一種或複數種添加劑。 The release film according to any one of claims 1 to 4, wherein the thermoplastic elastomer 2 component composition and the three component composition further comprise a lubricant and an anti-wear agent. One or a plurality of additives of an agglomerating agent, a phenolic antioxidant, and a phosphorus antioxidant. 如請求項1至4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)及膜橫方向(TD)上均為10~500N/mm2 之範圍內。The release film according to any one of claims 1 to 4, wherein the tensile modulus of the film is in the range of 10 to 500 N/mm 2 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. . 如請求項1至4中任一項之離型用膜,其中膜之50%模數(50% Mo)於膜縱方向(MD)與膜橫方向(TD)上之比(MD)/(TD)為0.9~1.2之範圍內。 The release film according to any one of claims 1 to 4, wherein a 50% modulus (50% Mo) of the film is in a ratio of a film longitudinal direction (MD) to a film transverse direction (TD) (MD)/( TD) is in the range of 0.9 to 1.2. 如請求項1至4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之範圍內。 The release film according to any one of claims 1 to 4, wherein a ratio of a 50% modulus (50% Mo) of the film to a 100% modulus (100% Mo) (100% Mo) / (50% Mo It is in the range of 1.0 to 1.6 in the longitudinal direction (MD) of the film and the transverse direction (TD) of the film. 如請求項1至4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%。 The release film according to any one of claims 1 to 4, wherein the tensile elongation of the film exceeds 350% in both the longitudinal direction (MD) and the transverse direction (TD) of the film. 如請求項1至4中任一項之離型用膜,其由含有包含熱塑性樹脂之膜、或包含上述熱塑性聚胺基甲酸酯系彈性體以外之其他熱塑性彈性體之膜的多層膜所構成。The release film according to any one of claims 1 to 4, which is provided by a multilayer film comprising a film comprising a thermoplastic resin or a film comprising a thermoplastic elastomer other than the thermoplastic polyurethane elastomer. Composition.
TW101138135A 2012-02-20 2012-10-16 Release film TWI492829B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012034151A JP5541468B2 (en) 2012-02-20 2012-02-20 Release film

Publications (2)

Publication Number Publication Date
TW201334938A TW201334938A (en) 2013-09-01
TWI492829B true TWI492829B (en) 2015-07-21

Family

ID=48958845

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101138135A TWI492829B (en) 2012-02-20 2012-10-16 Release film

Country Status (4)

Country Link
JP (1) JP5541468B2 (en)
KR (1) KR101435274B1 (en)
CN (1) CN103254612B (en)
TW (1) TWI492829B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104425290B (en) * 2013-08-27 2017-08-08 硕正科技股份有限公司 Applied to wafer level packaging from shape element
JP6601921B2 (en) * 2015-04-27 2019-11-06 株式会社寺岡製作所 Release adhesive tape
CN105313516B (en) * 2015-09-23 2018-09-28 武汉华工图像技术开发有限公司 A kind of anti-fake blocking film and preparation method thereof with 3D effect
CN107043531A (en) * 2017-03-14 2017-08-15 浙江环龙新材料科技有限公司 A kind of TPU film and its manufacture method and purposes with good rate of perviousness
CN108587113B (en) * 2018-03-20 2020-11-24 浙江工业大学 Preparation method of self-cleaning polyurethane elastomer film
WO2020071386A1 (en) * 2018-10-04 2020-04-09 日東電工株式会社 Heat-resistant release sheet and thermocompression bonding method
KR102554241B1 (en) * 2022-12-02 2023-07-11 (주)상아프론테크 Fluorine-based release film, Semiconductor package manufacturing method using the same and Semiconductor package

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090114558A1 (en) * 2007-10-12 2009-05-07 Thomas Shilale Low melt plastic fastner

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2964590B2 (en) * 1990-09-06 1999-10-18 大日本印刷株式会社 Release paper
JP2001310336A (en) * 2000-04-28 2001-11-06 Asahi Glass Co Ltd Releasing film for molding resin mold
JP3888096B2 (en) 2000-11-10 2007-02-28 旭硝子株式会社 Release film for multilayer printed wiring boards
KR101395520B1 (en) * 2006-08-18 2014-05-14 아사히 가라스 가부시키가이샤 Mold release film for the resin encapsulation of semiconductors
JP4805806B2 (en) * 2006-12-31 2011-11-02 三菱樹脂株式会社 Release polyester film for hot press molding
WO2010047432A1 (en) * 2008-10-24 2010-04-29 Ja Eun Gu Removable lens protection coating agent comprising water-dispersion polyurethane
WO2010079812A1 (en) * 2009-01-08 2010-07-15 旭硝子株式会社 Mold-releasing film and method for manufacturing light emitting diode
JP5472997B2 (en) * 2010-03-24 2014-04-16 信越ポリマー株式会社 Release film
JP5165715B2 (en) * 2010-03-24 2013-03-21 信越ポリマー株式会社 Release film
JP5288422B2 (en) * 2011-03-30 2013-09-11 信越ポリマー株式会社 Release film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090114558A1 (en) * 2007-10-12 2009-05-07 Thomas Shilale Low melt plastic fastner

Also Published As

Publication number Publication date
JP2013169679A (en) 2013-09-02
KR20130095612A (en) 2013-08-28
CN103254612A (en) 2013-08-21
TW201334938A (en) 2013-09-01
KR101435274B1 (en) 2014-08-27
JP5541468B2 (en) 2014-07-09
CN103254612B (en) 2015-05-27

Similar Documents

Publication Publication Date Title
TWI492829B (en) Release film
TWI527856B (en) Mold release film
TW200932775A (en) Polyurethane composition
TWI534184B (en) Mold release film
JP5511757B2 (en) Release film
CN106461841B (en) The manufacturing method of optical film
TW202208185A (en) Multilayer film
JP5822810B2 (en) Release film
JP6105366B2 (en) Release film
JP2010174146A (en) Method for producing base material for gasket, gasket produced by using the base material for gasket, and use of gasket
JP2014037105A (en) Method for manufacturing a laminate sheet and method for manufacturing a thermoplastic elastomer sheet
KR20060094903A (en) Composition for paper feed roll manufacture, paper feed roll and method of manufacture thereof
JP5822811B2 (en) Release film
JP6105376B2 (en) Release film
JP2023129449A (en) Adhesive sheet for bonding, multilayer body and method for producing multilayer body
JP6105510B2 (en) Paper feed roller and manufacturing method thereof
JP2013071382A (en) Mold release film
JP3630820B2 (en) Thermoplastic resin composition
JP5333371B2 (en) Release film
KR102131734B1 (en) Manufacturing method for thermoplastic polyurethane film and thermoplastic polyurethane film manufactured by the same
JP2986690B2 (en) Thermoplastic polyurethane composition
WO2024048432A1 (en) Adhesive film, heat molded body and method for producing adhesive film
JP5568716B1 (en) Antifouling resin composition
JP2021025017A (en) Adhesive sheet for bonding, multilayer body and method for producing multilayer body
JPH0920863A (en) Production of thermoplastic polyurethane composite resin for molding and film and tube produced by using the resin

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees