TW202227269A - Polyester release film - Google Patents
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- TW202227269A TW202227269A TW110149575A TW110149575A TW202227269A TW 202227269 A TW202227269 A TW 202227269A TW 110149575 A TW110149575 A TW 110149575A TW 110149575 A TW110149575 A TW 110149575A TW 202227269 A TW202227269 A TW 202227269A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
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Abstract
Description
本發明涉及一種聚酯離型膜,具體涉及使用於多層陶瓷電容器(Multi-layer Ceramic condenser,以下MLCC)、偏光板保護用以及OCA用等電子材料的表面保護用離型膜。The invention relates to a polyester release film, in particular to a release film for surface protection of electronic materials such as Multi-layer Ceramic Condenser (MLCC), polarizer protection and OCA.
聚酯膜(Polyester film)在從低溫至高溫的寬廣的溫度範圍中,物性穩定性出色,並且與其他高分子樹脂相比,耐化學性優秀。另外,機械強度、表面特性、厚度的均勻性良好,因此,可應用於多種用途和工藝條件。因此,正在應用於電容器用、膠片用、標籤用、壓感膠帶、裝飾層壓紙、轉移膜、偏光板以及陶瓷離型用生料片等,並且隨著近期高速化和自動化的趨勢,其需求正在增加。Polyester film has excellent physical property stability in a wide temperature range from low temperature to high temperature, and has excellent chemical resistance compared with other polymer resins. In addition, the uniformity of mechanical strength, surface properties, and thickness is good, and therefore, it can be applied to various applications and process conditions. Therefore, it is being used for capacitors, films, labels, pressure-sensitive tapes, decorative laminates, transfer films, polarizers, and green sheets for ceramic release, etc., and with the recent trend of high speed and automation, its Demand is increasing.
近期,隨著電子設備小型化的趨勢,電容器及電感器等電子部件也在小型化,其中,陶瓷生料片本身也在薄膜化,並且重點在於將陶瓷片材製造成薄膜以在相同體積內層疊更多的陶瓷層。在形成於聚酯離型膜的表面的矽離型層上塗布將陶瓷粉體和粘合劑分散於液相介質而成的陶瓷漿料以製造薄膜狀的陶瓷片材,之後,在製造陶瓷電容器的過程中將離型膜去除。然而,當離型膜的表面粗糙度高時,能夠滿足離型膜本身的滑移性或對於輥的捲繞等物性,但是會發生在離型膜表面突出的粒子的突出形態轉印到陶瓷片材上的問題。另外,在製造離型膜時,將膜以與移送輥接觸的狀態高速移送時,粒子脫離而成為切屑並附著於與其接觸的輥上而導致污染,使得膜產生缺陷。所述切屑或脫離的粒子附著於移送輥,導致膜表面產生缺陷,並且成為後續工藝中的異物。Recently, with the trend of miniaturization of electronic equipment, electronic parts such as capacitors and inductors are also miniaturized, among which, the ceramic green sheet itself is also being thinned, and the emphasis is on making the ceramic sheet into a thin film so as to have the same volume in the same volume. Laminate more ceramic layers. On the silicon release layer formed on the surface of the polyester release film, a ceramic slurry obtained by dispersing ceramic powder and a binder in a liquid phase medium is applied to produce a thin-film ceramic sheet, and then the ceramic sheet is produced. The release film is removed during the capacitor process. However, when the surface roughness of the release film is high, physical properties such as the slippage of the release film itself and the winding to a roll can be satisfied, but the protruding form of the particles protruding from the surface of the release film may be transferred to the ceramic. Problems on the sheet. In addition, when a release film is produced, when the film is transferred at a high speed while being in contact with a transfer roller, particles are detached and become chips and adhere to the roller in contact therewith to cause contamination and cause defects in the film. The chips or detached particles adhere to the transfer roller, cause defects on the film surface, and become foreign matter in the subsequent process.
相反地,當膜的表面粗糙度過低時,塗布陶瓷漿料時的塗布穩定性、膜移動性、滑移性降低,並且在製造離型膜之後將其捲繞到輥上時,會發生脫輥現象等,並且在對離型膜的表面塗布矽離型層的過程中,膜表面會產生劃痕等。Conversely, when the surface roughness of the film is too low, the coating stability, film mobility, and slippage at the time of coating the ceramic slurry decrease, and when the release film is wound on a roll after it is produced, it occurs. Rolling off phenomenon, etc., and in the process of coating the surface of the release film with a silicon release layer, scratches and the like will occur on the surface of the film.
因此,要求開發一種薄膜狀的離型膜,其在製造離型膜時,儘量降低表面粗糙度,並且滑移性、對於輥的捲繞性優秀,即便高速移送,切屑產生得也少,而且在切割膜時,粉塵產生得少。 在先技術文獻 Therefore, there is a need to develop a film-like release film which, when manufacturing a release film, reduces the surface roughness as much as possible, has excellent slip properties, and is excellent in rollability to a roll, and which generates less chips even when transferred at a high speed, and also When cutting the film, less dust is generated. prior art literature
專利文獻 專利文獻1:韓國公開專利第2003-0055118號(2003.07.02) Patent Literature Patent Document 1: Korean Patent Publication No. 2003-0055118 (2003.07.02)
技術問題technical problem
本發明旨在提供使用於多層陶瓷電容器(MLCC)、偏光板保護用以及OCA用等電子材料的表面保護用離型膜。The present invention aims to provide a release film for surface protection of electronic materials such as multilayer ceramic capacitors (MLCC), polarizer protection, and OCA.
具體地,本發明旨在提供一種聚酯離型膜,其為厚度為50μm以下的薄膜,以便用作薄膜狀的多層陶瓷電容器(MLCC)的離型膜,並且對於輥的捲繞性以及滑移性優秀。Specifically, the present invention aims to provide a polyester release film, which is a film with a thickness of 50 μm or less, so as to be used as a release film for a film-like multilayer ceramic capacitor (MLCC), and which is good for rollability and smoothness of rolls. Excellent mobility.
另外,旨在提供一種聚酯離型膜,其在塗布陶瓷漿料以製造薄膜狀的陶瓷片材時,針孔產生得少。In addition, it is an object to provide a polyester release film in which pinholes are less generated when a ceramic slurry is applied to manufacture a thin-film ceramic sheet.
另外,旨在提供一種聚酯離型膜,其在制膜時,即便高速移送,切屑產生得也少,而且在切割膜時,粉塵產生得少。 技術方案 In addition, it is an object to provide a polyester release film in which, even if it is transferred at a high speed during film formation, less chips are generated and less dust is generated when the film is cut. Technical solutions
為了解決上述問題而進行研究的結果,發現能夠通過製造包含滿足特定物性的雙峰形態的粒子的膜來達成上述目的,從而完成了本發明。As a result of studies to solve the above-mentioned problems, the inventors have found that the above-mentioned objects can be achieved by producing a film containing particles having a bimodal shape satisfying specific physical properties, thereby completing the present invention.
本發明的一例提供一種聚酯離型膜,其為層疊一層以上而成的雙向拉伸聚酯膜,所述聚酯離型膜在至少一表面包含粒子,所述粒子具有粒子A和粒子B,當測量包含粒子的聚酯層中的粒子的細微性分佈,並以橫軸表示粒子直徑、縱軸表示粒子數的方式繪圖時,所述粒子A和粒子B的平均粒徑滿足關係式1和關係式2的範圍,所述粒子A與粒子B的重量比滿足關係式3。 0.1μm ≤ 粒子A的平均粒徑 ≤ 0.5μm 關係式1 0.6μm ≤ 粒子B的平均粒徑 ≤ 1.2μm 關係式2 2 ≤ 粒子A 的重量 / 粒子B的重量 關係式3 An example of the present invention provides a polyester release film, which is a biaxially oriented polyester film formed by laminating one or more layers, the polyester release film includes particles on at least one surface, and the particles have particles A and B , when the fineness distribution of particles in the polyester layer containing particles is measured and plotted in such a way that the horizontal axis represents the particle diameter and the vertical axis represents the number of particles, the average particle diameters of the particles A and B satisfy the relational expression 1 and the range of the relational expression 2, the weight ratio of the particles A and the particles B satisfies the relational expression 3. 0.1μm ≤ Average particle size of particle A ≤ 0.5μm Relational formula 1 0.6μm ≤ Average particle size of particle B ≤ 1.2μm Relational formula 2 2 ≤ weight of particle A / weight of particle B Relation 3
在本發明的一例中,所述關係式3可以是2 ≤ 粒子A 的重量 / 粒子B的重量 ≤ 10。In an example of the present invention, the relational expression 3 may be 2 ≤ weight of particle A / weight of particle B ≤ 10.
在本發明的一例中,所述粒子A和粒子B的平均粒徑可滿足關係式4。 粒子B的平均粒徑 ﹣ 粒子A的平均粒徑 ≤ 0.5μm 關係式4 In an example of the present invention, the average particle diameters of the particles A and B may satisfy the relational expression 4. Average particle size of particle B - Average particle size of particle A ≤ 0.5μm Relation 4
在本發明的一例中,所述離型膜的總厚度可以是10~50μm。In an example of the present invention, the total thickness of the release film may be 10 to 50 μm.
在本發明的一例中,相對於膜的總重,所述粒子的含量可以是0.01~0.3重量%。In one example of the present invention, the content of the particles may be 0.01 to 0.3% by weight relative to the total weight of the film.
在本發明的一例中,所述粒子可以是選自無機粒子和有機粒子中的一種或兩種以上混合而成的混合物。In one example of the present invention, the particles may be one or a mixture of two or more selected from inorganic particles and organic particles.
在本發明的一例中,所述無機粒子可選自碳酸鈣、氧化鈦、二氧化矽、高嶺土以及硫酸鋇,所述有機粒子可以是選自矽樹脂、交聯二乙烯基苯聚甲基丙烯酸酯、交聯聚甲基丙烯酸酯、交聯聚苯乙烯樹脂、苯代三聚氰胺-甲醛樹脂、苯代三聚氰胺-三聚氰胺-甲醛樹脂以及三聚氰胺-甲醛樹脂中的一種或兩種以上的混合物。In an example of the present invention, the inorganic particles can be selected from calcium carbonate, titanium oxide, silica, kaolin and barium sulfate, and the organic particles can be selected from silicone resin, cross-linked divinylbenzene polymethacrylic acid One or more mixtures of esters, cross-linked polymethacrylates, cross-linked polystyrene resins, benzo-substituted melamine-formaldehyde resins, benzo-substituted melamine-melamine-formaldehyde resins and melamine-formaldehyde resins.
在本發明的一例中,所述無機粒子可以是二氧化矽或碳酸鈣。In an example of the present invention, the inorganic particles may be silica or calcium carbonate.
在本發明的一例中,所述無機粒子可以是平均粒徑為0.1~0.5μm的二氧化矽(粒子A)和平均粒徑為0.6~1.0μm的碳酸鈣(粒子B),並且所述碳酸鈣(粒子B)的平均粒徑與二氧化矽(粒子A)的平均粒徑之差可以是0.5μm以下。 有益效果 In an example of the present invention, the inorganic particles may be silicon dioxide (particle A) with an average particle size of 0.1-0.5 μm and calcium carbonate (particle B) with an average particle size of 0.6-1.0 μm, and the carbonic acid The difference between the average particle size of calcium (particle B) and the average particle size of silica (particle A) may be 0.5 μm or less. beneficial effect
本發明的聚酯離型膜為薄膜且對於輥的捲繞性以及滑移性優秀,並且在塗布陶瓷漿料以製造薄膜狀的陶瓷片材時,針孔產生得少。The polyester release film of the present invention is a film, and is excellent in rollability and slipperiness to a roll, and pinholes are less generated when a ceramic slurry is applied to produce a thin-film ceramic sheet.
另外,能夠提供一種聚酯離型膜,其在制膜時,即便高速移送,切屑產生得也少,而且在切割膜時,粉塵產生得少。In addition, it is possible to provide a polyester release film in which, even when transferred at a high speed during film formation, less chips are generated and less dust is generated when the film is cut.
以下,對本發明進行更加詳細的說明。下述的具體例或實施例僅為用於對本發明進行詳細說明的一個參照,本發明不限於此,本發明能夠實現為多種形態。Hereinafter, the present invention will be described in more detail. The following specific example or embodiment is only a reference for describing the present invention in detail, and the present invention is not limited thereto, and the present invention can be implemented in various forms.
另外,除非另作定義,否則所有的技術術語及科學術語就具有與本領域技術人員通常所理解的含義相同的含義。本發明中用於說明的術語只是用於有效地敘述特定具體例,而不是限定本發明。Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by those skilled in the art. The terms used for description in the present invention are only used to effectively describe specific examples, and are not intended to limit the present invention.
另外,除非上下文中有特別的指示,否則說明書及所附的權利要求書中使用的單數形態就包括複數形態。Also, use of the singular in the specification and the appended claims includes the plural unless the context clearly dictates otherwise.
另外,當某部分“包括”某構成要素時,除非有相反的記載,否則就表示不是排除其它的構成要素,而是可進一步包括其他的構成要素。In addition, when a part "includes" a certain element, unless stated to the contrary, it means that other elements are not excluded, but other elements may be further included.
以下,對本發明的各個構成進行更加具體的說明。Hereinafter, each configuration of the present invention will be described in more detail.
在本發明的一例中,所述聚酯樹脂可用作用於製造聚酯膜的母料切片。In one example of the present invention, the polyester resin can be used as a masterbatch chip for producing polyester films.
本發明的發明人發現當混合使用粒徑不同的兩種無機粒子且將這些粒子以特定範圍的尺寸和含量組合使用時,能夠提供一種膜,該膜的表面平坦且包括用於改善後加工處理和膜的捲繞性的有效突起,並且在切割時,粉塵產生得少,從而完成了本發明。The inventors of the present invention have found that when two kinds of inorganic particles having different particle diameters are mixed and used and these particles are used in combination in a specific range of size and content, it is possible to provide a film which has a flat surface and includes features for improving post-processing. The present invention has been completed with an effective protrusion of the windability of the film and the generation of less dust at the time of cutting.
在本發明的一例中,所述聚酯樹脂沒有特別的限制,可使用通常所使用的聚酯樹脂。具體例如,可以是由以二羧酸為主要組分的酸組分和以亞烷基二醇為主要組分的二醇組分縮聚而成的。對於上述二羧酸沒有限制,可使用對苯二甲酸或其烷基酯或苯基酯等,一部分可替換使用間苯二甲酸、氧基乙氧基苯甲酸(oxyethoxy benzoic acid)、己二酸、皮脂酸以及間苯二甲酸-5-磺酸鈉等雙官能性羧酸或其成酯衍生物。另外,對於二醇組分沒有限制,主要使用乙二醇,可混合使用1,2-丙二醇、新戊二醇、1,3-丙二醇、1,4-環己二醇、1,4-環己二甲醇、1,4-雙氧乙氧基苯、雙酚以及聚氧乙二醇等,也可部分並用單官能性化合物或三官能性化合物。In one example of the present invention, the polyester resin is not particularly limited, and commonly used polyester resins can be used. For example, it can be obtained by polycondensation of an acid component mainly composed of dicarboxylic acid and a diol component mainly composed of alkylene glycol. The above-mentioned dicarboxylic acid is not limited, and terephthalic acid, its alkyl ester, phenyl ester, etc. can be used, and a part of isophthalic acid, oxyethoxy benzoic acid, adipic acid can be used instead. , sebacic acid and difunctional carboxylic acids such as sodium isophthalic acid-5-sulfonate or their ester-forming derivatives. In addition, there is no restriction on the diol component, but ethylene glycol is mainly used, and 1,2-propanediol, neopentyl glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanediol can be mixed and used. For example, hexanedimethanol, 1,4-dioxyethoxybenzene, bisphenol, polyoxyethylene glycol, etc., a monofunctional compound or a trifunctional compound may be partially used in combination.
除此之外,還可包含聚合聚酯樹脂時通常所使用的添加劑,即,選自釘紮(pinning)劑、抗靜電劑、紫外線穩定劑、防水劑、增滑劑以及熱穩定劑中的一種或兩種以上組分,但不限於此。In addition to this, additives commonly used when polymerizing polyester resins, that is, additives selected from the group consisting of pinning agents, antistatic agents, ultraviolet stabilizers, water repellants, slip agents, and heat stabilizers may be included. One or two or more components, but not limited thereto.
所述聚酯樹脂可通過作為本領域常規的聚合方法的TPA(Terephthalic acid,對苯二甲酸)聚合法或DMT(dimethyl terephthalate,對苯二甲酸二甲酯)聚合法等製備,但不限於此。The polyester resin can be prepared by TPA (Terephthalic acid, terephthalic acid) polymerization method or DMT (dimethyl terephthalate, dimethyl terephthalate) polymerization method, etc., which are conventional polymerization methods in the art, but not limited thereto .
在本發明的一例中,所述聚酯樹脂可以是聚對苯二甲酸乙二酯。即,所述聚酯樹脂可以是使用對苯二甲酸(Terephthalic acid)作為二羧酸並且使用乙二醇(Ethylene glycol)作為二醇以製備的聚對苯二甲酸乙二酯。In one example of the present invention, the polyester resin may be polyethylene terephthalate. That is, the polyester resin may be polyethylene terephthalate prepared using Terephthalic acid as a dicarboxylic acid and using Ethylene glycol as a diol.
另外,本發明的聚酯膜優選包含特定的兩種無機粒子,以降低表面粗糙度,防止在用作離型膜的基膜時,因表面粗糙度的轉印而使得塗布到離型層上的層產生針孔或厚度不均勻,同時,改善輥移動性、捲繞性等處理(Handling)性,從而大幅提高生產性。In addition, the polyester film of the present invention preferably contains two specific inorganic particles to reduce surface roughness and prevent coating on the release layer due to transfer of surface roughness when used as a base film for a release film Pinholes or uneven thickness occur in the layer, and at the same time, the handling (Handling) properties such as roll mobility and winding properties are improved, thereby greatly improving productivity.
更具體地,可包含同時滿足關係式1至3的粒子。More specifically, particles satisfying Relational Expressions 1 to 3 at the same time may be contained.
具體地,所述粒子具有粒子A和粒子B,當測量包含粒子的聚酯層中的粒子的細微性分佈,並以橫軸表示粒子直徑、縱軸表示粒子數的方式繪圖時,所述粒子A和粒子B的平均粒徑滿足關係式1和關係式2的範圍,並且所述粒子A與粒子B的重量比滿足關係式3。 0.1μm ≤ 粒子A的平均粒徑 ≤ 0.5μm 關係式1 0.6μm ≤ 粒子B的平均粒徑 ≤ 1.2μm 關係式2 2 ≤ 粒子A 的重量 / 粒子B的重量 關係式3 Specifically, the particles have particles A and B, and when the fineness distribution of the particles in the polyester layer containing the particles is measured and plotted in such a manner that the horizontal axis represents the particle diameter and the vertical axis represents the number of particles, the particle The average particle diameters of the particles A and B satisfy the ranges of the relational expressions 1 and 2, and the weight ratio of the particles A and the particles B satisfy the relational expressions 3. 0.1μm ≤ Average particle size of particle A ≤ 0.5μm Relational formula 1 0.6μm ≤ average particle size of particle B ≤ 1.2μm Relational formula 2 2 ≤ weight of particle A / weight of particle B Relation 3
即,所述關係式1和2表示在粒子直徑為0.1~0.5μm、0.6~1.2μm的範圍內分別具有一個以上的平均粒徑,所述關係式3可以是具有上述0.1~0.5μm的範圍的平均粒徑的粒子A與具有0.6~1.2μm範圍的平均粒徑的粒子B的含量比(重量比,粒子A 的重量 / 粒子B的重量)為2以上、3以上,更具體為2至10、2至11、3至10、3至11、3至11.5。That is, the relational expressions 1 and 2 indicate that the particle diameters have one or more average particle diameters in the ranges of 0.1 to 0.5 μm and 0.6 to 1.2 μm, respectively, and the relational expression 3 may have the above-mentioned range of 0.1 to 0.5 μm. The content ratio (weight ratio, weight of particle A/weight of particle B) of particles A having an average particle diameter of 0.6 to 1.2 μm and particle B having an average particle diameter in the range of 0.6 to 1.2 μm is 2 or more, 3 or more, more specifically 2 to 10, 2 to 11, 3 to 10, 3 to 11, 3 to 11.5.
在同時滿足所述關係式1至3的範圍內,能夠如目的那樣提供一種聚酯離型膜,其為薄膜,且在制膜時,對於輥的捲繞性以及滑移性優秀,並且平滑性優秀,因此,在塗布陶瓷漿料以製造薄膜狀的陶瓷片材時,針孔產生少。As long as the above-mentioned relational expressions 1 to 3 are satisfied at the same time, a polyester release film can be provided as intended, which is a film, which is excellent in rollability and slipperiness to a roll during film formation, and is smooth Because of its excellent properties, pinholes are less generated when a ceramic slurry is applied to produce a thin-film ceramic sheet.
即,能夠提供同時滿足彼此為折中關係的平滑性、滑移性以及捲繞性的膜。具體地,能夠提供一種膜,該膜的表面平坦且包括用於改善後加工處理和膜的捲繞性的有效突起,並且能夠減少因轉印表面粗糙度而產生的針孔以及多層陶瓷電容器短路(MLCC Short)不良率。That is, it is possible to provide a film that simultaneously satisfies smoothness, slipperiness, and windability which are in a trade-off relationship with each other. Specifically, it is possible to provide a film which has a flat surface and includes effective protrusions for improving post-processing and film rollability, and which can reduce pinholes and short circuits in multilayer ceramic capacitors due to transfer surface roughness (MLCC Short) defective rate.
另外,能夠提供一種聚酯離型膜,其在制膜時,即便高速移送,切屑產生得也少,而且在切割膜時,粉塵產生得少。In addition, it is possible to provide a polyester release film in which, even when transferred at a high speed during film formation, less chips are generated and less dust is generated when the film is cut.
另外,所述粒子A和粒子B的平均粒徑可滿足關係式4。 粒子B的平均粒徑 ﹣ 粒子A的平均粒徑 ≤ 0.5μm 關係式4 In addition, the average particle diameters of the particles A and B may satisfy the relational expression 4. Average particle size of particle B - Average particle size of particle A ≤ 0.5μm Relation 4
如所述關係式4所示,上述的0.1~0.5μm的平均粒徑與0.6~1.2μm的範圍內的平均粒徑之差為0.5μm以下,更具體地,可以是0.1~0.5μm。在上述範圍內,表面平滑性更加優秀,當用於陶瓷電容器時,能夠進一步減少針孔的產生,並且在切割膜時,能夠減少切屑的含量,以減少異物的產生。As shown in the relational expression 4, the difference between the above-mentioned average particle diameter of 0.1 to 0.5 μm and the average particle diameter in the range of 0.6 to 1.2 μm is 0.5 μm or less, more specifically, 0.1 to 0.5 μm. Within the above range, the surface smoothness is more excellent, the generation of pinholes can be further reduced when used in ceramic capacitors, and the content of chips can be reduced when the film is cut to reduce the generation of foreign matter.
在本發明的一例中,所述粒子可以是選自無機粒子和有機粒子中的一種或兩種以上混合而成的混合物。In one example of the present invention, the particles may be one or a mixture of two or more selected from inorganic particles and organic particles.
所述無機粒子選自碳酸鈣、氧化鈦、二氧化矽、高嶺土以及硫酸鋇等,所述有機粒子可以是選自矽樹脂、交聯二乙烯基苯聚甲基丙烯酸酯、交聯聚甲基丙烯酸酯、交聯聚苯乙烯樹脂、苯代三聚氰胺-甲醛樹脂、苯代三聚氰胺-三聚氰胺-甲醛樹脂以及三聚氰胺-甲醛樹脂等中的一種或兩種以上的混合物,但不限於此。The inorganic particles are selected from calcium carbonate, titanium oxide, silicon dioxide, kaolin, barium sulfate, etc., and the organic particles can be selected from silicone resin, cross-linked divinyl benzene polymethacrylate, cross-linked polymethyl methacrylate, etc. One or more mixtures of acrylates, cross-linked polystyrene resins, benzo-substituted melamine-formaldehyde resins, benzo-substituted melamine-melamine-formaldehyde resins, and melamine-formaldehyde resins, etc., but not limited thereto.
優選地,所述粒子可混合使用平均粒徑為0.1~0.5μm的粒子A和平均粒徑為0.6~1.2μm的粒子B。另外,所述粒子B的平均粒徑與粒子A的平均粒徑之差可以是0.5μm以下,更具體地,可以是0.1~0.5μm。Preferably, the particles can be mixed with particles A having an average particle diameter of 0.1-0.5 μm and particles B having an average particle diameter of 0.6-1.2 μm. In addition, the difference between the average particle diameter of the particles B and the average particle diameter of the particles A may be 0.5 μm or less, and more specifically, may be 0.1 to 0.5 μm.
更優選地,所述粒子可以是平均粒徑為0.1~0.5μm的二氧化矽粒子(粒子A)和平均粒徑為0.6~1.2μm的碳酸鈣(粒子B)。另外,所述碳酸鈣(粒子B)的平均粒徑與二氧化矽粒子(粒子A)的平均粒徑之差可以是0.5μm以下,更具體地,可以是0.1~0.5μm。More preferably, the particles may be silica particles (particles A) with an average particle size of 0.1-0.5 μm and calcium carbonate (particles B) with an average particle size of 0.6-1.2 μm. In addition, the difference between the average particle size of the calcium carbonate (particles B) and the average particle size of the silica particles (particles A) may be 0.5 μm or less, more specifically, 0.1 to 0.5 μm.
在本發明的一例中,相對於膜的總重,所述粒子的含量可以是0.01~0.3重量%,優選為0.05~0.25重量%,更優選為0.1~0.2重量%。在上述範圍內,能夠提供一種膜,其粒子的分散性優秀,並且防止粒子凝聚,而且切屑產生得少。In one example of the present invention, the content of the particles may be 0.01 to 0.3 wt %, preferably 0.05 to 0.25 wt %, and more preferably 0.1 to 0.2 wt % relative to the total weight of the film. Within the above range, it is possible to provide a film which is excellent in particle dispersibility, prevents particle aggregation, and reduces generation of chips.
在本發明的一例中,在合成聚酯樹脂時,將所述粒子以分散於二醇組分的粒子漿料形態添加時,分散性優秀,並且能夠防止粒子之間再凝聚,因此有效,但不限於此。即,可以從酯化反應或酯交換反應結束起加入到縮聚反應開始前,但不限於此。In one example of the present invention, when the particles are added in the form of a particle slurry dispersed in a diol component when synthesizing a polyester resin, the dispersibility is excellent and reaggregation between particles can be prevented, so it is effective, but Not limited to this. That is, it may be added from the end of the esterification reaction or the transesterification reaction to before the start of the polycondensation reaction, but is not limited thereto.
本發明的一例的聚酯離型膜為層疊一層以上而成的雙向拉伸聚酯膜,並且在至少一表面包含滿足所述關係式1至3的粒子。The polyester release film of one example of the present invention is a biaxially oriented polyester film in which one or more layers are laminated, and contains particles satisfying the above-mentioned relational expressions 1 to 3 on at least one surface.
具體地,例如,可以是層疊兩層或三層而成的雙向拉伸聚酯膜,並且其中至少一表面包含滿足所述關係式1至3的粒子。Specifically, for example, it may be a biaxially oriented polyester film in which two or three layers are laminated, and in which at least one surface contains particles satisfying the relational expressions 1 to 3.
更優選地,可以是層疊三層以上而成的雙向拉伸聚酯膜,並且至少一側的表層包含滿足所述關係式1至3的粒子。通過層疊三層以上而成,在不影響表層的粗糙度的範圍內,以在內層部中混合制膜工藝中所產生的邊緣部分的回收原料或其他制膜工藝的再利用原料等的方式,進行再利用,從而在對資源進行再利用的同時降低價格。More preferably, it may be a biaxially oriented polyester film in which three or more layers are laminated, and at least one surface layer may contain particles satisfying the above-mentioned relational expressions 1 to 3. It is formed by laminating three or more layers, and within the range that does not affect the roughness of the surface layer, in the inner layer part, the recovered raw material of the edge portion generated in the film forming process or the recycled raw material of other film forming process is mixed in the inner layer part. , reuse, thereby reducing prices while reusing resources.
所述雙向拉伸表示通過X射線衍射來顯示雙軸取向的圖案。所述拉伸可以是逐次雙向拉伸,可通過執行沿長度方向(縱向)拉伸後再沿寬度方向(橫向)拉伸的工藝而達成。能夠通過以這種方式進行雙向拉伸,使得長度方向和寬度方向的強度和結晶度均勻,並且有效地沿各個方向進行切割。The biaxial stretching means that a pattern of biaxial orientation is exhibited by X-ray diffraction. The stretching may be successive biaxial stretching, which may be achieved by performing a process of stretching in the length direction (longitudinal direction) and then stretching in the width direction (transverse direction). By performing biaxial stretching in this way, the strength and crystallinity in the lengthwise and widthwise directions can be made uniform, and cutting can be efficiently performed in all directions.
本發明的一例的聚酯離型膜滿足所述關係式1至3,因此,能夠提供一種膜,其基於JIS B-0601,使用表面粗糙度測量儀(東京精密(Tokyo seimitsu),Surfcom 590A-3DF-12)測得的表面粗糙度峰值計數Pc為2.0個/mm 2以下,更具體地,為0.1~2個/mm 2以下。在上述範圍內,能夠在降低表面粗糙度的同時滿足捲繞性和移動性,因此,能夠提供生產性得到提高的膜,因此優選,但不限於此。 The polyester release film of an example of the present invention satisfies the above-mentioned relational expressions 1 to 3, and therefore, it is possible to provide a film based on JIS B-0601 using a surface roughness measuring instrument (Tokyo seimitsu, Surfcom 590A- 3DF-12) The surface roughness peak count Pc measured is 2.0 pieces/mm 2 or less, and more specifically, 0.1 to 2 pieces/mm 2 or less. Within the above-mentioned range, the surface roughness can be reduced while the windability and mobility can be satisfied, and therefore, a film with improved productivity can be provided, which is preferable, but not limited to this.
本發明的一例的聚酯離型膜利用接觸式三維表面粗糙度儀並且採用0.08mm的截止值來測得的中心線平均表面粗糙度Ra可以是20nm以下,更優選為15nm以下。具體地,中心線平均表面粗糙度Ra可以是1~20nm,更具體地,可以是4~15nm。在上述範圍內,能夠提供一種膜,其表面粗糙度低,因此平滑性優秀,並且當用作MLCC的離型膜時,幾乎不產生針孔,因此優選,但不限於此。The polyester release film of an example of the present invention may have a centerline average surface roughness Ra measured by a contact three-dimensional surface roughness meter with a cutoff value of 0.08 mm of 20 nm or less, more preferably 15 nm or less. Specifically, the centerline average surface roughness Ra may be 1 to 20 nm, and more specifically, 4 to 15 nm. Within the above range, a film can be provided which has a low surface roughness and thus is excellent in smoothness, and which hardly generates pinholes when used as a release film for MLCC, which is preferable, but not limited thereto.
所述離型膜的總厚度可以是10~50μm,更具體地,可以是20~40μm。在上述範圍內,可充分用作離型膜的基膜,但不限於此。用作MLCC用離型膜的基膜的聚酯膜呈現出其使用厚度持續地薄型化的趨勢,因此,適合在上述範圍內應用。另外,當以三層以上層疊時,可形成芯層以及形成於其兩面的表層,並且芯層與表層的厚度比可以是50%∶50%至90%∶10%,更優選為60%∶40%至80%∶20%。在上述範圍內,能夠提供一種膜,其移動性優秀,並且滑移性優秀,對於輥的捲繞性得到提高,切屑產生得少,因此優選。The total thickness of the release film may be 10-50 μm, more specifically, 20-40 μm. Within the above range, it can be sufficiently used as a base film for a release film, but is not limited thereto. Since the polyester film used as the base film of the release film for MLCC shows the tendency for the thickness to be continuously reduced in use, it is suitable to be used in the above-mentioned range. In addition, when three or more layers are stacked, the core layer and the skin layers formed on both sides thereof may be formed, and the thickness ratio of the core layer to the skin layer may be 50%:50% to 90%:10%, more preferably 60%:10% 40% to 80%: 20%. Within the above range, it is possible to provide a film which is excellent in mobility, excellent in slippage, improved in windability to a roll, and less generation of chips, which is preferable.
在本發明的一例中,所述聚酯膜可以是雙向拉伸膜。具體地,所述聚酯膜可以是進行沿機械方向拉伸3至5倍以及沿寬度方向拉伸4至6倍的雙向拉伸而成的。在上述拉伸比內,高分子結構的熱尺寸穩定性能夠進一步提高,從而減少熱收縮,因此優選,但不限於此。In one example of the present invention, the polyester film may be a biaxially stretched film. Specifically, the polyester film may be biaxially stretched by stretching 3 to 5 times in the machine direction and 4 to 6 times in the width direction. Within the above stretching ratio, the thermal dimensional stability of the polymer structure can be further improved, thereby reducing thermal shrinkage, which is preferable, but not limited to this.
在本發明的一例中,所述聚酯膜可在雙向拉伸之後在200~250℃下進行熱處理並鬆弛1%至10%。具體地,可在進行熱處理的同時使其鬆弛,更具體地,可沿寬度方向鬆弛1%至10%,更具體地,可鬆弛2%至4%。在上述範圍內,膜能夠保持沿寬度方向緊張的狀態,以提高高分子結構的緻密性並減少熱變形,因此優選,但不限於此。In an example of the present invention, the polyester film may be heat-treated at 200˜250° C. and relaxed by 1% to 10% after biaxial stretching. Specifically, it may be relaxed while being heat-treated, more specifically, it may be relaxed by 1% to 10% in the width direction, and more specifically, it may be relaxed by 2% to 4%. Within the above range, the film can be kept in a state of tension in the width direction to improve the density of the polymer structure and reduce thermal deformation, which is preferable, but not limited to this.
以下,基於實施例和比較例對本發明進行更加詳細的說明。只是,下述實施例和比較例僅為用於對本發明進行更詳細說明的一個示例,本發明不限於下述實施例和比較例。Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely examples for illustrating the present invention in more detail, and the present invention is not limited to the following Examples and Comparative Examples.
以下,以下述方式對物性進行評價。Hereinafter, physical properties were evaluated in the following manner.
[平均粒徑][The average particle size]
使用細微性分佈測量儀(Beckman公司的LS13 320)進行測量。The measurement was performed using a fineness distribution measuring instrument (LS13 320 from Beckman Corporation).
[表面粗糙度(Ra)][Surface Roughness (Ra)]
基於JIS B-0601,在對聚酯膜的左/中/右三個位置切片之後,使用三維表面粗糙度測量儀(東京精密(Tokyo seimitsu),Surfcom 590A-3DF-12),以測量速度為0.03mm/sec、觸針半徑為2μm、荷重為0.7mm/N、測量面積為1.0mm 2、截止值為0.08mm的條件進行測量。 Based on JIS B-0601, after slicing the left/center/right three positions of the polyester film, a three-dimensional surface roughness measuring instrument (Tokyo seimitsu, Surfcom 590A-3DF-12) was used at a measuring speed of The measurement was performed under the conditions of 0.03 mm/sec, a stylus radius of 2 μm, a load of 0.7 mm/N, a measurement area of 1.0 mm 2 , and a cutoff value of 0.08 mm.
以x軸為中心線,以y軸為垂直方向,用y=f(x)表示粗糙度曲線,此時,通過下式進行計算。 Taking the x-axis as the center line and the y-axis as the vertical direction, the roughness curve is represented by y=f(x). At this time, the calculation is performed by the following formula.
其中,L:基準長度(Cut-Off)。Among them, L: reference length (Cut-Off).
[捲繞收率][winding yield]
對於在實施例和比較例中製成的聚酯膜,通過計算製造時產品生產量與投入量之比,評價如下。 捲繞收率(%) = (產品生產量 / 投入量) × 100 ◎:當收率為65%以上時 ○:當收率為55%以上且小於65%時 △:當收率小於55%時 The polyester films produced in Examples and Comparative Examples were evaluated as follows by calculating the ratio of the production amount to the input amount at the time of production. Winding yield (%) = (product production / input) × 100 ◎: When the yield is 65% or more ○: When the yield is 55% or more and less than 65% △: When the yield is less than 55%
[切屑產生程度][degree of chip generation]
將製成的膜以300m/min的速度切割為500mm的寬度,並在膜卷材表面上確認是否存在由切割後的500mm的膜卷材的PET切屑所致的粒子,設定當每1m 2中的顆粒數為0個時為1級,1個~3個為2級,4個~6個為3級,7個~9個為4級,10~12個為5級,13個以上為6級,其中,1級、2級為合格,其餘為不合格。 The produced film was cut into a width of 500 mm at a speed of 300 m/min, and the presence or absence of particles caused by PET chips of the cut 500 mm film roll was confirmed on the surface of the film roll, and the setting was as follows: When the number of particles is 0, it is grade 1, 1 to 3 are grade 2, 4 to 6 are grade 3, 7 to 9 are grade 4, 10 to 12 are grade 5, and more than 13 are grade 5. Level 6, of which, Level 1 and Level 2 are qualified, and the rest are unqualified.
[生產收率][Production yield]
使用一卷在實施例和比較例中製成的聚酯膜的母卷作為基膜,在形成矽離型層之後,塗布陶瓷漿料,以製造厚度為1.5~3.0μm的陶瓷生料片。此時,根據是否產生針孔來進行如下評價。生產收率為最終生產的陶瓷生料片的面積與所供給的一卷聚酯膜的母卷的面積之比。 生產收率(%) = (陶瓷生料片的面積 / 一卷聚酯膜的母卷的面積) × 100 優秀:對於一卷聚酯膜的母卷,未產生針孔 良好:對於一卷聚酯膜的母卷,一部分產生了針孔,並且生產收率為70%以上 普通:對於一卷聚酯膜的母卷,一部分產生了針孔,並且生產收率為30%以上 不良:對於一卷聚酯膜的母卷,大部分產生了針孔,並且生產收率低於30% A master roll of the polyester film produced in the Examples and Comparative Examples was used as a base film, and after the silicon release layer was formed, a ceramic slurry was applied to manufacture a ceramic green sheet having a thickness of 1.5-3.0 μm. At this time, the following evaluation was performed based on whether or not pinholes were generated. The production yield is the ratio of the area of the final produced ceramic green sheet to the area of the parent roll of one roll of polyester film supplied. Production yield (%) = (area of ceramic green sheet / area of parent roll of one roll of polyester film) × 100 Excellent: No pinholes for a parent roll of polyester film Good: For a master roll of polyester film, pinholes occurred in a part, and the production yield was 70% or more Ordinary: For the parent roll of one roll of polyester film, pinholes are generated in a part, and the production yield is more than 30% Defect: For a master roll of polyester film, most of the pinholes are generated, and the production yield is less than 30%
[實施例1][Example 1]
1)製備聚酯切片(1)1) Preparation of polyester chips (1)
相對於100重量份的對苯二甲酸二甲酯,將50重量份的乙二醇、400ppm的乙酸鎂和200ppm的乙酸鈣、150ppm的三氧化二銻投入酯化反應器中,之後,在從常溫到230℃進行4小時的酯交換反應,以製備預聚物對苯二甲酸雙羥乙酯(bis-β-hydroxyethyl terephthalate,BHET),其中,乙酸鎂和乙酸鈣用作靜電釘紮劑,三氧化二銻用作聚合催化劑。使反應中產生的副產物甲醇向反應器外流出,並通過蒸餾塔進行分離,酯化反應結束後額外產生的乙二醇也通過蒸餾塔進行分離。此時,在添加200ppm的磷酸三甲酯作為熱穩定劑之後,在緩慢升溫至285℃的同時,將壓力減小至0.3torr。在高真空下進行4小時的縮聚反應,以製造出固有粘度為0.630dL/g的聚對苯二甲酸乙二酯(PET)樹脂切片。With respect to 100 parts by weight of dimethyl terephthalate, 50 parts by weight of ethylene glycol, 400 ppm of magnesium acetate, 200 ppm of calcium acetate, and 150 ppm of antimony trioxide were put into the esterification reactor, and after that, from A transesterification reaction was carried out at room temperature to 230 °C for 4 hours to prepare the prepolymer bis-β-hydroxyethyl terephthalate (BHET), in which magnesium acetate and calcium acetate were used as electrostatic pinning agents, Antimony trioxide was used as a polymerization catalyst. The by-product methanol produced in the reaction flows out of the reactor and is separated by a distillation column, and the additionally produced ethylene glycol after the esterification reaction is completed is also separated by a distillation column. At this time, after adding 200 ppm of trimethyl phosphate as a thermal stabilizer, the pressure was reduced to 0.3 torr while the temperature was slowly raised to 285°C. The polycondensation reaction was carried out under high vacuum for 4 hours to produce polyethylene terephthalate (PET) resin chips with an intrinsic viscosity of 0.630 dL/g.
2)製備聚酯切片(2)2) Preparation of polyester chips (2)
向所述聚酯切片(1)添加1重量%的平均粒徑為0.3μm的二氧化矽(粒子A)並利用雙軸捏合機進行熔融擠出以製備聚酯切片(2)。To the polyester chip (1), 1% by weight of silica (particle A) having an average particle diameter of 0.3 μm was added and melt-extruded using a biaxial kneader to prepare a polyester chip (2).
3)製備聚酯切片(3)3) Preparation of polyester chips (3)
向所述聚酯切片(1)添加1重量%的平均粒徑為0.7μm的碳酸鈣(粒子B)並利用雙軸捏合機進行熔融擠出以製備聚酯切片(3)。To the polyester chip (1), 1% by weight of calcium carbonate (particle B) having an average particle diameter of 0.7 μm was added and melt-extruded using a biaxial kneader to prepare a polyester chip (3).
4)制膜4) Film making
芯層使用不包含無機粒子的聚對苯二甲酸乙二酯(PET)切片(1),表層以如表1中所示的含量混合使用所述聚對苯二甲酸乙二酯(PET)切片(1)、聚酯切片(2)以及聚酯切片(3)。The core layer uses a polyethylene terephthalate (PET) chip (1) that does not contain inorganic particles, and the surface layer uses the polyethylene terephthalate (PET) chip mixed with the content shown in Table 1 (1), polyester chips (2), and polyester chips (3).
以層疊為表層/芯層/表層的三層膜形式共擠出,並在冷卻輥上流延以製造未拉伸片材。此時,上述的芯層占膜的總重的80重量%,表層占膜的總重的20重量%。Coextruded as a skin/core/skin three-layer film laminated and cast on chill rolls to make unstretched sheets. At this time, the above-mentioned core layer occupies 80% by weight of the total weight of the film, and the skin layer occupies 20% by weight of the total weight of the film.
通過擠出機進行熔融擠出之後,利用表面溫度為20℃的流延鼓進行急冷、固化,以製造片材。在95℃下,將製成的片材沿機械方向拉伸3.5倍,沿橫向拉伸4.0倍,並在230℃下進行熱處理,最終製造出了膜中的粒子含量為0.2重量%且厚度為31μm的雙向拉伸膜。芯層的厚度為24.8μm,表層的厚度分別為3.1μm。對製成的膜的物性進行測量並將其示於表2中。After melt extrusion by an extruder, rapid cooling and solidification were performed with a casting drum having a surface temperature of 20° C. to manufacture a sheet. The resulting sheet was stretched 3.5 times in the machine direction and 4.0 times in the transverse direction at 95°C, and heat-treated at 230°C, and finally produced a film with a particle content of 0.2 wt % and a thickness of 31 μm biaxially oriented film. The thickness of the core layer was 24.8 μm, and the thickness of the surface layers was 3.1 μm, respectively. The physical properties of the produced films were measured and shown in Table 2.
[實施例2至6][Examples 2 to 6]
如表1中所示,除了調節了粒子的含量比以外,以與實施例1相同的方式制膜。對製成的膜的物性進行測量並將其示於表2中。As shown in Table 1, a film was formed in the same manner as in Example 1 except that the content ratio of the particles was adjusted. The physical properties of the produced films were measured and shown in Table 2.
[比較例1][Comparative Example 1]
如表1中所示,除了調節了粒子的含量比以外,以與實施例1相同的方式制膜。對製成的膜的物性進行測量並將其示於表2中。As shown in Table 1, a film was formed in the same manner as in Example 1 except that the content ratio of the particles was adjusted. The physical properties of the produced films were measured and shown in Table 2.
[比較例2][Comparative Example 2]
除了在實施例1中使用聚酯切片(4)來替代聚酯切片(3)以外,以與實施例1相同的方式制膜。對製成的膜的物性進行測量並將其示於表2中。A film was formed in the same manner as in Example 1, except that the polyester chip (4) was used instead of the polyester chip (3) in Example 1. The physical properties of the produced films were measured and shown in Table 2.
所述聚酯切片(4)通過向所述聚酯切片(1)添加1重量%的平均粒徑為1.0μm的交聯聚苯乙烯粒子(粒子B)並利用雙軸捏合機進行熔融擠出以製備聚酯切片(4)。
表1
如表2中所示,即便使用了兩種粒子,當粒子之間的粒徑比和雙峰細微性分佈脫離了本發明的範圍時,生產收率也會發生不良。另外,經確認,切屑增加,捲繞收率降低,並且表面粗糙度增加。As shown in Table 2, even if two kinds of particles were used, when the particle size ratio between the particles and the bimodal fineness distribution were outside the scope of the present invention, the production yield was poor. In addition, it was confirmed that the chips increased, the winding yield decreased, and the surface roughness increased.
綜上,通過特定的事項和經限定的實施例對本發明進行了說明,但這僅用於幫助更加全面地理解本發明,本發明不限於上述的實施例,並且本領域技術人員能夠基於這種記載進行多種修改和變形。In conclusion, the present invention has been described through specific matters and limited embodiments, but this is only for helping a more comprehensive understanding of the present invention, the present invention is not limited to the above-mentioned embodiments, and those skilled in the art can Records undergo various modifications and variations.
因此,本發明的思想不限於所說明的實施例,所附的權利要求書及其等同和等效變形均屬於本發明的思想範疇。Therefore, the idea of the present invention is not limited to the described embodiments, and the appended claims and their equivalents and equivalent modifications all belong to the scope of the idea of the present invention.
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