201238761 jyyy^pif 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種搬送半導體裝置及供小型零件安 裝的印刷配線基板等基板的基板搬送用載具及其製造方 法。 【先前技術】 自先前以來’供電子零件安裝的印刷配線基板被用於 所有電子機器中。通常，該印刷配線基板於表面具備導體 圖案，近年來’為了應對電子機器的小型化、輕量化，而 提供有各種印刷配線基板。 於該印刷配線基板中，存在於膜狀的絕緣基板表面具.. 備導體圖案、且可使基板本身彎曲的可撓性印刷配線基板 (以下，略記為「FPC (Flexible Printed Circuit)」）0 因該FPC是薄的膜狀的基板，故若為單體，則容易產 生扭曲或翹曲。因此，當對該FPC進行電子零件安裝或化 學品清洗、電漿處理等時，使用了所謂基板的搬送用載具 的夾具（專利文獻1)〇 於專利文獻1中，使自包含矽酸酯化合物及具有規定 的、、、。構的聚一甲基石夕氣燒的混合物所獲得的樹脂片密接於 基體上’而製造基板的搬送載具。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第4438891號說明書 FPC於其製造製程中，與驗性的鍍敷液等各種化學品 201238761 39994pif 進行接觸。因此’搬送用載具亦同樣地曝露於各種化心 中尤其，搬送載具通常被重複使用，因此於化學 露多次。 于°口甲曝 本發明者等人料利文獻丨巾所記_基板搬送 = 於搬送步驟中存在與驗性溶: 寺化〜進灯接觸的步驟時，於該步驟後將配置在 „載具上的FPC等被搬送物自載具上剝離時，^ ^月曰片的—部分剝^，而附著於被搬送物上的問題 落等，則會導致-的良率下降。 綠民，鑒於上述實際情況，本發明的目的在於提供一 黏著ί的尤其鹼性溶液進行接觸後’亦較少產生 黏者層的财的基板搬送用載具及其製造方法。 結果了努力研究， 細的密接性未必充分。本發明者等(t 現藉由以下的構成可解決課題者專人基於5亥發現，發 於基储㈣造紐，其是包括用 層，及固定勒著層的；可剝離地密接的黏著 法，該製造转故如H的純_賴具的製造方 行化S二撐體進行接觸’對支撐體表面進 一』衣面修飾步驟；以及 ;c飾的支樓體上形成黏著層的黏著層形成步 4 201238761 jyyy^pif 甘a (2)如（1)所述之基板搬送用載具的製造方法， -矽酸醋化合物是由Sin〇㈣(r〇)2㈣（R=炫基 ，n=4 〜16)所表示的矽酸酯化合物。 、（3)如（1)或（2)所述之基板搬送用載具的製造 方法，其更包括於表面修飾步驟之前，利用鹼性水溶液清 洗支撐體的鹼清洗步驟。 (4) 如（1)至（3)中任一項所述之基板搬送用載 具的製造方法，其中支撐體是玻璃支撐體。 (5) 如（1)至（4)中任一項所述之基板搬送用載 具的製造方法，其中黏著層包含聚矽氧樹脂。 (6) —種基板搬送用載具，其包括： 用於基板的搬送、並與基板的下表面可剝離地密接的 黏著層；以及 固定黏著層的支撐體；且 固定黏著層之侧的支撐體表面由石夕酸g旨化合物進行了 化學修飾。 (7) 如（6)所述之基板搬送用載具，其中石夕酸酯 化合物是由SinO(n_i)(R〇)2(n+i) (R=烧基，n=4〜16)所表 示的梦酸酯化合物。 [發明的效果] 根據本發明，可提供一種即便與化學品，尤其鹼性溶 液進行接觸後，亦較少產生黏著層的剝離的基板搬送用載 具及其製造方法。 5 201238761 39994pif 【實施方式】 以下，對本發明的基板搬送用載具及其製造方法進行 詳述。 首先，作為與先前技術進行比較的本發明的特徵點， 可列舉於製造黏著層之前，實施使矽酸酯化合物與支撐體 進行接觸的步驟這一點。藉由實施該步驟，支撐體表面上 由石夕酸酿化合物進行修飾，該矽酸酯化合物有助於支撐體 與點著層之間的密接性提昇。其中’當支撐體為玻璃支樓 體，’與發酸酯化合物的親和性及反應性優異，黏著層更 ，於支樓體上，黏著層的剝離得到抑制。另外，當黏 聚錢她時’與化學鍵結於切體表面上的石夕 =接i物具有親和性，黏著層與支魏之間的密接性進 層日二：二當使用魏醋改質聚石夕氧樹脂製造黏著 的對於支=:;==牢固的共價鍵，黏著層 序實施 而貫施的任意步驟。 θ洗^驟是視需要 =清洗步驟）_雜讀崎洗 (表面修飾步驟）使矽酸 ，的…驟 觸’對切體表面進行化學修飾的步驟切體進行接 (黏著層形成步驟）於叙表 著層的㈣ 表__切體上形成黏 以下，對各步驟進行詳述。 6 201238761 iyyy4pif <鹼清洗步驟> 鹼清洗步驟是利用鹼性水溶液清洗支 ==可去除附著於支 支搶體表面與後述的魏酯化合物的反應性 後述的黏著層與支撐體的密接性進一步提昇。’’、、、、’° 程序下對所使用的材料進行詳述，其後對步驟的 面ίίΓϊ;再ΐ ’當所使用的支撐體已具有所期望的 「王狀時，亦可不貫施該步驟。 (驗性水溶液） =财所使㈣水溶賴祕性。其巾，就去除雜 :乂汁支龍表面的反應性的觀點而言 ” 以上，PH更佳為9〜12。 P"乂佳為8 該水溶液中的溶劑通常使用水。再者， 用有機溶劑（例如，醇系溶劑等）。 而’、0 所蚀i 了將該水溶義整祕性，通常添加祕化合物。 鈉、知，驗性化合物並無特別限制，例如可列舉：氫氧化 化人ί虱化鉀、碳酸鈉、烷基銨鹽、烷基芳基銨鹽等。該 宜=的添加量是錄騎成為上述ρΗ的範_方式適 (支撐體） 限剖支樓體只要可支撐後述的黏著層，則其種類並無特別 ^例如可為矽晶圓、玻璃基板、樹脂基板、金屬基板。 ，就與後述的矽酸酯化合物的反應性優異，與黏著層 毪接更優異，並且耐化學品性、耐熱性優異的觀點而言， 201238761 jyyy^tpif 較佳為玻璃基板。玻璃基板並無特別限制，可列舉·· 玻璃、鈉鈣鋁玻璃、硼矽玻璃等基板。 、一 mm 所使用的支撑體的長度及寬度是對應於被搬送物的大 小而適宜碰。另外，支撐體的厚度亦無特職制，但 抑制搬送時的破損等的觀點而言，多為〇 3 mm〜一’ 左右 (步驟的程序） 利用驗性水溶液清洗支樓體的方法並無特別限制 列舉將鹼性水溶液塗佈於支撐體表面上的塗佈方法、將 擇體浸潰於驗性水溶液中的浸潰方法等。 ： 支舰躲性水溶_接_暇對胁所使用的支 =體的種類料適宜設定’但就雜f的去雜、及生 專的觀點而言，較佳為〇·5分鐘〜1〇分鐘左右。 再者’於上述清洗中，視需要亦可照射超音波。 另外，於紐清洗步㈣，視f要亦可彻水進一步 ’月洗支樓體表面，並進行乾燥。 <表面修飾步驟> 表面修飾步驟是於上述鹼清洗步驟後 化合物與支制進行接觸的步驟。藉由=牛= 酸酿化合物進行化學修飾。更具“言，藉： 支她1化合物的層。藉由如上述般對 體表φ&了化予料，形成於其上的 之間的密接性進一步提昇。 者s"支撐體 8 201238761 39994pif 首先’以下對所使用的材料進行詳述’其後對步驟的 程序進行詳述。 (石夕酸醋化合物） 本發明的矽酸酯化合物是指由矽（Si)所形成的金屬 烷氧化物（烷氧基矽烷化合物（尤其，四烷氧基矽烷化合 物））或其寡聚物。所謂寡聚物是指主鏈上具有矽氧烷 (-Si-O-Si-)骨架’側鏈上導入有烧氧基（RO)的化合物。 此處，作為烷氧基（R〇)的烷基部分的（R)可例示甲基、 乙基、丙基等。該矽酸酯化合物具有與水進行反應的特性。 其中’就黏著層的密接性進一步提昇及低分子的游離 物變少的觀點而言，較佳為使用寡聚物。更具體而言，矽 酸酿化合物較理想的是四聚物〜十六聚物（四聚物以上、 十六聚物以下）。其原因在於：若未達四聚物，則矽酸酯化 合物所具有的特性的效果小，另外，若為大於十六聚物者， 則石夕酸酯化合物的黏度變高，故於製造時難以處理。 另外’作為本發明中所使用的矽酸酯化合物的種類， 例如可列舉矽酸曱酯、矽酸乙酯（原矽酸四乙酯（丁故狀比” ^thosihcate’ TE0S))、矽酸丙酯等或該些的寡聚物。就品 貝的穩定性及安全性的觀點而言，較佳為矽酸乙酯（TE〇s) 或其募聚物。 作為矽酸酯化合物的較佳形態，可列舉由[化學式 (R=烧基，n = 4〜16)所表示的石夕酸 =化&物。虽使用上述化合物時’黏著層的對於支樓體的 密接性進-步提昇。尤其’於黏著層為聚魏樹脂層的情 201238761. 增的情況）下，本發明的效果更優異。 作為由化學式1所表示的石夕酸酯化合物的較佳 可列舉由以下的式（χ)所表示的化合物。 /1R1 \ ?R1[Technical Field] The present invention relates to a substrate transfer carrier for transporting a semiconductor device and a substrate such as a printed wiring board for mounting small parts, and a method of manufacturing the same. [Prior Art] Printed wiring substrates for electronic component mounting have been used in all electronic machines since the past. In general, the printed wiring board is provided with a conductor pattern on the surface. In recent years, various printed wiring boards have been provided in order to cope with the miniaturization and weight reduction of electronic equipment. In the printed wiring board, a flexible printed wiring board (hereinafter, abbreviated as "FPC (Flexible Printed Circuit)") having a conductor pattern and having a conductor pattern which is formed on the surface of the film-shaped insulating substrate is used. Since the FPC is a thin film-like substrate, if it is a single body, it tends to be distorted or warped. Therefore, when the FPC is subjected to electronic component mounting, chemical cleaning, plasma processing, or the like, a jig using a substrate transfer carrier (Patent Document 1) is disclosed in Patent Document 1, and a self-contained phthalate is included. Compounds and have defined,, and. A transfer carrier in which a resin sheet obtained by a mixture of polymethyl ketone gas is adhered to a substrate is used to manufacture a substrate. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent No. 44388891 FPC is in contact with various chemicals such as an electroplating solution 201238761 39994pif in its manufacturing process. Therefore, the carrier for transport is similarly exposed to various types of cores. In particular, the transport carrier is usually reused, so that it is chemically exposed a plurality of times. In the case of the mouth of the inventor, the inventor of the inventor has documented the document. _Substrate transport = In the transfer step, there is a step of inspecting the solution: the step of contacting the temple into the lamp, after which it will be placed in the „ When the conveyed material such as the FPC is peeled off from the carrier, the part of the film is peeled off, and the problem of adhering to the object to be conveyed falls, etc., and the yield of the film is lowered. In view of the above-described actual circumstances, an object of the present invention is to provide a substrate transfer carrier which is less likely to cause an adhesive layer after contact with an alkaline solution, and a method for producing the same. The inventors are not necessarily sufficient. The present inventors have found that the following problems can be solved by a person who is based on the discovery of the 5th, and is based on the foundation (4), which includes the layer and the fixed layer; The adhesion method of the ground connection, the manufacturing process such as the manufacture of the pure _ 赖 方 进行 二 二 二 进行 进行 进行 进行 进行 ' ' ' 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 Adhesive layer of adhesive layer forms step 4 201238761 jyyy^pif 甘a (2) (1) The method for producing a substrate transfer carrier, wherein the citric acid phthalate compound is a phthalate compound represented by Sin(R) (r) 2 (four) (R = 炫, n = 4 to 16). (3) The method for producing a substrate transfer carrier according to (1) or (2), further comprising an alkali cleaning step of washing the support with an aqueous alkaline solution before the surface modification step. The method of manufacturing the substrate transfer carrier according to any one of the above aspects, wherein the support is a glass support. (5) The substrate transfer according to any one of (1) to (4) In the method of manufacturing a carrier, the adhesive layer comprises a polyoxyl resin. (6) A substrate transfer carrier comprising: an adhesive layer for transporting a substrate and being detachably adhered to a lower surface of the substrate; And a support for fixing the adhesive layer; and the surface of the support on the side where the adhesive layer is fixed is chemically modified by a compound of the substrate. (7) The carrier for substrate transfer according to (6), wherein The ester compound is a dream ester compound represented by SinO(n_i)(R〇)2(n+i) (R=alkyl group, n=4~16). According to the present invention, it is possible to provide a substrate transfer carrier which is less likely to cause peeling of an adhesive layer even after contact with a chemical, particularly an alkaline solution, and a method for producing the same. 5 201238761 39994pif [Embodiment] Hereinafter, The substrate transfer carrier of the present invention and the method for producing the same are described in detail. First, as a feature of the present invention which is compared with the prior art, the phthalate compound is brought into contact with the support before the production of the adhesive layer. This step is carried out. By carrying out this step, the surface of the support is modified with a sulphuric acid smelting compound which contributes to the improvement of the adhesion between the support and the plied layer. Among them, 'when the support is a glass branch, the affinity and reactivity with the acid ester compound are excellent, and the adhesive layer is more, and the peeling of the adhesive layer is suppressed on the support body. In addition, when cohesive money, she has affinity with the chemical bond on the surface of the body, and the adhesion between the adhesive layer and the Wei is in the second layer: two when using Wei vinegar to improve The polysulfide resin produces any step of adhesion to the support =:; == firm covalent bond, and the adhesive sequence is applied. θ washing step is as needed = cleaning step) _ misreading the smear (surface modification step) to make the sputum, the squid, the step of chemically modifying the surface of the body, the cutting body is connected (adhesive layer forming step) The sub-layers (4) of the table are formed below the viscera, and the steps are detailed. 6 201238761 iyyy4pif <alkaline washing step> The alkali cleaning step is to wash the branch with an alkaline aqueous solution == remove the adhesion between the adhesive layer adhered to the surface of the support and the reactivity of the Wei ester compound described later, and the adhesive layer and the support described later. Further improvement. The '',,,,' ° program details the materials used, and then the surface of the steps ίίΓϊ; then ΐ 'When the support used has the desired "king shape, it can also be applied This step. (Experimental aqueous solution) = The financial system makes (4) water soluble and filthy. The towel is removed from the viewpoint of the reactivity of the surface of the oyster sauce." Above, the PH is preferably 9 to 12. P"乂佳为8 The solvent in this aqueous solution usually uses water. Further, an organic solvent (for example, an alcohol solvent or the like) is used. And ', 0 etched i to dissolve the water in the secret, usually added secret compounds. The sodium, the compound, and the test compound are not particularly limited, and examples thereof include oxidized potassium sulfate, sodium carbonate, alkylammonium salt, and alkylarylammonium salt. The amount of addition is such that the number of additions to the above-mentioned ρ 适 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 支撑 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要, resin substrate, metal substrate. From the viewpoint of excellent reactivity with a phthalate compound to be described later, and excellent adhesion to an adhesive layer, and excellent in chemical resistance and heat resistance, 201238761 jyyy^tpif is preferably a glass substrate. The glass substrate is not particularly limited, and examples thereof include substrates such as glass, soda lime aluminum glass, and borosilicate glass. The length and width of the support used for one mm are suitable for the size of the object to be conveyed. In addition, there is no special system for the thickness of the support. However, from the viewpoint of suppressing damage during transportation, etc., it is mostly 〇3 mm to one' (procedure of procedure). There is no special method for cleaning the branch body with an aqueous solution. The coating method in which the alkaline aqueous solution is applied onto the surface of the support, the impregnation method in which the selected body is impregnated into the aqueous solution, and the like are exemplified. : The ship is escaping from water _ _ _ 暇 暇 胁 胁 胁 胁 胁 胁 体 体 体 体 体 体 适宜 适宜 适宜 胁 胁 胁 胁 胁 胁 胁 胁 胁 胁 胁 胁 胁 胁 适宜 适宜 适宜 适宜 适宜 适宜 适宜 适宜 适宜 适宜 适宜Minutes or so. Further, in the above cleaning, ultrasonic waves may be irradiated as needed. In addition, in the New Zealand cleaning step (4), it is necessary to further wash the surface of the building and dry it. <Surface modification step> The surface modification step is a step of contacting the compound with the support after the above alkali cleaning step. Chemically modified by = cow = acid brewing compound. More "words, borrow: support the layer of her compound. By the above-mentioned surface φ & chemical composition, the adhesion formed between them is further improved. s" support 8 201238761 39994pif First, 'the material used will be described in detail below'. The procedure of the step will be described in detail later. (The acid vinegar compound of the present invention) The phthalate compound of the present invention means a metal alkoxide formed of cerium (Si). (Alkoxydecane compound (especially, tetraalkoxydecane compound)) or an oligomer thereof. The so-called oligomer refers to a side chain having a fluorene alkane (-Si-O-Si-) skeleton on the main chain. A compound having an alkoxy group (RO) is introduced. Here, as the alkyl group of the alkoxy group (R〇), a methyl group, an ethyl group, a propyl group or the like can be exemplified. The phthalate compound has water and water. The characteristics of the reaction are carried out. Among them, the oligomer is preferably used from the viewpoint of further improving the adhesion of the adhesive layer and reducing the amount of the low molecular weight free radical. More specifically, the tannic acid brewing compound is preferably four. Polymer to hexadecane (tetramer or higher, hexadecimal or lower). This is because if the tetramer is not reached, the effect of the properties of the phthalate compound is small, and if it is larger than the hexadecane, the viscosity of the oxalate compound becomes high, so that it is difficult to manufacture. Further, the type of the phthalate compound used in the present invention may, for example, be decyl citrate or ethyl decanoate (tetraethyl phthalate (the ratio of "throosihcate" TE0S)). Propyl citrate or the like or oligomers thereof. From the viewpoint of stability and safety of the product, ethyl decanoate (TE〇s) or a polymer thereof is preferred. A preferred embodiment of the phthalic acid ester compound is an anthracite/chemical compound represented by a chemical formula (R = alkyl group, n = 4 to 16). When the above compound is used, the adhesion of the adhesive layer to the branch body is further improved. In particular, the effect of the present invention is more excellent in the case where the adhesive layer is a polywei resin layer (201238761.). The compound represented by the following formula (χ) is preferably used as the oxalate compound represented by Chemical Formula 1. /1R1 \ ?R1
Rl0"tr~0 j ?*一〇Ri 式（X) ^0R1 ORi 上述式中’ R!為碳數4以下的烷基，η為4〜16的整 數。 上述矽酸酯化合物可根據公知的方法而合成，亦可使 用市售品（例如，多摩化學工業製造）。 (步驟的程序） 使矽酸酯化合物與支撐體表面進行接觸的方法並無特 別限制，可列舉將矽酸酯化合物塗佈於支撐體表面上的塗 佈方法、將支撐體浸潰於矽酸酯化合物中的浸潰方法等。 .广 再者，作為塗佈方法的具體例，可列舉：棒塗法、旋塗法、 刀塗法、到刀法等。 再者，當矽酸酯化合物黏調或為固體形狀時，視需要 亦可將各種溶劑（例如，水、醇系溶劑、酮溶系媒等）添 加至石夕酸酯化合物中來調整黏度。 支撐體與矽酸酯化合物的接觸時間（處理時間）是對 應於所使用的矽酸酯化合物的種類等而適宜設定’但就生 201238761 ^yyy4pif =物的反應性等的觀點而言，較佳為〇5 勿在里以上，更佳為1分鐘〜1〇分鐘左右。 實二化合物舆編的接觸後 <黏者層形成步驟> 黏著層形成步驟是於上述表面修飾步驟 撑體的經化學修飾的表面上形絲著層的步^藉由實施 述 該步Ϊ先於對t上形成配置FPC等基板的黏著^。、 百先，對黏者層進行詳述，其後對步驟的程序進行詳 (黏著層） 置，從而可防止基板的翹曲或扭曲。表面上的基板的位 結果，不會產生黏著層的剝離 基板。 ㈣層與支撐體之間的密接力比黏著斧與配署 :i=i，,:fpc)之間的密接力更 ，可自點著層上容易地剥離 所形成的黏著層若為其表面可與 地密接的層’職無軸_，〶面可制離 觀點而言 樹脂層 聚石夕氧樹脂。gp ’黏著層較佳為 謂聚彻脂層，是指含有聚心::::成:者，所 ’較佳為 二:例C列舉胺基_旨樹脂、聚乙稀二 =的樹 f::其中，就耐化學品性及剝離性的觀」，矽氣 201238761 39994pif =層的厚度是對應於配置於其上的基板的種類等而 οοΓΓ ^ 0.01 mm〜10 mm，更佳為〇 03 mm〜5職。 (步驟的程序） 著乂 程序並無特別限制，可列舉將獏狀的黏 ^疋於支龍上的方法或者將包含構成轉層的成分 驅物的液狀組成物塗佈於切體上來形成點著層的 由繼化合物進行了表面處理的支撐體 物塗佈於支撐體上的方法。 取 ，者’於塗佈組成物後’為了溶劑的去除、前驅 硬化專’簡要進行加減理。加祕 3 而厂齡為於抓〜_下進行0.5小時〜12;^點 (黏著層形成步驟的較佳形態） 2黏著層形成步驟的較佳形態，可列舉將使用如下 料得㈣魏義層形成於支魏上的步驟， 機聚權的混合物進行水解反應及縮:i ==成物。若為物氧樹脂層，則與上述由石夕 曰物進仃了化學修飾的支撐體的密接性更優異。罝 料氧燒，就本剌的效果更優異的觀點^ 5較佳為使用聚二曱基矽氧烷。 再者’以下對有機聚石夕氧垸為聚二曱基石夕氧燒的情況 12 201238761 ：3yyy4pif 進行洋述。將聚二曱基石夕备ρ ^ 「Rl0"tr~0 j ?*一〇Ri Formula (X) ^0R1 ORi In the above formula, 'R! is an alkyl group having 4 or less carbon atoms, and η is an integer of 4 to 16. The above phthalate compound can be synthesized by a known method, and a commercially available product (for example, manufactured by Tama Chemical Industry Co., Ltd.) can also be used. (Procedure of the procedure) The method of bringing the phthalate compound into contact with the surface of the support is not particularly limited, and examples thereof include a coating method in which a phthalate compound is applied onto the surface of a support, and the support is immersed in citric acid. A method of impregnation in an ester compound, and the like. Further, specific examples of the coating method include a bar coating method, a spin coating method, a knife coating method, and a knife-to-knife method. Further, when the phthalate compound is viscous or has a solid shape, various solvents (for example, water, an alcohol solvent, a ketone solvent, etc.) may be added to the oxalate compound to adjust the viscosity. The contact time (treatment time) of the support with the phthalate compound is appropriately set in accordance with the type of the phthalate compound to be used, etc., but it is preferable to have a reactivity of 201238761 ^yyy4pif = substance, etc. For 〇5, do not in the above, more preferably 1 minute ~ 1 〇 minutes or so. After the contact of the bismuth compound & &&; 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘 粘Adhesion of a substrate such as an FPC is formed on t. The first layer of the adhesive layer is detailed, and then the procedure of the step is detailed (adhesive layer) to prevent warpage or distortion of the substrate. As a result of the position of the substrate on the surface, the peeling substrate of the adhesive layer is not generated. (4) The adhesion between the layer and the support is more than the adhesion between the adhesive axe and the distribution: i=i,,:fpc), and the adhesive layer formed by the easy peeling off from the layer can be The layer which can be closely connected with the ground has no shaft _, and the surface of the enamel can be made of a resin layer. The gp 'adhesive layer is preferably a poly-clear layer, which means that it contains a polycentric:::: into:, preferably 'two: C is an amine-based resin, a polyethylene II = a tree f :: Among them, the viewpoint of chemical resistance and peelability", helium 201238761 39994pif = the thickness of the layer corresponds to the type of the substrate disposed thereon, etc. οοΓΓ ^ 0.01 mm to 10 mm, more preferably 〇03 Mm~5 posts. (Procedure of Procedure) The procedure for the present invention is not particularly limited, and a method of applying a braided adhesive to a dragon or a liquid composition containing a component of a constituent layer of a transition layer may be applied to the cut body to form A method in which a support material surface-treated with a subsequent compound is applied to a support. The extraction is performed after the application of the composition, in order to remove the solvent and to cure the precursor. Adding the secret 3 and the factory age is 0.5 hours to 12 times under the grasping ~_; ^ point (the preferred form of the adhesive layer forming step) 2 The preferred form of the adhesive layer forming step, it can be enumerated that the following materials are used (4) Wei Yi The layer is formed on the branch, and the mixture of the polymer is subjected to hydrolysis reaction and shrinkage: i == adult. In the case of the oxygen-containing resin layer, the adhesion to the support chemically modified by the above-mentioned stone scorpion is more excellent. In view of the fact that the effect of the present invention is more excellent, it is preferred to use polydidecyloxyne. In addition, the following is the case where the organopolychlorinated oxime is polyfluorenyl oxynene. 201238761 : 3yyy4pif is carried out. Poly 曱 曱 夕 夕 ρ ^ ^
签7氣烷略記為「PDMS (PolydimethyisUoxane)」，將對末端進行了矽酸醋改質的 聚二甲基矽氧烷略記為「改質1>1)]^8。 矽酸酯化合物如上所述，其較佳範圍亦同義。 所謂改質PDMS是指利用石夕酸醋化合物對pDMS的末 端進行改質處理而成者，例如，使兩末端具有矽醇基的 PDMS、與PDMS的主鏈的一側或兩側具有作為可水解的 B能基的烷氧基的烷氧基矽燒部分縮合物進行反應而獲得 者。 該改質PDMS右與通常的PDMS相比，則具有特別高 的官能基濃度。另外’由於改質PDMS與矽酸酯化合物的 縮合反應性高，因此改質PDMS中所含有的烷氧基矽烷部 分縮合物可順利地進行縮合反應，從而硬化並聚合物化。 本發明中所使用的改質PDMS較佳為使用質量平均分 子量處於5000以上、100000以下的範圍内者。 作為改質PDMS的較佳形態，可列舉由[化學式 2]SinO(n.1)(RO)2(n+i)(OSi(CH3)2)m(R〇)2(n+l)Sin〇(n-l) ( R = 基，n = 4〜16，m>50)所表示的改質PDMS。當使用上 述改質PDMS時，黏著層的對於支撐體的密接性進一步提 昇。 改質PDMS可參照公知的合成方法（例如，日本專利 4255088號）等合成，亦可使用市售品。 另外，矽酸酯化合物（A)與改質PDMS (B)的調配 比例以A/B的莫耳比計，較佳為0.1以上、10以下的範圍。 13 201238761. 最佳的調配比例以A/B的莫耳比計為1左右。 當對黏著層要求柔軟性時，可増加改質PDMS，相反 地’當要求高硬度時，可增加矽酸酯化合物。 (組成物的生成） 使具有上述矽酸酯化合物與上述改質pDMs的混合物 進行水解及縮合反應’藉此製造組成物。 由於矽酸酯化合物於水的存在下容易地進行水解，因 此石夕酸S旨化合物的分子内·氡基成為反應性高的稍基 (-OH 基）。 “另一方面，由於改質PDMS亦同樣地進行水解，因此 藉由水的存在而成為矽醇基（亦稱為「矽烷醇改質」）。 上述兩者的石夕醇基具有高反應性，同時具有相㈣反 應性，因此藉由職有石夕酸醋化合物與改質pDMs的混成 物進行水解，石夕烧醇化合物的凝聚不會加速，與改質印廳 的縮合反應綱地進行。藉此，改f pDMS帽含有的低 分子的魏烧亦被導人至反應產物（組成物）中。 (黏著層的成形） 由於組成物為液狀（亦稱為「溶膠」），因此將該組成 物如上述般塗佈於支樓體上，視需要實施加熱處理，藉此 可於支碰上軸關望_著層。㈣方法、加熱條件 如tl所琉。 *另1作為其他方法，將組成物塗佈於模具等的托盤 燒處理使其硬化而成形為片狀(板狀)，然 後使成形為別狀的黏著層熟或接著於支獅的表面並 201238761The 7-gas alkane is abbreviated as "PDMS (Polydimethyis Uoxane)", and the polydimethylsiloxane which has been modified with citrate at the end is abbreviated as "Modification 1 > 1)]^8. The phthalate compound is as above. The preferred range is also synonymous. The so-called modified PDMS refers to the modification of the end of pDMS by using a sulphuric acid vinegar compound, for example, PDMS having a sterol group at both ends, and a main chain of PDMS. The one side or both sides are obtained by reacting an alkoxy oxime partial condensate which is a hydrolyzable B-group alkoxy group. The modified PDMS right is particularly high compared with the usual PDMS. Functional group concentration. In addition, since the modified PDMS has high condensation reactivity with the phthalate compound, the alkoxydecane partial condensate contained in the modified PDMS can be smoothly subjected to a condensation reaction to be hardened and polymerized. The modified PDMS used in the invention preferably has a mass average molecular weight of 5,000 or more and 100,000 or less. As a preferred embodiment of the modified PDMS, [Chemical Formula 2] SinO (n.1) (RO) ) 2(n+i)(OSi(CH3)2)m(R〇)2(n+l)Sin〇(n -l) (R = base, n = 4 to 16, m > 50) The modified PDMS is indicated. When the modified PDMS is used, the adhesion of the adhesive layer to the support is further improved. Commercially available products can also be synthesized by a known synthesis method (for example, Japanese Patent No. 4255088), etc. Further, the ratio of the phthalate compound (A) to the modified PDMS (B) is measured by the molar ratio of A/B. Preferably, it is in the range of 0.1 or more and 10 or less. 13 201238761. The optimum blending ratio is about 1 in terms of the molar ratio of A/B. When softness is required for the adhesive layer, the modified PDMS can be added, and conversely 'When high hardness is required, a phthalate compound can be added. (Formation of a composition) A mixture having the above phthalate compound and the above-mentioned modified pDMs is subjected to hydrolysis and condensation reaction to thereby produce a composition. Since the compound is easily hydrolyzed in the presence of water, the intramolecular thiol group of the compound of the oxalic acid S is a highly reactive (-OH group). "On the other hand, the modified PDMS is also carried out in the same manner. Hydrolyzed, thus becoming a sterol group by the presence of water (Also known as "stanol conversion"). The above-mentioned two-star alcohol group has high reactivity and phase (iv) reactivity, so the hydrolysis of the compound of the sulphuric acid is not accelerated by the hydrolysis of the mixture of the sulphuric acid vinegar compound and the modified pDMs. The condensation reaction with the modified printing hall is carried out. Thereby, the low-molecular Wei burn contained in the f pDMS cap is also introduced into the reaction product (composition). (Forming of Adhesive Layer) Since the composition is liquid (also referred to as "sol"), the composition is applied to the support body as described above, and if necessary, heat treatment is performed, whereby the composition can be supported. The axis is looking at the _ layer. (4) Method, heating conditions, such as tl. *Further, as another method, the composition is applied to a mold such as a mold and hardened to form a sheet (plate shape), and then the adhesive layer formed into a different shape is cooked or attached to the surface of the lion. 201238761
Dyyynytf 加以固定（保持）。 <基板搬送用载具> 如圖1所示 ln t藉由上述製造方法所獲得的基板搬送用 接二Λ二作為被搬送物的基板的下表面可剝離地密 接的黏者層12及固定_著層的支撐體14。 該基板搬送用载具 板貼合於黏著層12表面 送基板的載具。 10是將可撓性基板等片狀的薄基 ’並可向實施化學品處理的步驟搬 再者，基板並不限定於FPC等印刷配線基板，若為片 狀的基板，則並無特別限制。 [實例] 以下’藉由實例來具體地說明本發明，但本發明並不 受該些例所限定。 (組成物的製造） 本實例中所使用的黏著層使用如下的組成物而形成， 該組成物是藉由使具有矽酸酯化合物、及對末端進行了石夕 酸醋改質的聚二甲基矽氧烷的混合物進行水解反應及縮合 反應而獲得的组成物。以下，對該組成物的製造進行具體 說明。 向安裝有攪拌裝置、溫度計、滴液管的反應容器中， 加入矽酸乙酯（多摩化學工業股份有限公司製造，Silicate 45 (Sin〇(n l)(R〇)2(n+1) : η=8〜10)) 1·〇 g、及於兩末端對 矽酸乙酯進行烷氧基改質而成的聚二曱基矽氧烷（質量平 均分子量；相當於32,000)(荒川化學股份有限公司製造 201238761, 的HBSIL039) 32.0 g，然後於大氣中（室溫）攪拌混合約 30分鐘’獲得作為混成物的原料液A。 此處，矽酸乙酯及於兩末端對矽酸乙酯進行烷氧基改 質而成的聚二甲基矽氧烷中所使用的矽酸酯使用相同種類 及具有相同特性的矽酸酯。 然後，於水解步驟及縮合步驟中，歷時約1小時滴加 水0.93 g來加入至原料液a中，並進行攪拌混合。 其後，一面進行攪拌一面歷時約30分鐘自然冷卻至室 溫為止，從而獲得組成物。 (鹼清洗步驟） 將玻璃基板（松浪玻璃（Matsunami Glass)公司製造， 長度：100 mm，寬度：1〇〇 mm，厚度：0.7 mm)浸潰於 Semico Clean56 (Furuuchi化學股份有限公司製造：pH12) 中’進行5分鐘超音波清洗。清洗後，取出玻璃基板並進 行5分鐘流水清洗，其後於i20°C的烘箱中乾燥2分鐘。 (表面修飾步驟） 根據以下的（A)〜（C)的任一種程序，將矽酸酯化 合物塗佈於玻璃基板表面上。 (A) 藉由〇號棒來棒塗Silicate 45 (多摩化學工業股 份有限公司製造）。 (B) 藉由旋塗（1000 rpm)來塗佈四乙氧基石夕烧（東 京化成股份有限公司製造）。 (C) 藉由旋塗（1500 rpm)來塗佈Silicate 40 (多摩 化學工業股份有限公司製造，Sin〇(n i)(R〇)2(n+i) : n = 4〜 201238761. jyyy^yif 6)0 (黏著層形成步驟） 利用到刀塗佈法，以使煅燒乾燥後的膜厚成為ι〇〇 μιη 的方式將上述所製造的組成物塗佈於由石夕酸酯化合物進行 了化學修飾的玻璃基板上。其後，於烘箱中以2〇〇(>c實施工 小時的乾燥锻燒，而於玻璃基板上形成黏著層。 <實例1> 依序實施上述（表面修飾步驟）中所說明的（人）處 理、及上述（黏著層形成步驟），製造基板搬送用载具。再 者，於該實例中，不對玻璃基板進行鹼清洗，而實施上述 (A) 處理。 ' <實例2> 依序實施上述（表面修飾步驟）中所說明的（B)處 理及上述（黏著層形成步驟）’製造基板搬送用載且。再 者’於該實例中，不對玻璃基板進行鹼清洗，而實施上述Dyyynytf is fixed (held). <Substrate transfer carrier> As shown in Fig. 1, the substrate transfer port 2 obtained by the above-described manufacturing method is a sticky layer 12 which is detachably adhered to the lower surface of the substrate to be transported and The support layer 14 is fixed. The substrate transfer carrier plate is bonded to the carrier on which the substrate is transferred to the surface of the adhesive layer 12. 10 is a sheet-shaped thin base such as a flexible substrate, and can be transported to a chemical processing step. The substrate is not limited to a printed wiring board such as FPC, and is not particularly limited as a sheet-shaped substrate. . [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. (Manufacture of Composition) The adhesive layer used in the present example was formed by using a composition having a phthalate compound and a polydimethylene modified with oleic acid vinegar at the end. A composition obtained by subjecting a mixture of oxane to a hydrolysis reaction and a condensation reaction. Hereinafter, the production of the composition will be specifically described. To a reaction vessel equipped with a stirring device, a thermometer, and a drip tube, ethyl decanoate (manufactured by Tama Chemical Industry Co., Ltd., Silicate 45 (Sin〇(nl)(R〇)2(n+1) : η) was added. =8~10)) 1·〇g, and polydifluorenyl oxirane (mass average molecular weight; equivalent to 32,000) obtained by alkoxy modification of ethyl decanoate at both ends (Arakawa Chemical Co., Ltd.) The company manufactures 32.0 g of HBSIL039, 201238761, and then mixes it in the atmosphere (room temperature) for about 30 minutes to obtain a raw material liquid A as a mixture. Here, the phthalate ester used in the polydimethyl methoxy oxane in which the decanoic acid ethyl ester and the decanoic acid ethyl ester are modified at both ends are the same type and the phthalic acid ester having the same characteristics. . Then, in the hydrolysis step and the condensation step, 0.93 g of water was added dropwise over about 1 hour to be added to the raw material liquid a, and the mixture was stirred and mixed. Thereafter, while stirring, the composition was naturally cooled to room temperature for about 30 minutes to obtain a composition. (Alkali cleaning step) A glass substrate (manufactured by Matsunami Glass Co., Ltd., length: 100 mm, width: 1 mm, thickness: 0.7 mm) was immersed in Semico Clean56 (manufactured by Furuuchi Chemical Co., Ltd.: pH 12) In the '5 minute ultrasonic cleaning. After washing, the glass substrate was taken out and washed with running water for 5 minutes, and then dried in an oven at i20 ° C for 2 minutes. (Surface modification step) The phthalate compound is applied onto the surface of the glass substrate according to any one of the following procedures (A) to (C). (A) Apply Silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.) with a nickname stick. (B) Tetraethoxy zebra (manufactured by Tokyo Chemical Industry Co., Ltd.) was applied by spin coating (1000 rpm). (C) Coating Silicate 40 (Sin〇(ni)(R〇)2(n+i) by spin coating (1500 rpm): n = 4~ 201238761. jyyy^yif 6) 0 (adhesive layer forming step) The composition produced by applying the above-described composition to the chemical compound by the sulphuric acid ester compound by the knife coating method so that the film thickness after the baking and drying is ι〇〇μηη On a modified glass substrate. Thereafter, drying and calcination were carried out in an oven at 2 Torr (>c for an hour, and an adhesive layer was formed on the glass substrate. <Example 1> The above-described (surface modification step) was carried out in sequence ( In the above-described (adhesive layer forming step), a substrate transfer carrier is manufactured. Further, in this example, the glass substrate is subjected to alkali cleaning without performing the above-described (A) treatment. '<Example 2> The (B) process described in the above (surface modification step) and the above (adhesive layer formation step) are used to manufacture the substrate transfer carrier. Further, in this example, the glass substrate is not subjected to alkali cleaning, and the above is carried out.
(B) 處理。 ' ’L <實例3 > 依序實施上述（鹼清洗步驟）、上述（表面修飾步驟 中所說明的（A)處理、及上述（黏著層形成步驟），贺！ 基板搬送用載具。 <實例4> 依序實施上述（臉清洗步驟）、上述（表面修傅步 中所說明的（C)處理、及上述（黏著層形成步驟）,) 基板搬送用載具。 17 201238761 <比較例l> 貫施上述（黏著層形成步驟），製造基板搬送用載具。 於該比較例1中，不實施上述（鹼清洗步驟）及上述（表 面修飾步驟），而於玻璃基板上形成黏著層。 於上述實例1〜實例4、及比較例1中所製造的基板搬 送用載具的黏著層上貼付作為被黏著物的5〇 mnl><30 mm 的聚醢亞胺膜（Kapton 500H :東麗杜邦公司製造，厚度為 125 μηι)’然後於25°C下在鹼性顯影液（i〇%Cj>l :富士 電子材料（Fujifilm Electronic Materials)股份有限公司製 造）中浸潰2分鐘。 自顯影液中取出帶有聚醯亞胺膜的載具，加以乾燥 後’自載具上剝離^^酿亞胺膜。將自於上述驗性顯影液中 的浸潰至聚醯亞胺膜的剝離為止的處理重複1〇〇次後，以 目視確認黏著層的自玻璃基板的剝落，並根據以下的基準 進行評價。 「◎」：黏著層的與聚醯亞胺膜的被黏著面積之中，黏 著層的剝落面積為3%以下的情況 「〇」：黏著層的與聚醯亞胺膜的被黏著面積之中，黏 著層的剝落面積超過3%、且為5%以下的情況 「△」：黏著層的與聚醯亞胺膜的被黏著面積之中，黏 著層的剝落面積超過5%、且為10%以下的情況 「x」：黏著層的與聚醢亞胺膜的被黏著面積之中，黏 著層的剝落面積超過10%的情況 再者，較佳為實用上並非為「X」。 18 201238761 3yyy4pif 飾 將實例1〜實例4、及比較例1的實驗條件、及 果示於以下的表1中。再者，鹼清洗步驟欄、及表面 步驟欄中的「-」表示未實施。 ) 表1(B) Processing. 'L<Example 3> The above (alkaline washing step), the above (A) treatment described in the surface modification step, and the above (adhesive layer forming step) were carried out in that order, and the substrate transporting carrier was carried out. <Example 4> The above-described (face cleaning step), the above-described (C) treatment described in the surface finishing step, and the above (adhesive layer forming step) are carried out in sequence. 17 201238761 <Comparative Example l The above-mentioned (adhesive layer forming step) was carried out to produce a substrate transfer carrier. In the comparative example 1, the above (alkaline cleaning step) and the above (surface modification step) were not performed, and an adhesive layer was formed on the glass substrate. The adhesive layer of the substrate transfer carrier manufactured in the above-mentioned Examples 1 to 4 and Comparative Example 1 was attached with a 5 μm > 30 mm polyimine film as an adherend (Kapton 500H: It was manufactured by Toray DuPont, having a thickness of 125 μm) and then impregnated for 2 minutes at 25 ° C in an alkaline developer (i〇% Cj>l: manufactured by Fujifilm Electronic Materials Co., Ltd.). Self-developing The carrier with the polyimide film is taken out and dried, and then the imine film is peeled off from the carrier. The impregnation from the above-mentioned test developer to the peeling of the polyimide film After the treatment was repeated once, the peeling of the adhesive layer from the glass substrate was visually observed and evaluated according to the following criteria. "◎": Adhesive area of the adhesive layer and the polyimide film adhered. In the case where the peeling area of the layer is 3% or less, "〇" is the case where the peeling area of the adhesive layer exceeds 3% and is 5% or less among the adhered areas of the adhesive layer and the polyimide film: "△": Among the adhered areas of the adhesive layer and the polyimide film, the peeling area of the adhesive layer exceeds 5% and is 10% or less. "x": the adhered area of the adhesive layer and the polyimide film In the case where the peeling area of the adhesive layer exceeds 10%, it is preferably not practically "X". 18 201238761 3yyy4pif The experimental conditions and results of Examples 1 to 4 and Comparative Example 1 are shown below. In Table 1. Again, the alkali cleaning step column and the surface step column "-" means not implemented.) Table 1
如上述表1所示，藉由本發明的製造方法所獲得的基 板搬送用載具即便於多次的化學品處理之後，亦不產生^ 著層的剝落等，支撐體與黏著層之間保持優異的密接性。 根據實例1及實例2的比較而確認，若使用寡聚物作為石夕 酸酯化合物，則可獲得更優異的效果。另外，根據實例^ 及實例3的比較而確認’藉由實施驗清洗步驟，可獲得更 .優異的效果。 另一方面’於使用未實施上述表面修飾步驟的支撐體 的比較例1中’看到許多黏著層的剝落。若使用此種基板 搬送用載具，則黏著層殘留於作為被搬送物的FPC上，而 引起良率的下降等。 【圖式簡單說明】 圖1是本發明的基板用搬送用載具的立體圖。 【主要元件符號說明】 W:基板搬送用載具 201238761 39994pif 12 14 黏著層支撐體 20As shown in the above-mentioned Table 1, the substrate transfer carrier obtained by the production method of the present invention does not cause peeling of the layer or the like even after a plurality of chemical treatments, and the support body and the adhesive layer are excellent. The adhesion. From the comparison of Example 1 and Example 2, it was confirmed that when an oligomer was used as the ascorbate compound, more excellent effects were obtained. Further, it was confirmed from the comparison of the example and the example 3 that a more excellent effect can be obtained by performing the cleaning step. On the other hand, the peeling of many adhesive layers was observed in Comparative Example 1 using a support which was not subjected to the above surface modification step. When such a substrate transfer carrier is used, the adhesive layer remains on the FPC as the object to be conveyed, resulting in a decrease in yield or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view of a carrier for substrate transfer of the present invention. [Description of main component symbols] W: Carrier for substrate transfer 201238761 39994pif 12 14 Adhesive support 20