TWI614324B - Film, protective film mask and semiconductor component manufacturing method - Google Patents
Film, protective film mask and semiconductor component manufacturing method Download PDFInfo
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- TWI614324B TWI614324B TW104138833A TW104138833A TWI614324B TW I614324 B TWI614324 B TW I614324B TW 104138833 A TW104138833 A TW 104138833A TW 104138833 A TW104138833 A TW 104138833A TW I614324 B TWI614324 B TW I614324B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
- G03F1/64—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof characterised by the frames, e.g. structure or material, including bonding means therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Adhesive Tapes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明係關於一種於製造LSI(Large Scale Integration,大型積體電路)、超LSI等半導體元件或液晶顯示板等半導體裝置時,用以防止異物附著於光罩(mask)(光罩(photomask))之光微影用護膜。 The present invention relates to a method of preventing a foreign matter from adhering to a mask (photomask) when manufacturing a semiconductor device such as an LSI (Large Scale Integration) or a semiconductor device such as a super LSI or a liquid crystal display panel. ) The light lithography film.
於半導體製造之光微影步驟中,為於晶圓上形成與積體電路對應之光阻圖案,使用步進機(縮小投影曝光裝置)等半導體製造裝置。護膜係於具有框形狀之護膜框體之一端面張設透明薄膜而成,防止異物直接附著於光罩上而形成電路圖案之缺陷。具體而言,即便假設於光微影步驟中異物附著於護膜上,該等異物亦不會於塗佈有光阻劑之晶圓上成像。藉此,可防止因異物之像所引起之電路圖案之缺陷而導致半導體積體電路短路及斷線等,從而可提高光微影步驟之製造良率。 In the photolithography step of semiconductor manufacturing, a semiconductor manufacturing apparatus such as a stepper (reduced projection exposure apparatus) is used to form a photoresist pattern corresponding to an integrated circuit on a wafer. The protective film is formed by arranging a transparent film on one end surface of the frame having the frame shape to prevent the foreign matter from directly adhering to the reticle to form a circuit pattern. Specifically, even if foreign matter adheres to the protective film in the photolithography step, the foreign matter is not imaged on the wafer coated with the photoresist. Thereby, it is possible to prevent short-circuiting and disconnection of the semiconductor integrated circuit due to defects in the circuit pattern caused by the image of the foreign matter, and it is possible to improve the manufacturing yield of the photolithography step.
近年來,伴隨半導體裝置之高積體化,用於光微影步驟之曝光之光之短波長化不斷發展。即,要求於晶圓上描繪積體電路圖案時,可以更窄之線寬描繪微細之電路圖案的技術。為應對該情況,例如欲使用自先前之g線(波長436nm)、i線(波長365nm)進一步之KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)、進而F2準分子雷射(波長157nm)等波長更短之光作為光微影用步進機之曝光之光。 In recent years, with the high integration of semiconductor devices, the short wavelength of light for exposure in the photolithography step has been increasing. That is, when it is required to draw an integrated circuit pattern on a wafer, it is possible to draw a fine circuit pattern with a narrower line width. In order to cope with this situation, for example, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F 2 standard are used from the previous g line (wavelength 436 nm), i line (wavelength 365 nm). Light having a shorter wavelength such as a molecular laser (wavelength 157 nm) is used as a light for exposure of a stepper for photolithography.
伴隨近年來之曝光之光之短波長化、高能量化,隨曝光產生護膜膜體或光罩之污染之頻度變高,藉此,護膜及光罩之更換頻度亦變 高。此處,作為將護膜固定於光罩上之方法,通常使用以黏著劑可剝離地固定之方法。作為黏著劑,已知有丙烯酸系、橡膠系、聚丁烯系、聚胺基甲酸酯系、聚矽氧系等者(參照專利文獻1),又,已知有熱塑性彈性體系者(參照專利文獻2)。 With the short-wavelength and high energy of the exposure light in recent years, the frequency of contamination of the film or the mask by exposure increases, and the frequency of replacement of the film and the mask also changes. high. Here, as a method of fixing the film to the photomask, a method in which the adhesive is detachably fixed by an adhesive is generally used. Acrylic, rubber, polybutene, polyurethane, and polyoxygen are known as adhesives (see Patent Document 1), and thermoplastic elastomers are known (see Patent Document 2).
[專利文獻1]日本專利特開平05-281711號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 05-281711
[專利文獻2]國際公報第2012-004951號 [Patent Document 2] International Gazette No. 2012-004951
期望黏著劑穩定地具有適當之黏著力,並且於更換護膜時,防止自光罩剝離護膜時黏著劑發生內聚破壞而成為黏著劑之一部分附著於光罩之狀態的情況(以下,將該現象稱為糊劑殘留)。然而,伴隨近年來之曝光之光之短波長化、高能量化,專利文獻1中所記載之黏著劑容易因漏光所引起之黏著劑之分解而與光罩結合,於將護膜自光罩剝離時,於光罩表面上容易產生黏著劑之糊劑殘留。又,關於專利文獻2中所記載之黏著劑,丙烯酸系黏著劑亦於防止糊劑殘留之方面存在問題。尤其於使用200nm以下之短波長之情形時,產生被稱為霧靄之光罩之污染。因此,護膜之更換頻度變高,故而要求於自光罩進行剝離時,黏著劑不會殘留於光罩上。 It is desirable that the adhesive stably has an appropriate adhesive force, and when the protective film is replaced, the cohesive agent is prevented from being cohesively broken when the protective film is peeled off from the photomask, and the adhesive is partially attached to the photomask (hereinafter, This phenomenon is called paste residue). However, with the short-wavelength and high energy of the exposure light in recent years, the adhesive described in Patent Document 1 is easily combined with the photomask due to the decomposition of the adhesive due to light leakage, and the protective film is attached to the mask. When peeling off, the paste residue of the adhesive is liable to occur on the surface of the mask. Further, in the adhesive described in Patent Document 2, the acrylic pressure-sensitive adhesive also has a problem in preventing the residue from remaining in the paste. Especially when a short wavelength of 200 nm or less is used, contamination of a photomask called a haze is generated. Therefore, the frequency of replacement of the protective film becomes high, and therefore it is required that the adhesive does not remain on the photomask when peeling off from the photomask.
本發明係鑒於上述問題,目的在於提供一種可充分防止自光罩剝離護膜時之糊劑殘留的護膜、附護膜之光罩及半導體元件之製造方法。 The present invention has been made in view of the above problems, and it is an object of the invention to provide a protective film, a mask for an adhesive film, and a method for producing a semiconductor element, which can sufficiently prevent the paste from remaining when the protective film is peeled off from the mask.
本發明提供以下(1)~(11)。 The present invention provides the following (1) to (11).
(1)一種護膜,其包含:護膜框體; 護膜膜體,其張設於護膜框體之一端面;及非交聯型之丙烯酸系黏著劑,其附著於護膜框體之另一端面;且黏著劑中之重量平均分子量800以下之化合物之含量為18質量%以下。 (1) A protective film comprising: a protective film frame; a film film body which is stretched on one end surface of the film frame; and a non-crosslinking type acrylic adhesive adhered to the other end surface of the film frame; and the weight average molecular weight of the adhesive is 800 or less The content of the compound is 18% by mass or less.
(2)如(1)之護膜,其中非交聯型之丙烯酸系黏著劑之彈性模數為20mN/mm2以上且180mN/mm2以下。 (2) The protective film of (1), wherein the non-crosslinked acrylic adhesive has an elastic modulus of 20 mN/mm 2 or more and 180 mN/mm 2 or less.
(3)如(1)或(2)之護膜,其中非交聯型之丙烯酸系黏著劑之玻璃轉移溫度未達-25℃。 (3) The film of (1) or (2), wherein the glass transition temperature of the non-crosslinked acrylic adhesive is less than -25 °C.
(4)如(1)至(3)中任一項之護膜,其中非交聯型之丙烯酸系黏著劑含有丙烯酸系聚合物(A)、及丙烯酸系基礎聚合物(B)。 (4) The protective film of any one of (1) to (3), wherein the non-crosslinking type acrylic adhesive contains an acrylic polymer (A) and an acrylic base polymer (B).
(5)如(4)之護膜,其中丙烯酸系聚合物(A)之玻璃轉移溫度為-30℃以下,丙烯酸系基礎聚合物(B)之玻璃轉移溫度為-25℃以上。 (5) The film of (4), wherein the glass transition temperature of the acrylic polymer (A) is -30 ° C or lower, and the glass transition temperature of the acrylic base polymer (B) is -25 ° C or higher.
(6)如(4)或(5)之護膜,其中非交聯型之丙烯酸系黏著劑中之丙烯酸系聚合物(A)之含量為15~80質量%。 (6) The film of (4) or (5), wherein the content of the acrylic polymer (A) in the non-crosslinked acrylic adhesive is 15 to 80% by mass.
(7)如(4)至(6)中任一項之護膜,其中丙烯酸系聚合物(A)為具有碳數1~14之烷基之(甲基)丙烯酸烷基酯之聚合物或共聚物。 (7) The film according to any one of (4) to (6), wherein the acrylic polymer (A) is a polymer of an alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms or Copolymer.
(8)如(4)至(7)中任一項之護膜,其中丙烯酸系基礎聚合物(B)為嵌段聚合物。 (8) The film according to any one of (4) to (7) wherein the acrylic base polymer (B) is a block polymer.
(9)如(8)之護膜,其中嵌段聚合物於聚合物主鏈中具有下述通式(I)所表示之結構,式(I)中,(a1)及(a2)分別表示玻璃轉移溫度80℃以上之聚合物,(b)表示玻璃轉移溫度30℃以下之聚合物,-(a1)-(b)-(a2)- (I)。 (9) The film of (8), wherein the block polymer has a structure represented by the following formula (I) in the polymer main chain, and in the formula (I), (a1) and (a2) respectively represent (a) a polymer having a glass transition temperature of 80 ° C or higher, and (b) a polymer having a glass transition temperature of 30 ° C or lower, -(a1)-(b)-(a2)-(I).
(10)如(9)之護膜,其中通式(I)中之(a1)及(a2)分別主要包含碳數1 ~14之甲基丙烯酸烷基酯,通式(I)中之(b)主要包含碳數1~14之(甲基)丙烯酸烷基酯。 (10) The film of (9), wherein (a1) and (a2) in the formula (I) mainly contain carbon number 1 The alkyl methacrylate of ~14, (b) in the formula (I) mainly contains an alkyl (meth) acrylate having a carbon number of 1 to 14.
(11)如(4)至(10)中任一項之護膜,其中丙烯酸系聚合物(A)之重量平均分子量為850以上且70000以下,丙烯酸系基礎聚合物(B)之重量平均分子量為10000以上且500000以下。 (11) The film of any one of (4) to (10), wherein the weight average molecular weight of the acrylic polymer (A) is 850 or more and 70,000 or less, and the weight average molecular weight of the acrylic base polymer (B) It is 10,000 or more and 500,000 or less.
(12)一種附護膜之光罩,其安裝有如(1)至(11)中任一項之護膜。 (12) A mask for an attachment film, which is provided with a protective film according to any one of (1) to (11).
(13)一種半導體元件之製造方法,其包括如下步驟:利用如(12)之附護膜之光罩而對基板進行曝光。 (13) A method of manufacturing a semiconductor device, comprising the steps of: exposing a substrate by using a photomask of the protective film of (12).
根據本發明,可充分防止自光罩剝離護膜時之糊劑殘留。 According to the present invention, the residue of the paste when the film is peeled off from the photomask can be sufficiently prevented.
1‧‧‧護膜 1‧‧‧ film
2‧‧‧護膜框體 2‧‧‧Shield casing
2e、2f‧‧‧護膜框體之端面 2e, 2f‧‧‧ end face of the casing
3‧‧‧護膜膜體 3‧‧‧Shield film body
10‧‧‧黏著劑 10‧‧‧Adhesive
20‧‧‧光罩 20‧‧‧Photomask
20p‧‧‧圖案 20p‧‧‧ pattern
20f‧‧‧端面 20f‧‧‧ end face
30‧‧‧附護膜之光罩 30‧‧‧Photomask with protective film
40‧‧‧曝光之光 40‧‧‧Exposure light
50‧‧‧光學系統 50‧‧‧Optical system
60‧‧‧基板 60‧‧‧Substrate
62‧‧‧光阻劑 62‧‧‧ photoresist
F‧‧‧保護膜 F‧‧‧Protective film
圖1係表示本發明之一實施形態之護膜之立體圖。 Fig. 1 is a perspective view showing a protective film according to an embodiment of the present invention.
圖2係圖1中之II-II線剖面圖。 Figure 2 is a cross-sectional view taken along line II-II of Figure 1.
圖3係模式性地表示利用本發明之一實施形態之附護膜之光罩而對基板進行曝光之步驟的圖。 Fig. 3 is a view schematically showing a step of exposing a substrate by using a mask of an envelope film according to an embodiment of the present invention.
以下,對用以實施本發明之形態(以下,簡稱為「本實施形態」)詳細地進行說明。以下之本實施形態係用以說明本發明之例示,並非將本發明限定於以下內容之含義。本發明可於其主旨之範圍內適當變化而實施。 Hereinafter, the form for carrying out the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail. The following examples are intended to illustrate the invention and are not intended to limit the invention to the following. The present invention can be carried out with appropriate changes within the scope of the gist of the invention.
圖1係表示本實施形態之護膜之立體圖,圖2係圖1中之II-II線剖面圖。如圖1及圖2所示,護膜1包含:護膜框體2;護膜膜體3,其張設於護膜框體2之一端面2e;黏著劑10,其附著於護膜框體2之另一端面2f;及保護膜F,其黏著於黏著劑10,保護該黏著劑10。圖3係模式性地表示利用本實施形態之附護膜之光罩而對基板進行曝光之步驟的 圖。如圖3所示,本實施形態之附護膜之光罩30包含護膜1與光罩20。護膜1之另一端面2f經由黏著劑10而安裝於光罩20之形成有圖案20P之側之端面20f。為對基板60進行曝光,自附護膜之光罩30之上方對該附護膜之光罩30照射曝光之光40。曝光之光40經過附護膜之光罩30後,藉由例如投光光學系統50聚光,並照射至表面設置有光阻劑62之基板60。其後,藉由經過顯影步驟、蝕刻步驟等特定之步驟,而將光罩20之圖案20P轉印於基板60之表面。基板60例如包含半導體材料。使用如上所述之附護膜之光罩30而將光罩20之圖案20P轉印至基板60之表面的步驟例如為半導體元件之製造步驟之一部分。 Fig. 1 is a perspective view showing a protective film of the embodiment, and Fig. 2 is a cross-sectional view taken along line II-II of Fig. 1. As shown in FIG. 1 and FIG. 2, the protective film 1 includes: a protective film frame 2; a protective film body 3 which is stretched over one end surface 2e of the protective film frame 2; and an adhesive 10 attached to the protective film frame The other end face 2f of the body 2; and the protective film F adhere to the adhesive 10 to protect the adhesive 10. 3 is a view schematically showing a step of exposing a substrate by using a mask of the protective film of the embodiment; Figure. As shown in FIG. 3, the mask 30 of the protective film of this embodiment includes the film 1 and the mask 20. The other end surface 2f of the film 1 is attached to the end surface 20f of the mask 20 on the side where the pattern 20P is formed via the adhesive 10. In order to expose the substrate 60, the mask 30 of the protective film is irradiated with the exposed light 40 from above the mask 30 of the protective film. The exposed light 40 passes through the photomask 30 of the protective film, is condensed by, for example, the light projecting optical system 50, and is irradiated onto the substrate 60 on the surface of which the photoresist 62 is provided. Thereafter, the pattern 20P of the photomask 20 is transferred onto the surface of the substrate 60 by a specific step such as a development step or an etching step. Substrate 60 includes, for example, a semiconductor material. The step of transferring the pattern 20P of the reticle 20 to the surface of the substrate 60 using the reticle 30 of the protective film as described above is, for example, part of the manufacturing steps of the semiconductor element.
用於本實施形態之護膜之黏著劑(丙烯酸系黏著劑)為非交聯型之丙烯酸系黏著材料,且丙烯酸系黏著劑中之重量平均分子量800以下之化合物之含有比率為18質量%以下。此處所謂之非交聯型亦包括如下情形:於發揮本發明之效果之範圍內包含與硬化材料之反應產物。 The adhesive (acrylic adhesive) used for the film of the present embodiment is a non-crosslinking type acrylic adhesive, and the content ratio of the compound having a weight average molecular weight of 800 or less in the acrylic adhesive is 18% by mass or less. . The non-crosslinking type referred to herein also includes a case where a reaction product with a hardening material is contained within a range in which the effects of the present invention are exerted.
又,本實施形態之丙烯酸系黏著劑之玻璃轉移溫度較佳為未達-25℃,更佳為-27℃以下,進而較佳為-30℃以下。於本實施形態之丙烯酸系黏著劑具有複數之玻璃轉移溫度之情形時,只要該複數之玻璃轉移溫度中之至少一者存在於該範圍內即可。若玻璃轉移溫度處於上述範圍內,則成為彈性模數較低且柔軟之黏著劑,因此可更有效地發揮減少下述光罩形變之效果。再者,本實施形態之丙烯酸系黏著劑之玻璃轉移溫度之下限並無特別限制,但就操作之容易性或光罩黏著劑之成型性之觀點而言,較佳為-90℃以上。 Further, the glass transition temperature of the acrylic pressure-sensitive adhesive of the present embodiment is preferably less than -25 ° C, more preferably -27 ° C or less, still more preferably -30 ° C or less. In the case where the acrylic pressure-sensitive adhesive of the present embodiment has a plurality of glass transition temperatures, at least one of the plurality of glass transition temperatures may be present in the range. When the glass transition temperature is within the above range, the adhesive having a low modulus of elasticity and being soft is used, so that the effect of reducing the deformation of the mask described below can be more effectively exhibited. In addition, the lower limit of the glass transition temperature of the acrylic pressure-sensitive adhesive of the present embodiment is not particularly limited, but is preferably -90 ° C or more from the viewpoint of ease of handling or moldability of the mask adhesive.
又,本實施形態之丙烯酸系黏著劑之彈性模數較佳為20mN/mm2以上且180mN/mm2以下。若彈性模數處於上述範圍內,則可一面維持柔軟度一面抑制護膜自光罩之偏移,並且可緩和對光罩施加之貼附荷重,因此可減少自護膜對光罩施加之形變。本實施形態之丙烯酸系 黏著劑之彈性模數更佳為30mN/mm2以上且160mN/mm2以下,進而較佳為40mN/mm2以上且140mN/mm2以下。黏著劑之彈性模數可考慮黏著劑中使用之原料聚合物之彈性模數、及於使用複數種原料聚合物之情形時該等之相溶性而調整。 Moreover, the elastic modulus of the acrylic pressure-sensitive adhesive of the present embodiment is preferably 20 mN/mm 2 or more and 180 mN/mm 2 or less. When the modulus of elasticity is within the above range, the film can be prevented from shifting from the mask while maintaining the softness, and the adhesion applied to the mask can be alleviated, thereby reducing the deformation of the mask applied to the mask. . Elastic modulus aspect of this embodiment of the acrylic adhesive agent is more preferably 30mN / mm 2 or more and 160mN / mm 2 or less, and preferably 40mN / mm 2 or more and 140mN / mm 2 or less. The modulus of elasticity of the adhesive can be adjusted in consideration of the modulus of elasticity of the base polymer used in the adhesive and the compatibility in the case of using a plurality of base polymers.
又,就賦予良好之彈性接著性之觀點而言,用於本實施形態之護膜之丙烯酸系黏著劑較佳為包含丙烯酸系聚合物(A)、與丙烯酸系基礎聚合物(B)。此處,上述化合物等之重量平均分子量係藉由GPC(Gel Permeation Chromatograph,凝膠滲透層析儀)測定所得之值。 Further, the acrylic adhesive used in the protective film of the present embodiment preferably contains an acrylic polymer (A) and an acrylic base polymer (B) from the viewpoint of imparting excellent elastic adhesion. Here, the weight average molecular weight of the above compound or the like is a value measured by GPC (Gel Permeation Chromatograph).
重量平均分子量800以下之化合物係用作黏著賦予劑,其用以使非交聯型之丙烯酸系黏著劑顯現黏著性、或提高黏著、接著性能。黏著賦予劑不僅要求與成為黏著劑之基礎之聚合物(基礎聚合物)之相溶性良好,亦要求對黏著劑賦予優異之黏性流動特性即於黏著劑之變形或形變速度下立刻結合之性質,從而重要的是分子量大幅低於基礎聚合物。因此,通常使用重量平均分子量800以下之低分子量化合物作為黏著賦予劑。 A compound having a weight average molecular weight of 800 or less is used as an adhesion-imparting agent for exhibiting adhesion of a non-crosslinked acrylic adhesive or improving adhesion and adhesion properties. The adhesion-imparting agent not only requires good compatibility with the polymer (base polymer) which is the basis of the adhesive, but also imparts excellent viscous flow characteristics to the adhesive, that is, the immediate bonding property at the deformation or deformation speed of the adhesive. It is therefore important that the molecular weight is substantially lower than the base polymer. Therefore, a low molecular weight compound having a weight average molecular weight of 800 or less is usually used as an adhesion-imparting agent.
如上所述,黏著劑中之重量平均分子量800以下之化合物之含有比率為18質量%以下。藉由使重量平均分子量800以下之化合物之含有比率為上述範圍內,而適當防止上述化合物滲出至黏著劑之表面。 藉此,可抑制黏著劑之內聚破壞,減少糊劑殘留。上述化合物之含有比率越少越佳,更佳為15質量%以下、10質量%以下、7質量%以下、或3質量%以下。上述化合物亦可不含有於黏著劑中,於上述化合物含有於黏著劑中之情形時之上述化合物之含有比率可為0.5質量%以上、或1質量%以上。 As described above, the content ratio of the compound having a weight average molecular weight of 800 or less in the adhesive is 18% by mass or less. When the content ratio of the compound having a weight average molecular weight of 800 or less is within the above range, the above compound is appropriately prevented from oozing out to the surface of the adhesive. Thereby, cohesive failure of the adhesive can be suppressed, and the residue of the paste can be reduced. The content ratio of the above compound is preferably as small as possible, and more preferably 15% by mass or less, 10% by mass or less, 7% by mass or less, or 3% by mass or less. The compound may not be contained in the adhesive, and when the compound is contained in the adhesive, the content of the compound may be 0.5% by mass or more or 1% by mass or more.
再者,先前之丙烯酸系黏著劑大致分為交聯型與非交聯型之黏 著劑。通常,於非交聯型之丙烯酸系黏著劑之情形時,含有基礎聚合物與黏著賦予劑。作為黏著賦予劑係包含松香系樹脂、萜烯系樹脂或石油系樹脂等、分子量為數百~數千且無定形之化合物。認為最多地應用於丙烯酸系黏著劑之黏著賦予劑為松香系樹脂。松香系樹脂具有立體且龐大之環狀結構,因此與顯示相同之軟化點之其他石油系樹脂相比,成為低分子量且較窄之分子量分佈。又,松香系樹脂具有酯鍵等極性基,而與基礎聚合物之相溶性優異,因此最多地作為丙烯酸系黏著劑之黏著賦予劑而應用。然而,松香系樹脂由於包含代用松香酸之具有不飽和鍵之結構,故而容易氧化,耐光性等較差。因此,開發將經氫化、聚合化之改性松香進行酯化而成之樹脂,或藉由超淺色化技術而開發光學用途等亦優異之松香衍生物。 Furthermore, the previous acrylic adhesives are roughly classified into crosslinked and non-crosslinked adhesives. Attention. Usually, in the case of a non-crosslinked acrylic adhesive, a base polymer and an adhesion-imparting agent are contained. The adhesive agent is a compound containing a rosin-based resin, a terpene-based resin, a petroleum-based resin, or the like, and having a molecular weight of several hundreds to several thousands and being amorphous. The adhesion-imparting agent which is most widely used for an acrylic adhesive is a rosin-based resin. Since the rosin-based resin has a three-dimensional and bulky ring structure, it has a low molecular weight and a narrow molecular weight distribution as compared with other petroleum-based resins exhibiting the same softening point. Further, since the rosin-based resin has a polar group such as an ester bond and is excellent in compatibility with a base polymer, it is applied at most as an adhesion-imparting agent for an acrylic pressure-sensitive adhesive. However, since the rosin-based resin contains a structure having an unsaturated bond of a substitute rosin acid, it is easily oxidized, and the light resistance and the like are inferior. Therefore, a resin obtained by esterifying a hydrogenated or polymerized modified rosin or a rosin derivative excellent in optical use such as an ultra-light coloring technique has been developed.
關於先前之丙烯酸系黏著劑,為使基礎聚合物與黏著賦予劑相溶以顯現黏著性與橡膠彈性,而於基礎聚合物中以20質量%以上且80質量%以下之量調配黏著賦予劑。其原因在於,通常於黏著賦予劑未達20質量%時,黏著性之提高可謂之為不足。然而,若將黏著賦予劑設為上述含有比率,則黏著賦予劑與基礎聚合物之間會產生分離等。 因此,黏著賦予劑滲出至表面,黏著賦予劑移動至光罩側而殘留於光罩側。認為其成為使用先前之丙烯酸系黏著劑時產生糊劑殘留之原因之一。 In the conventional acrylic pressure-sensitive adhesive, the adhesion-imparting agent is prepared in an amount of 20% by mass or more and 80% by mass or less in the base polymer in order to make the base polymer and the adhesion-imparting agent compatible to exhibit adhesiveness and rubber elasticity. The reason for this is that the adhesion is generally insufficient when the adhesion-imparting agent is less than 20% by mass. However, when the adhesion-imparting agent is set to the above-described content ratio, separation or the like occurs between the adhesion-imparting agent and the base polymer. Therefore, the adhesion-imparting agent oozes to the surface, and the adhesion-imparting agent moves to the side of the mask to remain on the side of the mask. It is considered to be one of the causes of the occurrence of paste residue when the prior acrylic adhesive is used.
丙烯酸系聚合物(A)之玻璃轉移溫度為-30℃以下,較佳為-33℃以下,更佳為-35℃以下。藉由將丙烯酸系聚合物(A)之玻璃轉移溫度設為-30℃以下,即便於環境溫度較低之情形時亦具有良好之彈性接著性,作業性亦變得良好。下限並無特別限制,但就操作之容易性、獲取之容易性之方面而言,較佳為玻璃轉移溫度為-90℃以上。又,於丙烯酸系聚合物(A)具有複數之玻璃轉移溫度之情形時,只要該複 數之玻璃轉移溫度中之至少一者處於上述範圍內即可,較佳為上述複數之玻璃轉移溫度全部處於上述範圍內。再者,用於本實施形態之化合物等之玻璃轉移溫度係藉由DSC(Differential Scanning Calorimetry,示差掃描熱量測定)所得之值。 The glass transition temperature of the acrylic polymer (A) is -30 ° C or lower, preferably -33 ° C or lower, more preferably -35 ° C or lower. By setting the glass transition temperature of the acrylic polymer (A) to -30 ° C or lower, it has good elastic adhesion even when the ambient temperature is low, and the workability is also good. The lower limit is not particularly limited, but the glass transition temperature is preferably -90 ° C or higher in terms of ease of handling and ease of acquisition. Further, when the acrylic polymer (A) has a plurality of glass transition temperatures, as long as the complex It is sufficient that at least one of the plurality of glass transition temperatures is within the above range, and it is preferred that all of the plurality of glass transition temperatures are within the above range. Further, the glass transition temperature used for the compound or the like of the present embodiment is a value obtained by DSC (Differential Scanning Calorimetry).
於玻璃轉移溫度為上述範圍之情形時,丙烯酸系聚合物(A)於常溫下成為液體,故而容易操作。又,藉由使用丙烯酸系聚合物(A),即便不將松香系樹脂等先前之黏著賦予劑調配於丙烯酸系黏著劑中,亦可顯現可作為護膜之黏著劑使用之黏著力。認為其原因在於,藉由使用丙烯酸系聚合物(A),而與丙烯酸系基礎聚合物(B)中所含之具有接著性及柔軟性之單體成分的相溶性變得良好。又,丙烯酸系聚合物(A)由於與丙烯酸系基礎聚合物(B)之相溶性良好,故而不易相分離且耐光性良好等,因此如先前之黏著賦予劑般滲出至表面之比率變小,黏著劑之糊劑殘留得到抑制。 When the glass transition temperature is in the above range, the acrylic polymer (A) becomes a liquid at normal temperature, so that it is easy to handle. In addition, by using the acrylic polymer (A), it is possible to exhibit an adhesive force which can be used as an adhesive for a protective film, without disposing a conventional adhesive agent such as a rosin-based resin in an acrylic adhesive. The reason for this is that the compatibility with the monomer component having the adhesiveness and flexibility contained in the acrylic base polymer (B) is improved by using the acrylic polymer (A). Further, since the acrylic polymer (A) has good compatibility with the acrylic base polymer (B), it is not easily phase-separated and has good light resistance. Therefore, the ratio of exudation to the surface as in the conventional adhesion-imparting agent becomes small. The paste residue of the adhesive is suppressed.
又,伴隨最近之曝光之光之短波長化、高能量化,圖案之微細化不斷發展。作為微細化之方法,已知有雙重圖案化,通常使用2片光罩曝光2次。因此,提高所形成之2個圖案彼此之位置精度變得重要。即,若藉由第1次曝光所獲得之圖案與藉由第2次曝光所獲得之圖案之位置精度較低,則無法獲得所期望之圖案。因此,必須減小所形成之2個圖案之位置偏移,故而對光罩要求之平坦性為必需。此時,若於光罩貼附護膜,則有產生光罩形變之情況。 In addition, with the short-wavelength and high energy of the recent exposure light, the miniaturization of the pattern has been progressing. As a method of miniaturization, double patterning is known, and it is usually exposed twice using two masks. Therefore, it is important to improve the positional accuracy of the two patterns formed. That is, if the positional accuracy of the pattern obtained by the first exposure and the pattern obtained by the second exposure is low, the desired pattern cannot be obtained. Therefore, it is necessary to reduce the positional deviation of the two patterns formed, so that the flatness required for the mask is necessary. At this time, if the protective film is attached to the photomask, the mask may be deformed.
作為產生該光罩形變之原因之一,認為於將護膜經由黏著劑而壓接於光罩時,護膜框體之形變會通過黏著劑而傳遞。因此,為不使護膜框體之形變傳遞至光罩,考慮藉由使黏著劑柔軟以變形,而緩和護膜框體之形變能量,結果為減少光罩形變。若丙烯酸系聚合物(A)之玻璃轉移點為上述範圍內,則與丙烯酸系基礎聚合物(B)之相溶性良好,故而可發揮柔軟性。藉此,可減少上述光罩形變。 As one of the causes of the deformation of the mask, it is considered that when the film is pressure-bonded to the mask via the adhesive, the deformation of the film frame is transmitted by the adhesive. Therefore, in order to prevent the deformation of the film casing from being transmitted to the reticle, it is considered that the deformation energy of the film casing is moderated by softening the adhesive, and as a result, the reticle deformation is reduced. When the glass transition point of the acrylic polymer (A) is within the above range, the compatibility with the acrylic base polymer (B) is good, and flexibility can be exhibited. Thereby, the above-described mask deformation can be reduced.
上述丙烯酸系聚合物(A)之含量較佳為相對於黏著劑整體為15~80質量%。更佳為18~75質量%,進而較佳為20~70質量%,尤佳為30~70質量%,尤其更佳為40~70質量%。藉由使該含量為15質量%以上,可獲得適當之接著力,藉由為80質量%以下,可使凝集力為適當之範圍,從而保持力提高。藉由將丙烯酸系聚合物(A)之含量設為上述範圍,可防止於將護膜貼附於光罩後護膜自光罩掉落。 The content of the acrylic polymer (A) is preferably from 15 to 80% by mass based on the total amount of the adhesive. More preferably, it is 18 to 75 mass%, further preferably 20 to 70 mass%, particularly preferably 30 to 70 mass%, and more preferably 40 to 70 mass%. When the content is 15% by mass or more, an appropriate adhesive force can be obtained, and when the content is 80% by mass or less, the cohesive force can be set to an appropriate range, and the holding power can be improved. By setting the content of the acrylic polymer (A) to the above range, it is possible to prevent the protective film from being dropped from the mask after the film is attached to the mask.
就亦可兼具作為軟化劑之功能之觀點而言,丙烯酸系聚合物(A)較佳為包含具有碳數為1~14之烷基之(甲基)丙烯酸烷基酯系聚合物或共聚物。該等聚合物或共聚物亦包含二嵌段、三嵌段等,可使1種或2種以上之(甲基)丙烯酸烷基酯系單體聚合、或使1種或2種以上之(甲基)丙烯酸烷基酯系單體與(甲基)丙烯酸烷基酯系單體以外之其他單體之混合物聚合而獲得。又,亦可根據功能性,使用該等聚合物或共聚物中之1種或2種以上而獲得丙烯酸系聚合物(A)。再者,所謂本說明書中之「(甲基)丙烯酸」係指「丙烯酸」及與其對應之「甲基丙烯酸」。 The acrylic polymer (A) is preferably an alkyl (meth) acrylate polymer or copolymer having an alkyl group having 1 to 14 carbon atoms, from the viewpoint of functioning as a softening agent. Things. The polymer or copolymer may also contain a diblock or a triblock, and one or two or more kinds of alkyl (meth)acrylate monomers may be polymerized or one or more of them ( It is obtained by polymerizing a mixture of a methyl methacrylate monomer and a monomer other than the alkyl (meth) acrylate monomer. In addition, one or two or more of these polymers or copolymers may be used depending on the functionality to obtain the acrylic polymer (A). In addition, "(meth)acrylic" in this specification means "acrylic acid" and the corresponding "methacrylic acid".
作為(甲基)丙烯酸烷基酯系單體之具體例,可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸縮水甘油酯、丙烯酸甲氧基乙酯等直鏈脂肪族醇之(甲基)丙烯酸酯、或具有支鏈狀之烷基鏈之(甲基)丙烯酸酯等。又,作為上述其他單體,可使用能與(甲基)丙烯酸烷基酯系單體共聚合之單體,例如丙烯酸、乙酸乙烯酯、苯乙烯等。 Specific examples of the (meth)acrylic acid alkyl ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. , hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylate, (methyl) Isooctyl acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methoxy acrylate A (meth) acrylate of a linear aliphatic alcohol such as a ethyl ester or a (meth) acrylate having a branched alkyl chain. Further, as the other monomer, a monomer copolymerizable with an alkyl (meth)acrylate monomer, for example, acrylic acid, vinyl acetate, styrene or the like can be used.
其中,包含(甲基)丙烯酸丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基) 丙烯酸2-甲氧基乙酯、(甲基)丙烯酸異丁酯等具有碳數1~8之烷基之(甲基)丙烯酸烷基酯等的聚合物或共聚物易於具有與丙烯酸系基礎聚合物(B)之可顯現接著性之單體成分之相溶性,故而較佳。又,上述聚合物或共聚物亦可兼具作為軟化劑之功能。 Among them, butyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) A polymer or copolymer of an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms such as 2-methoxyethyl acrylate or isobutyl (meth)acrylate is apt to have an acrylic base polymerization. The substance (B) is preferred because it exhibits the compatibility of the monomer component of the adhesiveness. Further, the above polymer or copolymer may also function as a softening agent.
丙烯酸系聚合物(A)之分子量以重量平均分子量計較佳為850以上且70,000以下,更佳為900以上且68,000以下。藉由使丙烯酸系聚合物(A)之重量平均分子量為850以上,可獲得充分之接著強度,藉由為70,000以下,可將黏度控制為適當之範圍,就使作業性良好之觀點而言較佳。 The molecular weight of the acrylic polymer (A) is preferably 850 or more and 70,000 or less, more preferably 900 or more and 68,000 or less, by weight average molecular weight. When the weight average molecular weight of the acrylic polymer (A) is 850 or more, sufficient adhesive strength can be obtained, and if it is 70,000 or less, the viscosity can be controlled to an appropriate range, and the workability is improved. good.
又,藉由使重量平均分子量為850以上且70,000以下,而易於與丙烯酸系基礎聚合物(B)相溶。因此,可提高丙烯酸系基礎聚合物(B)之黏著性,亦可使丙烯酸系聚合物(A)作為黏著賦予劑發揮作用。進而,即便於將分子量800以下之化合物設為18質量%以下之情形時,亦可良好地顯現黏著劑之黏著力,並且改善糊劑殘留。 Moreover, by making the weight average molecular weight 850 or more and 70,000 or less, it is easy to be compatible with the acrylic base polymer (B). Therefore, the adhesiveness of the acrylic base polymer (B) can be improved, and the acrylic polymer (A) can also function as an adhesion-imparting agent. Further, even when the compound having a molecular weight of 800 or less is used in an amount of 18% by mass or less, the adhesive force of the adhesive can be favorably exhibited, and the residue of the paste can be improved.
就防止糊劑殘留之觀點而言,丙烯酸系聚合物(A)之平均分子量較佳為MW/MN為1.0~2.0之範圍。又,就可將黏著劑較厚地塗佈於護膜框體,且可減少將護膜貼附於光罩時之光罩形變之觀點而言,較佳為嵌段聚合物。 The average molecular weight of the acrylic polymer (A) is preferably in the range of 1.0 to 2.0 in terms of M W /M N from the viewpoint of preventing the residue of the paste. Further, a block polymer can be preferably used because the adhesive is applied to the sheath frame in a thick manner and the mask of the mask when the film is attached to the mask can be reduced.
作為丙烯酸系聚合物(A)之具體例,可列舉:商品名「ARUFON(註冊商標)」系列(東亞合成股份有限公司製造)、商品名「Kurarity(註冊商標)」系列(Kuraray股份有限公司製造)等。商品名「ARUFON(註冊商標)」系列由於不使用聚合起始劑、鏈轉移劑、溶劑等,故而雜質較少,若MW/MN為1.0~2.0,則分子量分佈較窄,因此抗糊劑殘留性尤其優異。又,商品名「Kurarity(註冊商標)」系列由於為具有硬段及軟段之三嵌段共聚物,故而可較厚地塗佈於護膜框體,因此光罩形變之減少尤其優異。進而,商品名「Kurarity(註冊商 標)」系列若MW/MN為1.0~2.0,則分子量分佈較窄,故而抗糊劑殘留性亦優異。 Specific examples of the acrylic polymer (A) include the product name "ARUFON (registered trademark)" series (manufactured by Toagosei Co., Ltd.) and the product name "Kurarity (registered trademark)" series (manufactured by Kuraray Co., Ltd.) )Wait. The product name "ARUFON (registered trademark)" series has less impurities because it does not use a polymerization initiator, a chain transfer agent, a solvent, etc., and if the M W /M N is 1.0 to 2.0, the molecular weight distribution is narrow, so the anti-paste is anti-paste. The residue of the agent is particularly excellent. Further, since the product name "Kurarity (registered trademark)" series is a triblock copolymer having a hard segment and a soft segment, it can be applied to the film casing in a thick manner, and therefore the reduction in the deformation of the mask is particularly excellent. Further, when the M W /M N of the product name "Kurarity (registered trademark)" is 1.0 to 2.0, the molecular weight distribution is narrow, and therefore the anti-paste residual property is also excellent.
於本實施形態中,丙烯酸系基礎聚合物(B)之玻璃轉移溫度較佳為-25℃以上且140℃以下。尤其較佳為-25℃以上且130℃以下,進而較佳為-25℃以上且120℃以下。於本實施形態之丙烯酸系基礎聚合物(B)具有複數之玻璃轉移溫度之情形時,只要該複數之玻璃轉移溫度中之至少一者存在於該範圍內即可。又,關於丙烯酸系基礎聚合物(B),就可將黏著劑較厚地塗佈於護膜框體,而可減少將護膜貼附於光罩時之光罩形變之觀點而言,較佳為嵌段聚合物。 In the present embodiment, the glass transition temperature of the acrylic base polymer (B) is preferably -25 ° C or more and 140 ° C or less. It is particularly preferably -25 ° C or more and 130 ° C or less, more preferably -25 ° C or more and 120 ° C or less. In the case where the acrylic base polymer (B) of the present embodiment has a plurality of glass transition temperatures, at least one of the plurality of glass transition temperatures may be present in the range. Further, in the acrylic base polymer (B), the adhesive can be applied to the sheath frame in a thick manner, and the mask can be reduced in the case where the mask is attached to the mask. It is a block polymer.
上述嵌段聚合物之玻璃轉移溫度較佳為-25℃以上,且較佳為140℃以下。尤其較佳為-10℃以上且130℃以下,進而較佳為0℃以上且120℃以下。 The glass transition temperature of the above block polymer is preferably -25 ° C or higher, and preferably 140 ° C or lower. It is particularly preferably -10 ° C or more and 130 ° C or less, and further preferably 0 ° C or more and 120 ° C or less.
上述嵌段聚合物包含通式(I)-(a1)-(b)-(a2)-。式(I)之(a1)及(a2)之玻璃轉移溫度較佳為80℃以上。式(I)之(b)之玻璃轉移溫度較佳為30℃以下。又,式(I)之(b)較佳為於主鏈中具有玻璃轉移溫度為30℃以下之聚合物之嵌段聚合物。 The above block polymer comprises the general formula (I)-(a1)-(b)-(a2)-. The glass transition temperature of (a1) and (a2) of the formula (I) is preferably 80 ° C or higher. The glass transition temperature of (b) of the formula (I) is preferably 30 ° C or lower. Further, (b) of the formula (I) is preferably a block polymer having a polymer having a glass transition temperature of 30 ° C or less in the main chain.
關於構成式(I)之(a1)及(a2)所表示之聚合物嵌段(以下,將該等聚合物嵌段稱為「聚合物嵌段a」)之單體成分,就將聚合物嵌段a之玻璃轉移溫度設為80℃以上之觀點而言,較佳為主要為碳數1~14之甲基丙烯酸烷基酯。作為上述甲基丙烯酸烷基酯,例如可列舉:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸戊酯、甲基丙烯酸異戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十五烷基酯、甲基丙烯酸環己酯、甲基丙烯酸月桂酯、甲基丙烯酸十三烷基酯、甲基丙 烯酸2-己基癸酯等之1種或2種以上。其中,就將聚合物嵌段a之玻璃轉移溫度設為80℃以上之觀點而言,更佳為以甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯等包含甲基丙烯酸及碳數3以下之醇的酯作為主體。此處,所謂「主要」係指超過聚合物嵌段a整體內之至少一半,較佳為80%以上由碳數為1~14之甲基丙烯酸烷基酯佔據。又,聚合物嵌段a中之至少任一者均可包含碳數為1~14之甲基丙烯酸烷基酯。 The polymer component of the polymer block represented by (a1) and (a2) of the formula (I) (hereinafter, the polymer block is referred to as "polymer block a") is a polymer. From the viewpoint that the glass transition temperature of the block a is 80 ° C or higher, it is preferably an alkyl methacrylate having a carbon number of 1 to 14. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid. Butyl ester, second butyl methacrylate, third butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, methyl Pentadecyl acrylate, cyclohexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, methyl propyl One type or two or more types of 2-hexyl decyl acrylate. Among them, from the viewpoint of setting the glass transition temperature of the polymer block a to 80 ° C or higher, it is more preferable to use methyl methacrylate, ethyl methacrylate, n-propyl methacrylate or methacrylic acid. An ester containing methacrylic acid and an alcohol having 3 or less carbon atoms as a main component such as propyl ester. Here, "mainly" means at least half of the entire polymer block a, and preferably 80% or more is occupied by an alkyl methacrylate having 1 to 14 carbon atoms. Further, at least one of the polymer blocks a may contain an alkyl methacrylate having 1 to 14 carbon atoms.
於式(I)之聚合物嵌段a中,若為較少之比率(例如未達一半,較佳為未達20%),則亦可包含例如源自如下等單體之構成成分:甲基丙烯酸三甲基矽烷基酯、甲基丙烯酸三甲氧基矽烷基丙酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸烯丙酯等烷基酯以外之甲基丙烯酸酯;丙烯酸甲酯、丙烯酸正丁酯、丙烯酸第三丁酯等丙烯酸烷基酯;乙烯、丙烯等烯烴;ε-己內酯、戊內酯等內酯。若聚合物嵌段a之玻璃轉移溫度為80℃以上,則充分地獲得高溫下之保持力及凝集力而較佳。 In the polymer block a of the formula (I), if it is a small ratio (for example, less than half, preferably less than 20%), it may also comprise a constituent component derived from, for example, a monomer such as: a methacrylate other than an alkyl ester such as trimethyl decyl acrylate, trimethoxy decyl propyl methacrylate, glycidyl methacrylate or allyl methacrylate; methyl acrylate or acrylic acid An alkyl acrylate such as butyl ester or tributyl acrylate; an olefin such as ethylene or propylene; and a lactone such as ε-caprolactone or valerolactone. When the glass transition temperature of the polymer block a is 80 ° C or more, it is preferable to sufficiently obtain the holding power and the cohesive force at a high temperature.
關於構成式(I)之(b)所表示之聚合物嵌段(以下,將其稱為「聚合物嵌段b」)之單體成分,就將聚合物嵌段b之玻璃轉移溫度設為30℃以下之觀點而言,較佳為主要為碳數1~14之丙烯酸烷基酯及/或甲基丙烯酸烷基酯。作為可構成聚合物嵌段b之丙烯酸烷基酯,例如可列舉:丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第二丁酯、丙烯酸第三丁酯、丙烯酸戊酯、丙烯酸異戊酯、丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸月桂酯等之1種或2種以上。又,作為可構成聚合物嵌段b之甲基丙烯酸烷基酯單體,例如可列舉:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸戊酯、甲基丙烯酸異戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己 酯、甲基丙烯酸十五烷基酯、甲基丙烯酸環己酯、甲基丙烯酸月桂酯、甲基丙烯酸十三烷基酯、甲基丙烯酸2-己基癸酯等之1種或2種以上。其中,於將甲基丙烯酸烷基酯用作主要之單體成分而構成聚合物嵌段b之情形時,為將其玻璃轉移溫度設為30℃以下,較佳為以甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸戊酯、甲基丙烯酸異戊酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十五烷基酯、甲基丙烯酸月桂酯、甲基丙烯酸十三烷基酯、甲基丙烯酸2-己基癸酯等甲基丙烯酸與碳數4以上之醇的酯作為主體。於聚合物嵌段b中,亦可於不會對光罩上之糊劑殘留與耐光性產生不良影響之範圍內包含其他構成成分。 The glass transition temperature of the polymer block b is set to the monomer component of the polymer block (hereinafter referred to as "polymer block b") represented by the formula (I) (b). From the viewpoint of 30 ° C or lower, it is preferably an alkyl acrylate and/or an alkyl methacrylate having a carbon number of 1 to 14. Examples of the alkyl acrylate which can constitute the polymer block b include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid second. One or more of ester, butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate. Further, examples of the alkyl methacrylate monomer which can constitute the polymer block b include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate. N-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, third butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, A 2-ethylhexyl acrylate One or two or more kinds of esters, pentadecyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, and 2-hexyl decyl methacrylate. In the case where the alkyl methacrylate is used as the main monomer component to form the polymer block b, the glass transition temperature is 30 ° C or lower, preferably n-butyl methacrylate. , isobutyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, lauric acid methacrylate An ester of methacrylic acid such as ester, tridecyl methacrylate or 2-hexyl decyl methacrylate with an alcohol having 4 or more carbon atoms is mainly used. In the polymer block b, other constituent components may be included in a range that does not adversely affect the paste residue and the light resistance on the photomask.
藉由使聚合物嵌段b之玻璃轉移溫度為30℃以下,而充分地獲得黏著力、保持力,故而較佳。 By setting the glass transition temperature of the polymer block b to 30 ° C or lower, the adhesion and the holding power are sufficiently obtained, which is preferable.
上述嵌段聚合物具有1個聚合物嵌段b位於如式(I)之(a1)及(a2)般2個聚合物嵌段a之間之結構。然而,只要以特定之順序包含上述3個聚合物嵌段,則不僅包含僅由該等3個聚合物嵌段所構成之嵌段共聚物,亦可包含由進而包含1個以上其他聚合物嵌段之4個以上聚合物嵌段所構成之嵌段共聚物。上述其他聚合物嵌段可為與聚合物嵌段a或b同種之聚合物嵌段,亦可為與其不同種之聚合物嵌段c。作為不同種之聚合物嵌段c,可例示包含乙烯、丙烯等烯烴及ε-己內酯、戊內酯等內酯等之聚合物嵌段。 The above block polymer has a structure in which one polymer block b is located between two polymer blocks a like (a1) and (a2) of the formula (I). However, if the above three polymer blocks are contained in a specific order, not only the block copolymer composed of only the three polymer blocks but also one or more other polymers may be contained. A block copolymer composed of four or more polymer blocks of the segment. The above other polymer blocks may be the same polymer block as the polymer block a or b, or may be a polymer block c of a different kind. Examples of the polymer block c of a different type include polymer blocks such as an olefin such as ethylene or propylene, and a lactone such as ε-caprolactone or valerolactone.
作為本實施形態中較佳之嵌段共聚物,可列舉:聚合物嵌段a-聚合物嵌段b-聚合物嵌段a、聚合物嵌段a-聚合物嵌段b-聚合物嵌段a-聚合物嵌段b、聚合物嵌段a-聚合物嵌段b-聚合物嵌段a-聚合物嵌段c等。 Preferred examples of the block copolymer in the present embodiment include a polymer block a-polymer block b-polymer block a, and a polymer block a-polymer block b-polymer block a. - polymer block b, polymer block a - polymer block b - polymer block a - polymer block c and the like.
嵌段共聚物之分子量以重量平均分子量計較佳為處於10,000~500,000之範圍內,更佳為處於30,000~450,000之範圍內,尤其更佳 為處於50,000~400,000之範圍內。藉由使嵌段共聚物之重量平均分子量為10,000~500,000之範圍,可利用活性聚合法等進行聚合,而獲得分子量分佈較窄且雜質較少之嵌段共聚物。藉此,就改善黏著劑之糊劑殘留,可將黏著劑較厚地塗佈之方面而言較佳。又,就上述觀點而言,作為分子量分佈,較佳為MW/MN為1.0~2.0。 The molecular weight of the block copolymer is preferably in the range of 10,000 to 500,000, more preferably in the range of 30,000 to 450,000, and still more preferably in the range of 50,000 to 400,000, in terms of weight average molecular weight. By making the weight average molecular weight of the block copolymer in the range of 10,000 to 500,000, polymerization can be carried out by a living polymerization method or the like to obtain a block copolymer having a narrow molecular weight distribution and a small amount of impurities. Thereby, it is preferable to improve the paste residue of the adhesive, and to apply the adhesive thicker. Further, from the above viewpoints, as the molecular weight distribution, M W /M N is preferably 1.0 to 2.0.
並且,嵌段共聚物中,以分子中所含之聚合物嵌段b之總質量為基準時之聚合物嵌段a之總質量之比率(a/b)較佳為5/95~80/20。進而,a/b更佳為10/90~75/25。藉由使a/b為5/95以上,而成為充分獲得黏著劑之凝集力,且獲得較高之保持力之傾向。又,藉由使a/b為80/20以下,而成為充分獲得黏著力之傾向。 Further, in the block copolymer, the ratio (a/b) of the total mass of the polymer block a based on the total mass of the polymer block b contained in the molecule is preferably 5/95 to 80/ 20. Further, a/b is more preferably 10/90 to 75/25. By setting a/b to 5/95 or more, the cohesive force of the adhesive is sufficiently obtained, and a high holding force tends to be obtained. Further, by setting a/b to 80/20 or less, the adhesive strength is sufficiently obtained.
若為上述嵌段共聚物,則可於聚合物中形成體積較大之具有分支結構之側鏈。因此,可將黏著劑較厚地塗佈,而可減少將護膜貼附於光罩時之光罩形變。又,丙烯酸系聚合物(A)由於與聚合物嵌段b之相溶性尤其良好,故而可提高接著性與柔軟性,並且,可減少光罩形變。 In the case of the above block copolymer, a side chain having a branched structure having a large volume can be formed in the polymer. Therefore, the adhesive can be applied thickly, and the deformation of the mask when the film is attached to the mask can be reduced. Further, since the acrylic polymer (A) is particularly excellent in compatibility with the polymer block b, the adhesion and flexibility can be improved, and the mask deformation can be reduced.
又,於嵌段共聚物中,亦可以不會對光罩上之糊劑殘留、與丙烯酸系基礎聚合物(B)之耐光性產生不良影響之程度,於分子側鏈中或分子主鏈末端具有羥基、羧基、酸酐基、胺基等官能基。 Further, in the block copolymer, it is possible to prevent the paste on the mask from remaining and to adversely affect the light resistance of the acrylic base polymer (B) in the molecular side chain or at the end of the molecular main chain. It has a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group or an amine group.
作為該等嵌段共聚物之具體例,可列舉:商品名「Kurarity(註冊商標)」系列(Kuraray股份有限公司製造)、商品名「Nanostrength」系列(Arkema股份有限公司製造)等。 Specific examples of such a block copolymer include a product name "Kurarity (registered trademark)" series (manufactured by Kuraray Co., Ltd.), a product name "Nanostrength" series (manufactured by Arkema Co., Ltd.), and the like.
除該等丙烯酸系聚合物(A)與丙烯酸系基礎聚合物(B)以外,亦可添加無機物質,以提高耐光性或改善糊劑殘留。 In addition to the acrylic polymer (A) and the acrylic base polymer (B), an inorganic substance may be added to improve light resistance or to improve paste residue.
本實施形態之護膜例如可利用以下方法而較佳地製造。 The protective film of the present embodiment can be preferably produced, for example, by the following method.
第一,將上述丙烯酸系聚合物(A)與丙烯酸系基礎聚合物(B)進行混合,獲得黏著劑組合物。於該情形時,為將黏著劑10附著(塗佈)於 護膜框體2之端面作為特定之厚度、寬度之光罩黏著劑層,而將黏著劑組合物進而利用溶劑稀釋,調整溶液濃度(黏度)。光罩黏著劑層之厚度較佳為0.25mm以上且3.0mm以下。於半導體用時,該厚度較佳為0.25mm以上且1.0mm以下,進而較佳為0.3mm以上且0.8mm以下。於液晶用時,該厚度較佳為1.0mm以上且2.5mm以下,進而較佳為1.2mm以上且2.0mm以下。又,光罩黏著劑層之寬度較佳為被施以塗佈之框架寬度之30%以上且90%以下,進而較佳為40%以上且80%以下。作為框架寬度,通常為1.0mm以上且20mm以下。 First, the acrylic polymer (A) and the acrylic base polymer (B) are mixed to obtain an adhesive composition. In this case, in order to attach (coat) the adhesive 10 to The end face of the film frame 2 is used as a mask adhesive layer of a specific thickness and width, and the adhesive composition is further diluted with a solvent to adjust the solution concentration (viscosity). The thickness of the mask adhesive layer is preferably 0.25 mm or more and 3.0 mm or less. In the case of semiconductors, the thickness is preferably 0.25 mm or more and 1.0 mm or less, and more preferably 0.3 mm or more and 0.8 mm or less. In the case of liquid crystal, the thickness is preferably 1.0 mm or more and 2.5 mm or less, and more preferably 1.2 mm or more and 2.0 mm or less. Further, the width of the mask adhesive layer is preferably 30% or more and 90% or less, more preferably 40% or more and 80% or less of the width of the applied frame. The frame width is usually 1.0 mm or more and 20 mm or less.
第二,將黏著劑組合物塗佈於具有張設於一端面2e之護膜膜體3的護膜框體2之另一端面2f。塗佈方法並無特別限定,但於利用溶劑稀釋黏著劑組合物之情形時,較佳為使用分注器或注射器進行塗佈。又,亦可使用將黏著劑組合物熱熔融而塗佈之熱熔法。 Second, the adhesive composition is applied to the other end surface 2f of the protective film casing 2 having the protective film body 3 stretched over the one end surface 2e. The coating method is not particularly limited. However, when the adhesive composition is diluted with a solvent, it is preferably applied by using a dispenser or a syringe. Further, a hot melt method in which the adhesive composition is thermally melted and applied can also be used.
第三,於利用溶劑稀釋黏著劑組合物之情形時,使藉由將所塗佈之黏著劑組合物進行加熱乾燥而成型之黏著劑10密接於護膜框體2之另一端面2f。於利用熱熔法塗佈黏著劑組合物之情形時,使將所塗佈之黏著劑組合物成型後進行冷卻而成之黏著劑10密接於護膜框體2之另一端面2f。亦可於將黏著物組合物進行乾燥或冷卻後,貼附用以保護黏著劑10之黏著面之保護膜F。保護膜F例如使用聚酯製之厚度30~200μm之膜等。又,若自黏著劑10將保護膜F剝離時之剝離力較大,則有於剝離時黏著劑10變形之虞。因此,亦可預先對與黏著劑10相接之保護膜F表面進行使用聚矽氧或氟等之脫模處理,以成為適當之剝離力。 Third, in the case where the adhesive composition is diluted with a solvent, the adhesive 10 molded by heat-drying the applied adhesive composition is adhered to the other end surface 2f of the protective cover 2 . When the adhesive composition is applied by a hot melt method, the adhesive 10 obtained by molding the applied adhesive composition and then cooled is adhered to the other end surface 2f of the protective cover 2 . The protective film F for protecting the adhesive side of the adhesive 10 may be attached after the adhesive composition is dried or cooled. As the protective film F, for example, a film made of polyester having a thickness of 30 to 200 μm or the like is used. Further, when the peeling force is large when the protective film F is peeled off from the adhesive 10, the adhesive 10 is deformed at the time of peeling. Therefore, the surface of the protective film F that is in contact with the adhesive 10 may be subjected to a release treatment using polyfluorene or fluorine or the like in advance to obtain a suitable peeling force.
亦可於貼附用以保護黏著劑10之黏著面之保護膜F後,施加負荷,使黏著劑表面成型為大致平坦。 After the protective film F for protecting the adhesive surface of the adhesive 10 is attached, a load is applied to form the surface of the adhesive to be substantially flat.
以下,藉由實施例及比較例進而具體地說明本實施形態,但本 實施形態並不受該等任何限定。 Hereinafter, the present embodiment will be specifically described by way of examples and comparative examples, but The embodiment is not limited by these.
丙烯酸系聚合物(A)、丙烯酸系基礎聚合物(B)、分子量800以下之化合物係使用下述者。又,關於丙烯酸系聚合物(A),將藉由GPC測定所獲得之組成之分子量800以下之比率一併表示。 The acrylic polymer (A), the acrylic base polymer (B), and the compound having a molecular weight of 800 or less are used as follows. In addition, the acrylic polymer (A) is represented by a ratio of a molecular weight of 800 or less which is obtained by GPC measurement.
‧ARUFON(註冊商標)UP1190(東亞合成股份有限公司製造)(28.2%) ‧ARUFON (registered trademark) UP1190 (manufactured by Toagosei Co., Ltd.) (28.2%)
(玻璃轉移溫度:-50℃) (glass transition temperature: -50 ° C)
‧ARUFON(註冊商標)UP1080(東亞合成股份有限公司製造)(5.9%) ‧ARUFON (registered trademark) UP1080 (manufactured by Toagosei Co., Ltd.) (5.9%)
(玻璃轉移溫度:-61℃) (glass transition temperature: -61 ° C)
‧ARUFON(註冊商標)UP1000(東亞合成股份有限公司製造)(13.7%) ‧ARUFON (registered trademark) UP1000 (manufactured by Toagosei Co., Ltd.) (13.7%)
(玻璃轉移溫度:-77℃) (glass transition temperature: -77 ° C)
‧Kurarity(註冊商標)LA1114(Kuraray股份有限公司製造)(0.0%) ‧Kurarity (registered trademark) LA1114 (manufactured by Kuraray Co., Ltd.) (0.0%)
(玻璃轉移溫度:-40℃) (glass transition temperature: -40 ° C)
‧i-BA/BA/AA/HEA(丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯)(2.4%) ‧i-BA/BA/AA/HEA (Isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate) (2.4%)
(玻璃轉移溫度:-51℃) (glass transition temperature: -51 ° C)
(丙烯酸系基礎聚合物(B)) (Acrylic base polymer (B))
‧Kurarity(註冊商標)LA2140e(Kuraray股份有限公司製造) ‧Kurarity (registered trademark) LA2140e (manufactured by Kuraray Co., Ltd.)
(玻璃轉移溫度:-38℃、85℃) (glass transition temperature: -38 ° C, 85 ° C)
‧Kurarity(註冊商標)LA2330(Kuraray股份有限公司製造) ‧Kurarity (registered trademark) LA2330 (manufactured by Kuraray Co., Ltd.)
(玻璃轉移溫度:-39℃、86℃) (glass transition temperature: -39 ° C, 86 ° C)
‧Nanostrength M-85(Arkema股份有限公司製造) ‧Nanostrength M-85 (manufactured by Arkema Co., Ltd.)
(玻璃轉移溫度:-54℃、100℃) (glass transition temperature: -54 ° C, 100 ° C)
‧Pine Crystal(註冊商標)KE-311(荒川化學工業股份有限公司製造) ‧Pine Crystal (registered trademark) KE-311 (made by Arakawa Chemical Industries Co., Ltd.)
丙烯酸系聚合物(A)、丙烯酸系基礎聚合物(B)之分子量、玻璃轉移溫度及各共聚成分之含量之測定、包含丙烯酸系聚合物(A)、丙烯酸系基礎聚合物(B)之黏著劑之玻璃轉移溫度及彈性模數係按以下所記載之裝置及條件進行。 The measurement of the molecular weight of the acrylic polymer (A), the acrylic base polymer (B), the glass transition temperature, and the content of each copolymer component, and the adhesion of the acrylic polymer (A) and the acrylic base polymer (B) The glass transition temperature and modulus of elasticity of the agent are carried out according to the apparatus and conditions described below.
‧裝置:Tosoh股份有限公司製造之凝膠滲透層析儀(HLC-8320) ‧Installation: Gel Permeation Chromatograph (HLC-8320) manufactured by Tosoh Co., Ltd.
‧管柱:將Tosoh股份有限公司製造之「TSKgel SUPER HZ3000×2」及「HZ2000×2」串列連接 ‧Tube: "TSKgel SUPER HZ3000×2" and "HZ2000×2" manufactured by Tosoh Co., Ltd. are connected in series
‧洗提液:四氫呋喃 ‧Eluent: Tetrahydrofuran
‧洗提液流量:0.6ml/min ‧ Eluent flow rate: 0.6ml/min
‧管柱溫度:40℃ ‧column temperature: 40 ° C
‧檢測器:示差折射率(RI)計 ‧Detector: differential refractive index (RI) meter
‧校準曲線:使用標準聚苯乙烯而製成 ‧ Calibration curve: made with standard polystyrene
‧裝置:TA Instruments公司製造之DSCQ2000 ‧Device: DSCQ2000 manufactured by TA Instruments
‧密封盤 ‧ Sealing plate
‧溫度範圍:-80℃~160℃ ‧ Temperature range: -80 ° C ~ 160 ° C
‧升溫速度:5℃/min ‧ Heating rate: 5 ° C / min
‧試樣重量:10mg ‧ sample weight: 10mg
於包含丙烯酸系聚合物(A)、丙烯酸系基礎聚合物(B)之黏著劑之玻璃轉移溫度測定出複數之情形時,將最低溫側之溫度作為玻璃轉移溫度Tg記載於表1中。 In the case where a plurality of glass transition temperatures of the adhesive containing the acrylic polymer (A) and the acrylic base polymer (B) are measured, the temperature on the lowest temperature side is shown in Table 1 as the glass transition temperature Tg.
‧裝置:日本電子股份有限公司製造之核磁共振裝置(JNM-LA400) ‧Device: Nuclear Magnetic Resonance Device (JNM-LA400) manufactured by JEOL Ltd.
‧溶劑:氘代氯仿 ‧ Solvent: Deuterated chloroform
再者,於1H-NMR光譜中,3.6ppm及4.0ppm附近之訊號分別屬於甲基丙烯酸甲酯單元之酯基(-O-CH3)及丙烯酸正丁酯單元之酯基(-O-CH2-CH2-CH2-CH3),因此藉由該等訊號之積分值之比而求出共聚成分之含量。 Further, in the 1 H-NMR spectrum, the signals in the vicinity of 3.6 ppm and 4.0 ppm belong to the ester group of the methyl methacrylate unit (-O-CH 3 ) and the ester group of the n-butyl acrylate unit (-O-, respectively). Since CH 2 -CH 2 -CH 2 -CH 3 ), the content of the copolymerization component is determined by the ratio of the integral values of the signals.
將附保護膜之護膜之一邊切斷,其後,以黏著劑層不變形之方式將保護膜緩緩剝離後,自護膜框體將光罩黏著劑層緩緩剝離。此時,難以剝離時一面使嬰兒爽身粉(Siccarol)附著於手與黏著劑層一面緩緩剝離,使所剝離之黏著劑層之伸長率成為5%以下。 One of the protective film with the protective film is cut, and then the protective film is gradually peeled off so that the adhesive layer is not deformed, and the mask adhesive layer is gradually peeled off from the protective film frame. At this time, when it is difficult to peel off, the baby talcum powder (Siccarol) is gradually peeled off from the hand and the adhesive layer, and the elongation of the peeled adhesive layer is 5% or less.
使用下述裝置於室溫(25℃)下對所剝離之黏著劑層進行測定。 The peeled adhesive layer was measured at room temperature (25 ° C) using the apparatus described below.
裝置名:Autograph(SHIMAZU EZ-S,島津製作所製造) Device name: Autograph (SHIMAZU EZ-S, manufactured by Shimadzu Corporation)
荷重元(load cell):1N(夾式夾頭) Load cell: 1N (clip chuck)
夾頭間隔:40mm Chuck spacing: 40mm
十字頭速度:100mm/min Crosshead speed: 100mm/min
利用上述裝置,將黏著劑層拉伸至伸長率20%。另外,測定黏著劑層之截面面積,將上述測定結果除以截面面積,藉此求出每單位面積之應力值。 Using the above apparatus, the adhesive layer was stretched to an elongation of 20%. Further, the cross-sectional area of the adhesive layer was measured, and the measurement result was divided by the cross-sectional area, thereby obtaining a stress value per unit area.
製作包含x軸為伸長率、y軸為每單位面積之應力值之曲線圖,在伸長率0%與伸長率20%時繪製直線,將此情況下之伸長率100%時之y軸之值設為彈性模數。 A graph is prepared which includes an elongation value of the x-axis and a stress value per unit area of the y-axis, and draws a straight line at an elongation of 0% and an elongation of 20%, and the value of the y-axis at an elongation of 100% in this case Set to the elastic modulus.
藉由周知之方法而調整i-BA/BA/AA/HEA組合物。具體而言,向具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容 器中加入乙酸乙酯(30重量份),且以48/48/1.5/2.5/1.0之重量比添加丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮二異丁腈之混合物(32重量份),於氮氣環境下,使該反應溶液於60℃下反應8小時。反應結束後,添加甲苯(38重量份),獲得不揮發分濃度32重量%之丙烯酸共聚物溶液。 The i-BA/BA/AA/HEA composition was adjusted by a known method. Specifically, the reaction capacity is provided to a mixer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube. Ethyl acetate (30 parts by weight) was added to the solvent, and isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2'- was added in a weight ratio of 48/48/1.5/2.5/1.0. A mixture of azobisisobutyronitrile (32 parts by weight) was reacted at 60 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution having a nonvolatile concentration of 32% by weight.
將作為丙烯酸系聚合物(A)之「Kurarity LA1114(Kuraray股份有限公司製造)」70質量份、及作為基礎系丙烯酸聚合物(B)之丙烯酸系嵌段共聚物「Kurarity LA2140e(Kuraray股份有限公司製造)」30質量份以整體成為48g之方式混合,而獲得原料混合物。將所獲得之原料混合物投入至Labo Plastomill(東洋精機製作所股份有限公司製造,內容量:60mL)後,將其密閉。於200℃、100rpm下混練20分鐘,獲得塊狀之光罩黏著劑。將約10g之光罩黏著劑投入至加熱槽(槽內溫度:200℃)使其熔融。 70 parts by mass of "Kurarity LA1114 (manufactured by Kuraray Co., Ltd.)" as the acrylic polymer (A) and an acrylic block copolymer "Kurarity LA2140e" (Kuraray Co., Ltd.) as a base-based acrylic polymer (B) 30 parts by mass were mixed in such a manner as to be 48 g as a whole, and a raw material mixture was obtained. The obtained raw material mixture was placed in a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd., content: 60 mL), and then sealed. The mixture was kneaded at 200 ° C and 100 rpm for 20 minutes to obtain a block-shaped reticle adhesive. About 10 g of the mask adhesive was placed in a heating bath (in-tank temperature: 200 ° C) to be melted.
另一方面,準備經陽極氧化處理之鋁合金製之護膜框體(外徑113mm×149mm,內徑109mm×145mm,高度2.9mm)。此處,作為銷孔,於距膜接著劑塗佈端面為1.7mm之位置,在距護膜框體外邊側面之角部分別為25mm之位置,設置4處孔徑1.6mm 、深度1.2mm之夾具孔。將自連通於加熱槽之針尖擠出之熔融狀態之光罩黏著劑塗佈於護膜框體之一端面上,而形成光罩黏著劑層。所形成之光罩黏著劑層之厚度為0.6mm。其後,於光罩黏著劑層之表面貼合經聚矽氧脫模處理之厚度100μm之聚酯製保護膜。於上述護膜框體之另一端面經由膜接著劑層而貼附護膜膜體,從而製作護膜。 On the other hand, a protective film frame made of an anodized aluminum alloy (outer diameter: 113 mm × 149 mm, inner diameter: 109 mm × 145 mm, height: 2.9 mm) was prepared. Here, as the pin hole, at a position of 1.7 mm from the end face of the film adhesive application, at a position of 25 mm from the corner of the outer side of the outer side of the film frame, four holes of 1.6 mm are provided. , 1.2mm depth of the fixture hole. A mask adhesive which is extruded from a needle tip which is connected to the heating bath is applied to one end surface of the sheath frame to form a mask adhesive layer. The thickness of the formed mask adhesive layer was 0.6 mm. Thereafter, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon oxide release treatment was attached to the surface of the mask adhesive layer. A protective film is attached to the other end surface of the above-mentioned protective film frame via a film adhesive layer to form a protective film.
針對所獲得之護膜,實施剝離性評價及光罩之形變評價。將各結果記載於表1中。 The peeling evaluation and the deformation evaluation of the mask were performed about the obtained film. Each result is shown in Table 1.
關於實施例1中所獲得之附黏著劑之護膜,剝離保護膜,利用簡易型貼片機對6025附鉻光罩空白基材進行負荷(30Kgf,60sec)貼附,獲得貼附有護膜之光罩基材。將光罩基材於室溫(20±3℃)下放置2小時後,將光罩基材水平地固定,利用拉伸試驗機,抓持護膜之各長邊各有2個而為共4個之銷孔,以5mm/min之速度將各長邊同時地相對於光罩面垂直地提拉,進行護膜之剝離。剝離性係觀察各被黏著體表面之情況,根據以下基準進行評價。所謂本實施例中之糊劑殘留係指因內聚破壞而黏著劑之一部份附著於光罩之狀態。 With respect to the protective film of the adhesive obtained in Example 1, the protective film was peeled off, and a 6025 chrome-mask blank substrate was attached (30 Kgf, 60 sec) by a simple mounter to obtain a film attached thereto. Photomask substrate. After the photomask substrate was allowed to stand at room temperature (20±3° C.) for 2 hours, the photomask substrate was horizontally fixed, and each of the long sides of the protective film was grasped by a tensile tester. The four pin holes were pulled at a speed of 5 mm/min at the same time with respect to the mask surface at the same time, and the film was peeled off. The peeling property was observed on the surface of each adherend, and evaluated based on the following criteria. The paste residue in the present embodiment means a state in which a part of the adhesive adheres to the photomask due to cohesive failure.
◎:糊劑殘留面積為貼附面積整體內之0%以上且5%以下 ◎: The residual area of the paste is 0% or more and 5% or less of the entire attached area.
○:糊劑殘留面積超過貼附面積整體內之5%且為10%以下 ○: The residual area of the paste exceeds 5% of the entire attached area and is 10% or less.
△:糊劑殘留面積超過貼附面積整體內之10%且為20%以下 △: The residual area of the paste exceeds 10% of the entire attached area and is 20% or less.
×:糊劑殘留面積超過貼附面積整體內之20%且為100%以下 ×: The residual area of the paste exceeds 20% of the entire attached area and is 100% or less.
因光罩之形變等所引起之變形之評價係使用Tropel公司製造之FlatMaster200進行測定。首先,對於光罩(6025石英),測定貼附護膜前之平坦度。其後,將實施例1中所獲得之附黏著劑之護膜貼附於該光罩,測定貼附護膜後之光罩之平坦度(測定範圍:135mm×110mm)。藉由將貼附前後之平坦度相減,算出因貼附護膜而6025石英變形何種程度。 The evaluation of the deformation caused by the deformation of the reticle or the like was carried out using a FlatMaster 200 manufactured by Tropel. First, for the photomask (6025 quartz), the flatness before attaching the protective film was measured. Then, the film of the adhesive agent obtained in Example 1 was attached to the mask, and the flatness of the mask after the film was attached (measurement range: 135 mm × 110 mm) was measured. By subtracting the flatness before and after the attachment, it is calculated how much the 6025 quartz is deformed by the attachment of the protective film.
護膜向石英之貼附係利用簡易型貼片機進行(負荷:15Kgf,60sec)。 The attachment of the film to the quartz is carried out using a simple placement machine (load: 15 Kgf, 60 sec).
◎:因貼附護膜所引起之光罩之變形量為25nm以下 ◎: The amount of deformation of the mask caused by attaching the protective film is 25 nm or less.
○:因貼附護膜所引起之光罩之變形量超過25nm且為35nm以下 ○: The amount of deformation of the mask caused by attaching the protective film exceeds 25 nm and is 35 nm or less.
△:因貼附護膜所引起之光罩之變形量超過35nm且為60nm以下 △: The amount of deformation of the mask caused by attaching the protective film exceeds 35 nm and is 60 nm or less.
×:因貼附護膜所引起之光罩之變形量超過60nm ×: The deformation of the reticle caused by attaching the protective film exceeds 60 nm
以成為表1中所記載之調配量之方式混合各成分而獲得混合物,除此以外,以與實施例1同樣地製作護膜。對所獲得之護膜實施與實施例1相同之評價。該等結果亦記載於表1中。 A film was prepared in the same manner as in Example 1 except that the components were mixed to obtain a mixture as shown in Table 1. The same evaluation as in Example 1 was carried out on the obtained film. These results are also shown in Table 1.
使用捏合機,將苯乙烯-乙烯-丁烯-苯乙烯共聚物100質量份、氫化型萜烯樹脂80質量份、石蠟系加工處理油40質量份及抗氧化劑(BHT)2質量份於220℃下進行熔融混合,藉此獲得塊狀之光罩黏著劑。將約10g之光罩黏著劑投入至加熱槽(槽內溫度:200℃)使其熔融。 100 parts by mass of a styrene-ethylene-butylene-styrene copolymer, 80 parts by mass of a hydrogenated terpene resin, 40 parts by mass of a paraffin-based processing oil, and 2 parts by mass of an antioxidant (BHT) at 220 ° C using a kneader Melt mixing is carried out to obtain a block-shaped reticle adhesive. About 10 g of the mask adhesive was placed in a heating bath (in-tank temperature: 200 ° C) to be melted.
另一方面,準備經陽極氧化處理之鋁合金製之護膜框體(外徑113mm×149mm,內徑109mm×145mm,高度2.9mm)。將自連通於加熱槽之針尖擠出之熔融狀態之光罩黏著劑塗佈於護膜框體之一端面上,而形成光罩黏著劑層。所形成之光罩黏著劑層之厚度為0.6mm。其後,於光罩黏著劑層之表面貼合經聚矽氧脫模處理之厚度100μm之聚酯製保護膜。於上述護膜框體之另一端面經由膜接著劑層而貼附護膜膜體,從而製作護膜。 On the other hand, a protective film frame made of an anodized aluminum alloy (outer diameter: 113 mm × 149 mm, inner diameter: 109 mm × 145 mm, height: 2.9 mm) was prepared. A mask adhesive which is extruded from a needle tip which is connected to the heating bath is applied to one end surface of the sheath frame to form a mask adhesive layer. The thickness of the formed mask adhesive layer was 0.6 mm. Thereafter, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon oxide release treatment was attached to the surface of the mask adhesive layer. A protective film is attached to the other end surface of the above-mentioned protective film frame via a film adhesive layer to form a protective film.
針對所獲得之護膜,與實施例1同樣地實施剝離性評價及光罩之形變評價。將各結果記載於表1中。 With respect to the obtained film, the peeling evaluation and the deformation evaluation of the mask were performed in the same manner as in Example 1. Each result is shown in Table 1.
向具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中投入乙酸乙酯(30質量份)。將以30/66/1.5/2.5/1之質量比混合丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮二異丁腈而成之混合物(32質量份)添加至乙酸乙酯中,於氮氣環境下,於60℃下反應8小時。反應結束後,將甲苯(38質量份)添加至反應溶 液中,獲得不揮發分濃度32質量%之丙烯酸共聚物溶液(重量平均分子量130萬)。於所獲得之丙烯酸共聚物溶液100質量份中,添加多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷之甲苯溶液,不揮發分濃度5%)0.3重量份,進行攪拌混合,而獲得黏著劑前驅物組合物。 Ethyl acetate (30 parts by mass) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. A mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2'-azobisisobutyronitrile in a mass ratio of 30/66/1.5/2.5/1 (32) The mass parts were added to ethyl acetate, and the mixture was reacted at 60 ° C for 8 hours under a nitrogen atmosphere. After the reaction was completed, toluene (38 parts by mass) was added to the reaction solution. In the solution, an acrylic copolymer solution (weight average molecular weight: 1.3 million) having a nonvolatile content of 32% by mass was obtained. To 100 parts by mass of the obtained acrylic copolymer solution, a toluene solution of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) is added, and no volatile matter is added. The concentration of 5%) 0.3 parts by weight was stirred and mixed to obtain an adhesive precursor composition.
另一方面,準備經陽極氧化處理之鋁合金製之護膜框體(外徑113mm×149mm,內徑109mm×145mm,高度3.2mm)。此處,作為銷孔,於距膜接著劑塗佈端面為1.7mm之位置,在距護膜框體外邊側面之角部分別為25mm之位置,設置4處孔徑1.6mm 、深度1.2mm之夾具孔。利用分注器將所調製之上述黏著劑組合物塗佈於護膜框體之一端面上。將其以兩個階段進行加熱乾燥、固化(第1階段:100℃、8分鐘,第2階段:180℃、8分鐘),而形成光罩黏著劑層。其後,於光罩黏著劑層之表面貼合經聚矽氧脫模處理之厚度100μm之聚酯製保護膜,於室溫(20±3℃)下熟化3天,使黏著力穩定化。所形成之光罩黏著劑層之厚度為0.3mm。於上述護膜框體之另一端面經由膜接著劑層而貼附護膜膜體,從而製作護膜。 On the other hand, a protective film frame made of an anodized aluminum alloy (outer diameter: 113 mm × 149 mm, inner diameter: 109 mm × 145 mm, height: 3.2 mm) was prepared. Here, as the pin hole, at a position of 1.7 mm from the end face of the film adhesive application, at a position of 25 mm from the corner of the outer side of the outer side of the film frame, four holes of 1.6 mm are provided. , 1.2mm depth of the fixture hole. The prepared adhesive composition is applied to one end surface of the sheathing frame by a dispenser. This was heat-dried and solidified in two stages (first stage: 100 ° C, 8 minutes, second stage: 180 ° C, 8 minutes) to form a mask adhesive layer. Thereafter, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon oxide release treatment was attached to the surface of the mask adhesive layer, and aged at room temperature (20 ± 3 ° C) for 3 days to stabilize the adhesive force. The thickness of the reticle adhesive layer formed was 0.3 mm. A protective film is attached to the other end surface of the above-mentioned protective film frame via a film adhesive layer to form a protective film.
針對所獲得之護膜,與實施例1同樣地實施剝離性評價及光罩之形變評價。將各結果記載於表1中。 With respect to the obtained film, the peeling evaluation and the deformation evaluation of the mask were performed in the same manner as in Example 1. Each result is shown in Table 1.
根據本發明,可充分防止曝光後之光罩上之糊劑殘留。本發明可較佳地用於IC(積體電路)、LSI(大規模積體電路)、LCD(液晶顯示器)等之光微影步驟中,尤其可於使用必需高解析度之曝光中所使用之準分子雷射之光微影步驟、較佳為使用200nm以下之紫外光曝光之光微影步驟時較佳地使用。 According to the present invention, the residue on the mask after exposure can be sufficiently prevented. The present invention can be preferably used in an optical lithography step of an IC (integrated circuit), an LSI (large-scale integrated circuit), an LCD (Liquid Crystal Display), or the like, and can be particularly used in exposure using a necessary high resolution. The photolithographic lithography step of the excimer laser is preferably used when a photolithography step of exposure to ultraviolet light of 200 nm or less is used.
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TWI618974B (en) * | 2016-12-28 | 2018-03-21 | Micro Lithography Inc | Dust-proof frame structure for reticle |
WO2018125699A2 (en) * | 2016-12-30 | 2018-07-05 | 3M Innovative Properties Company | Tapes and methods of use for masking aluminum surfaces in chromic acid anodization |
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- 2014-10-10 JP JP2015542607A patent/JP6326059B2/en active Active
- 2014-10-10 KR KR1020167009459A patent/KR102032601B1/en active IP Right Grant
- 2014-10-10 WO PCT/JP2014/077251 patent/WO2015056653A1/en active Application Filing
- 2014-10-15 TW TW103135723A patent/TWI526515B/en active
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JP2010155923A (en) * | 2008-12-26 | 2010-07-15 | Dainippon Printing Co Ltd | Pressure-sensitive adhesive film for protection |
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KR102032601B1 (en) | 2019-10-15 |
WO2015056653A1 (en) | 2015-04-23 |
KR20160055859A (en) | 2016-05-18 |
KR20180043404A (en) | 2018-04-27 |
JP6326059B2 (en) | 2018-05-16 |
CN105683834B (en) | 2021-03-02 |
JPWO2015056653A1 (en) | 2017-03-09 |
TW201608004A (en) | 2016-03-01 |
TW201520302A (en) | 2015-06-01 |
CN105683834A (en) | 2016-06-15 |
TWI526515B (en) | 2016-03-21 |
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