TWI841611B - Protective sheet and laminate - Google Patents
Protective sheet and laminate Download PDFInfo
- Publication number
- TWI841611B TWI841611B TW108137421A TW108137421A TWI841611B TW I841611 B TWI841611 B TW I841611B TW 108137421 A TW108137421 A TW 108137421A TW 108137421 A TW108137421 A TW 108137421A TW I841611 B TWI841611 B TW I841611B
- Authority
- TW
- Taiwan
- Prior art keywords
- protective sheet
- meth
- adhesive
- hard coating
- less
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims abstract description 163
- 239000012790 adhesive layer Substances 0.000 claims abstract description 118
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000009864 tensile test Methods 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 84
- 239000011347 resin Substances 0.000 claims description 84
- 239000000853 adhesive Substances 0.000 claims description 77
- 230000001070 adhesive effect Effects 0.000 claims description 77
- 239000000178 monomer Substances 0.000 claims description 68
- 229920000058 polyacrylate Polymers 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000011248 coating agent Substances 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 48
- 239000011247 coating layer Substances 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 46
- 239000003431 cross linking reagent Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000003522 acrylic cement Substances 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000002723 alicyclic group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 206010040844 Skin exfoliation Diseases 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
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- 239000011521 glass Substances 0.000 description 26
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- 238000012360 testing method Methods 0.000 description 24
- 238000002834 transmittance Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
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- 238000011156 evaluation Methods 0.000 description 9
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
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- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 4
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- 125000005907 alkyl ester group Chemical group 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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Abstract
本發明之課題係提供一種具有優異的耐熱性之保護片、及具備該保護片之積層體。 本發明之解決手段係提供一種保護片，其係具備基材、及層積在前述基材的一面側的黏著劑層之保護片，將前述黏著劑層藉由拉伸試驗而得到在23℃的伸長率(%)設為E1 ，將前述黏著劑層在100℃加熱30分鐘後在該黏著劑層藉由拉伸試驗而得到在23℃的伸長率(%)設為E2 時，前述伸長率E2 對前述伸長率E1 的比值(E2 /E1 )為0.9以上且5以下，將前述黏著劑層在100℃加熱30分鐘後，該黏著劑層在23℃之損失正切tanδ為0.1以上且1以下。The subject of the present invention is to provide a protective sheet with excellent heat resistance and a laminate having the protective sheet. The solution of the present invention is to provide a protective sheet comprising a substrate and an adhesive layer laminated on one side of the substrate, wherein the elongation (%) of the adhesive layer at 23°C obtained by a tensile test is set as E1 , and the elongation (%) of the adhesive layer at 23°C obtained by a tensile test after the adhesive layer is heated at 100°C for 30 minutes is set as E2 , the ratio of the elongation E2 to the elongation E1 ( E2 / E1 ) is 0.9 or more and 5 or less, and the loss tangent tanδ of the adhesive layer at 23°C after the adhesive layer is heated at 100°C for 30 minutes is 0.1 or more and 1 or less.
Description
本發明係有關於一種能夠適合使用在用以保護光學構件等的表面之保護片、及具備該保護片之積層體。 The present invention relates to a protective sheet that can be used to protect the surface of optical components, etc., and a laminate having the protective sheet.
先前在光學構件、電子構件等的裝置，為了防止在加工、裝配、檢査等的步驟中在表面產生損傷，係有將由基材及黏著劑層所構成之黏著片作為保護片而貼附在該裝置表面之情形。該保護片係在沒有保護的必要之時點，被從裝置剝離。 Previously, in order to prevent damage to the surface of optical components, electronic components, etc. during processing, assembly, inspection, etc., an adhesive sheet consisting of a substrate and an adhesive layer was attached to the surface of the device as a protective sheet. The protective sheet was peeled off from the device when it was no longer necessary to protect it.
在上述的步驟，係有將裝置曝露在高溫環境下而進行處理之情形。在此種處理，貼附在該裝置之保護片亦被加熱。因此保護片係被要求具有預定的耐熱性。例如，保護片係被要求即便被加熱時，亦能夠維持對裝置的密著性且不產生未蓄意地從裝置剝落之情形。而且，保護片被要求即便在被加熱時，能夠良好地維持剝離性，在將保護片從裝置剝離時能夠容易地進行。 In the above steps, the device is exposed to a high temperature environment for processing. In this process, the protective sheet attached to the device is also heated. Therefore, the protective sheet is required to have a predetermined heat resistance. For example, the protective sheet is required to maintain close adhesion to the device even when heated and not to be unintentionally peeled off from the device. In addition, the protective sheet is required to maintain good releasability even when heated, so that the protective sheet can be easily peeled off from the device.
專利文獻1，係揭示一種實現如上述的耐熱性作為課題的表面保護膜用黏著劑。特別是專利文獻1係揭示一種表面保護膜用黏著劑，其特徵在於：在a)具有碳數8~10的烷基之(甲基)丙烯酸烷酯作為主成分之(甲基)丙烯酸烷酯100重量份，添加b)含羧基的共聚合性化合物1~15重量份、及c)碳數1~5的脂肪族羧酸的乙烯酯3~100重量份而成之單體混合物的共聚物中，調配相對於上述b成分的羧基為當量以上的交聯劑。 Patent document 1 discloses an adhesive for a surface protective film that realizes the above-mentioned heat resistance. In particular, Patent document 1 discloses an adhesive for a surface protective film, which is characterized in that: a crosslinking agent is formulated in an equivalent amount or more to the carboxyl group of the above-mentioned component b in a copolymer of a monomer mixture formed by adding 100 parts by weight of a (meth)acrylic acid alkyl ester having an alkyl group with 8 to 10 carbon atoms as a main component, 1 to 15 parts by weight of a copolymerizable compound containing a carboxyl group, and 3 to 100 parts by weight of a vinyl ester of an aliphatic carboxylic acid with 1 to 5 carbon atoms.
[專利文獻1]日本特開平11-256111號公報 [Patent Document 1] Japanese Patent Publication No. 11-256111
但是近年來，當作保護對象之裝置的種類、或在步驟所進行的處理的種類為多樣化，如專利文獻1所揭示之先前的保護片的耐熱性，係逐漸地變為不充分。特別是近年來，保護設置有硬塗層之面之情形增加，對此種硬塗層的表面使用先前的保護片時，係難以兼具在加熱處理後之密著性與剝離性。 However, in recent years, as the types of devices to be protected or the types of treatments performed in the steps have diversified, the heat resistance of the previous protective sheet disclosed in Patent Document 1 has gradually become insufficient. In particular, in recent years, the number of cases where a surface with a hard coating is protected has increased. When the previous protective sheet is used on the surface of such a hard coating, it is difficult to have both adhesion and releasability after heat treatment.
本發明係鑒於上述實際情況而進行，其目的係提供一種具有優異的耐熱性之保護片、及具備該保護片之積層體。 The present invention is made in view of the above practical situation, and its purpose is to provide a protective sheet with excellent heat resistance, and a laminate having the protective sheet.
為了達成上述目的，本發明第1係提供一種保護片，係具備基材、及層積在前述基材的一面側的黏著劑層之保護片，將前述黏著劑層藉由拉伸試驗而得到在23℃的伸長率(%)設為E1，將前述黏著劑層在100℃加熱30分鐘後該黏著劑層藉由拉伸試驗而得到在23℃的伸長率(%)設為E2時，前述伸長率E2對前述伸長率E1的比值(E2/E1)為0.9以上且5以下，將前述黏著劑層在100℃加熱30分鐘後該黏著劑層在23℃之損失正切tanδ為0.1以上且1以下(發明1)。 In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a protective sheet comprising a substrate and an adhesive layer laminated on one side of the substrate, wherein the elongation (%) of the adhesive layer at 23°C obtained by a tensile test is set as E1 , and the elongation (%) of the adhesive layer at 23°C obtained by a tensile test after the adhesive layer is heated at 100°C for 30 minutes is set as E2 , the ratio of the elongation E2 to the elongation E1 ( E2 / E1 ) is greater than 0.9 and less than 5, and the loss tangent tanδ of the adhesive layer at 23°C after the adhesive layer is heated at 100°C for 30 minutes is greater than 0.1 and less than 1 (Invention 1).
上述發明(發明1)之保護片，係藉由黏著劑層的伸長率之比值(E2/E1)為上述範圍，即便將保護片加熱時亦能夠維持黏著劑層的性狀，對被黏著物顯示良好的密著性，同時剝離時也能夠從被黏著物良好地剝離。而且藉由在加熱後之黏著劑層的損失正切tanδ為上述範圍，即便將保護片貼合在如硬塗層表面之存在微細凹凸的面時，黏著劑層亦能夠適當地追隨該凹凸，而且即便加熱後，亦能夠以高水準兼具良好的密著性與剝離性。 The protective sheet of the invention (Invention 1) is such that the ratio of the elongation of the adhesive layer (E 2 /E 1 ) is within the above range, and the properties of the adhesive layer can be maintained even when the protective sheet is heated, and good adhesion to the adherend can be exhibited, and the protective sheet can be well peeled off from the adherend when peeled off. Furthermore, since the loss tangent tanδ of the adhesive layer after heating is within the above range, even when the protective sheet is attached to a surface with fine irregularities such as the surface of a hard coating, the adhesive layer can appropriately follow the irregularities, and even after heating, good adhesion and peeling properties can be achieved at a high level.
在上述發明(發明1)，其中針對將前述保護片之黏著劑層側的面，對具備樹脂板及層積在前述樹脂板的一面側的硬塗層之附硬塗層樹脂板的前述硬塗層側的面進行貼合而成之積層體，將前述積層體在23℃、50%RH的環境下放置24小時後，將前述保護片剝離而露出的前述附硬塗層樹脂板之前述硬塗層側的面所測定的水接觸角(°)設為W1，將前述積層體在23℃、50%RH的環境下放置24小時，接著在100℃加熱30分鐘，進而在23℃、50%RH的環境下放置30分鐘之後，將前述保護片剝離而露出的前述附硬塗層樹脂板之前述硬塗層側的面所測定的水接觸角(°)設為W2時，前述水接觸角W2對前述水接觸角W1之比值(W2/W1)係以0.8以上且1.2以下為佳(發明2)。 In the above invention (Invention 1), with respect to a laminate formed by laminating the adhesive layer side surface of the protective sheet to the hard coating layer side surface of a hard coating layer-attached resin sheet having a resin sheet and a hard coating layer laminated on one side of the resin sheet, after the laminate is left in an environment of 23° C. and 50% RH for 24 hours, the water contact angle (°) measured at the hard coating layer side surface of the hard coating layer-attached resin sheet exposed by peeling off the protective sheet is set as W 1 The laminate is placed in an environment of 23°C and 50% RH for 24 hours, then heated at 100°C for 30 minutes, and further placed in an environment of 23°C and 50% RH for 30 minutes. When the water contact angle (°) of the surface of the hard coating layer side of the resin board with hard coating layer exposed by peeling off the protective sheet is set as W 2 , the ratio of the water contact angle W 2 to the water contact angle W 1 (W 2 /W 1 ) is preferably greater than 0.8 and less than 1.2 (Invention 2).
在上述發明(發明1、2)，其中前述保護片對具備樹脂板及層積在前述樹脂板的一面側的硬塗層之附硬塗層樹脂板的前述硬塗層側的面之黏著力，係以0.5N/25mm以上且10N/25mm以下為佳(發明3)。 In the above inventions (Inventions 1 and 2), the adhesion of the protective sheet to the hard coating layer side of the hard coating layer-attached resin sheet having a resin sheet and a hard coating layer laminated on one side of the resin sheet is preferably 0.5N/25mm or more and 10N/25mm or less (Invention 3).
在上述發明(發明1~3)，其中前述保護片之黏著劑層側的面對具備樹脂板及層積在前述樹脂板的一面側的硬塗層之附硬塗層樹脂板的前述硬塗層側的面進行貼合而成之積層體，在100℃加熱30分鐘之後，前述保護片對構成前述積層體之前述硬塗層之黏著力係以0.3N/25mm以上且10N/25mm以下為佳(發明4)。 In the above inventions (Inventions 1 to 3), the adhesive layer side of the aforementioned protective sheet is bonded to the aforementioned hard coating layer side of a hard coating layer-attached resin sheet having a resin sheet and a hard coating layer laminated on one side of the aforementioned resin sheet. After heating at 100°C for 30 minutes, the adhesion of the aforementioned protective sheet to the aforementioned hard coating layer constituting the aforementioned laminate is preferably 0.3N/25mm or more and 10N/25mm or less (Invention 4).
在上述發明(發明1~4)，係較佳是為了保護具備樹脂板及層積在前述樹脂板的一面側的硬塗層之附硬塗層樹脂板之前述硬塗層側的面而使用(發明5)。 In the above inventions (Inventions 1 to 4), it is preferably used to protect the surface of the hard coating layer side of a hard coating layer-attached resin board having a resin board and a hard coating layer layered on one side of the resin board (Invention 5).
本發明第2係提供一種積層體，其特徵在於具備：具備樹脂板及層積在前述樹脂板的一面側的硬塗層之附硬塗層樹脂板；及前述保護片(發明1~5)，前述保護片之黏著劑層側的面，層積在前述附硬塗層樹脂板之前述硬塗層側的面(發明6)。 The second aspect of the present invention provides a laminate, which is characterized by comprising: a hard-coated resin sheet having a resin sheet and a hard-coated layer laminated on one side of the resin sheet; and the protective sheet (Inventions 1 to 5), wherein the adhesive layer side of the protective sheet is laminated on the hard-coated layer side of the resin sheet (Invention 6).
本發明之保護片係具有優異的耐熱性。又，本發明之積層體係具備具有優異的耐熱性之保護片。 The protective sheet of the present invention has excellent heat resistance. In addition, the laminate of the present invention has a protective sheet with excellent heat resistance.
以下，說明本發明的實施形態。 The following describes the implementation of the present invention.
(保護片) (Protective film)
本實施形態之保護片係具備基材、及層積在該基材的一面側之黏著劑層。又，在本實施形態之保護片之黏著劑層側的面亦可層積剝離片，用以保護黏著劑層至使用保護片時為止。 The protective sheet of this embodiment has a substrate and an adhesive layer stacked on one side of the substrate. In addition, a peeling sheet can be stacked on the adhesive layer side of the protective sheet of this embodiment to protect the adhesive layer until the protective sheet is used.
1.保護片的物性 1. Physical properties of protective film
(1)伸長率 (1) Elongation
在本實施形態之保護片，將黏著劑層藉由拉伸試驗而得到在23℃的伸長率(%)設為E1，將黏著劑層在100℃加熱30分鐘後在該黏著劑層藉由拉伸試驗而得到在23℃的伸長率(%)設為E2時，上述伸長率E2對上述伸長率E1之比值(E2/E1)為0.9以上且5以下。上述比值(E2/E1)為該範圍時，在本實施形態之黏著劑層係成為即便被加熱時亦能夠良好地維持其性狀之物。藉此，本實施形態之保護片，係能夠抑制在步驟中及步驟完成後未蓄意地從被黏著物剝落。另一方面，欲將保護片從被黏著物剝離時，保護片不會過度強力地密著在被黏著物而能夠容易地剝離。 In the protective sheet of the present embodiment, when the elongation (%) of the adhesive layer at 23°C obtained by a tensile test is defined as E1 , and the elongation (%) of the adhesive layer at 23°C obtained by a tensile test after the adhesive layer is heated at 100°C for 30 minutes is defined as E2 , the ratio ( E2 / E1 ) of the elongation E2 to the elongation E1 is 0.9 or more and 5 or less. When the ratio ( E2 / E1 ) is within this range, the adhesive layer of the present embodiment can maintain its properties well even when heated. Thus, the protective sheet of the present embodiment can be prevented from being unintentionally peeled off from the adherend during the step and after the step is completed. On the other hand, when the protective sheet is to be peeled off from the adherend, the protective sheet does not adhere to the adherend too strongly and can be easily peeled off.
上述比值(E2/E1)小於0.9時，將保護片加熱時，構成黏著劑層之黏 著劑的凝聚性大大地喪失。因此，對被黏著物之密著性低落且會產生保護片從被黏著物未蓄意的剝落。從該觀點而言，上述比值(E2/E1)係以0.95以上為佳，以1.0以上為特佳。 When the ratio (E 2 /E 1 ) is less than 0.9, the cohesion of the adhesive constituting the adhesive layer is greatly lost when the protective sheet is heated. Therefore, the adhesion to the adherend is reduced and the protective sheet may be unintentionally peeled off from the adherend. From this point of view, the ratio (E 2 /E 1 ) is preferably 0.95 or more, and particularly preferably 1.0 or more.
而且，上述比值(E2/E1)大於5時，黏著劑層在加熱後對被黏著物之密著性過度地上升，致使難以將從被黏著物容易地剝離使用後的保護片。從該的觀點而言，上述比值(E2/E1)係以3以下為佳，以2以下為特佳，以1.2以下為更佳。 Furthermore, when the ratio (E 2 /E 1 ) is greater than 5, the adhesive layer excessively increases its adhesion to the adherend after heating, making it difficult to easily peel the protective sheet from the adherend after use. From this viewpoint, the ratio (E 2 /E 1 ) is preferably 3 or less, particularly preferably 2 or less, and even more preferably 1.2 or less.
在本實施形態之保護片，上述伸長率E1係以100%以上為佳，以120%以上為較佳，以150%以上為特佳，進而以200%以上為佳。又，上述伸長率E1係以1000%以下為佳，以600%以下為特佳，進而以300%以下為佳。藉由上述伸長率E1為該等範圍，容易將比值(E2/E1)調整成為上述範圍。 In the protective sheet of the present embodiment, the elongation E1 is preferably 100% or more, more preferably 120% or more, particularly preferably 150% or more, and further preferably 200% or more. Furthermore, the elongation E1 is preferably 1000% or less, particularly preferably 600% or less, and further preferably 300% or less. By setting the elongation E1 within these ranges, it is easy to adjust the ratio ( E2 / E1 ) to the above range.
在本實施形態之保護片，上述伸長率E2係以90%以上為佳，以100%以上為較佳，以120%以上為特佳，進而以150%以上為佳，以200%以上為最佳。又，上述伸長率E2係以1000%以下為佳，以600%以下為特佳，進而以300%以下為佳。藉由上述伸長率E2為該等範圍，容易將比值(E2/E1)調整成為上述範圍。 In the protective sheet of the present embodiment, the elongation E2 is preferably 90% or more, more preferably 100% or more, particularly preferably 120% or more, further preferably 150% or more, and most preferably 200% or more. Furthermore, the elongation E2 is preferably 1000% or less, particularly preferably 600% or less, and further preferably 300% or less. By setting the elongation E2 within these ranges, it is easy to adjust the ratio ( E2 / E1 ) to the above range.
又，上述伸長率E1及伸長率E2的測定方法之詳細，係如後述的試驗例所記載。 The details of the measuring method of the above-mentioned elongation E1 and elongation E2 are described in the test examples described later.
(2)損失正切tanδ (2) Loss tangent tanδ
在本實施形態之保護片，係將黏著劑層在100℃加熱30分鐘後，該黏著劑層在23℃之損失正切tanδ為0.1以上且1以下。藉由損失正切tanδ為上述範圍，加熱後的黏著劑層亦能夠良好地追隨在被黏著物表面存在的微細構造。例如在防眩性硬塗層表面係存在微細的凹凸，加熱後的黏著劑層即便對此種凹凸亦能夠良好地追隨且顯示適當的密著性。其結果，本實施形態之保護片即便被貼合在存在微細的凹凸之面時，亦能夠以高水準兼具優異的密著性與剝離性。 In the protective sheet of this embodiment, after the adhesive layer is heated at 100°C for 30 minutes, the loss tangent tanδ of the adhesive layer at 23°C is greater than 0.1 and less than 1. With the loss tangent tanδ being within the above range, the heated adhesive layer can also well follow the fine structure existing on the surface of the adherend. For example, there are fine unevenness on the surface of the anti-glare hard coating layer, and the heated adhesive layer can well follow such unevenness and show appropriate adhesion. As a result, the protective sheet of this embodiment can have both excellent adhesion and releasability at a high level even when it is attached to a surface with fine unevenness.
損失正切tanδ為小於0.1時，在保護片被加熱時，黏著劑層對被黏著物表面的微細構造之追隨性為大大地低落。藉此，被貼合在存在微細的凹凸之面的保護片產生未蓄意地剝落之問題。從該的觀點而言，損失正切tanδ係以0.12以上為佳，以0.15以上為特佳。 When the loss tangent tanδ is less than 0.1, the adhesive layer's ability to follow the fine structure of the adherend surface is greatly reduced when the protective sheet is heated. As a result, the protective sheet adhered to a surface with fine irregularities may peel off unintentionally. From this point of view, the loss tangent tanδ is preferably 0.12 or more, and particularly preferably 0.15 or more.
又，損失正切tanδ為大於1時，黏著劑層的操作性、生產性及加工性為大大地低落。從該的觀點而言，損失正切tanδ係以0.5以下為佳，以0.3以下為特佳。 Furthermore, when the loss tangent tanδ is greater than 1, the operability, productivity and processability of the adhesive layer are greatly reduced. From this point of view, the loss tangent tanδ is preferably less than 0.5, and particularly preferably less than 0.3.
本實施形態之保護片，黏著劑層在23℃之損失正切tanδ(亦即針對未進行上述的加熱之黏著劑層在23℃之損失正切tanδ)係以0.1以上為佳，以0.12以上為佳，進而以0.15以上為佳。又，上述損失正切tanδ係以1以下為佳，以0.5以下為佳，進而以0.3以下為佳。藉由黏著劑層在23℃之損失正切tanδ為該等範圍，容易將上述加熱後的黏著劑層在23℃之損失正切tanδ調整成為上述的範圍。 In the protective sheet of this embodiment, the loss tangent tanδ of the adhesive layer at 23°C (i.e., the loss tangent tanδ of the adhesive layer at 23°C without the above-mentioned heating) is preferably 0.1 or more, preferably 0.12 or more, and further preferably 0.15 or more. In addition, the above-mentioned loss tangent tanδ is preferably less than 1, preferably less than 0.5, and further preferably less than 0.3. By setting the loss tangent tanδ of the adhesive layer at 23°C to such ranges, it is easy to adjust the loss tangent tanδ of the above-mentioned heated adhesive layer at 23°C to the above-mentioned range.
又，上述在加熱前後之黏著劑層在23℃之損失正切tanδ的測定方法的詳細，係如在後述的試驗例所記載。 In addition, the details of the method for measuring the loss tangent tanδ of the adhesive layer before and after heating at 23°C are described in the test examples described below.
(3)儲存彈性模數 (3)Store elastic modulus
在本實施形態之保護片，黏著劑層在23℃之儲存彈性模數係以0.01MPa以上為佳，以0.08MPa以上為特佳，進而以0.12MPa以上為佳。又，上述儲存彈性模數係以2MPa以下為佳，以1MPa以下為較佳，以0.8MPa以下為特佳，進而以0.4MPa以下為佳。 In the protective sheet of this embodiment, the storage elastic modulus of the adhesive layer at 23°C is preferably 0.01MPa or more, particularly preferably 0.08MPa or more, and further preferably 0.12MPa or more. In addition, the above storage elastic modulus is preferably 2MPa or less, more preferably 1MPa or less, particularly preferably 0.8MPa or less, and further preferably 0.4MPa or less.
又，本實施形態之保護片，將黏著劑層在100℃加熱30分鐘後，該黏著劑層在23℃之儲存彈性模數係以0.01MPa以上為佳，以0.08MPa以上為特佳，進而以0.12MPa以上為佳。又，上述儲存彈性模數係以2MPa以下為佳，以1MPa以下為較佳，以0.8MPa以下為特佳，進而以0.4MPa以下為佳。 In addition, in the protective sheet of this embodiment, after the adhesive layer is heated at 100°C for 30 minutes, the storage elastic modulus of the adhesive layer at 23°C is preferably 0.01MPa or more, particularly preferably 0.08MPa or more, and further preferably 0.12MPa or more. In addition, the above storage elastic modulus is preferably 2MPa or less, more preferably 1MPa or less, particularly preferably 0.8MPa or less, and further preferably 0.4MPa or less.
藉由在上述加熱前後之儲存彈性模數係各自為上述範圍，容易將 前述加熱後的黏著劑層在23℃之損失正切tanδ調整成為上述的範圍。又，在上述加熱前後之儲存彈性模數的測定方法的詳細係各自如在後述的試驗例所記載。 By making the storage elastic modulus before and after the above heating each within the above range, it is easy to adjust the loss tangent tanδ of the adhesive layer at 23°C after the above heating to the above range. In addition, the details of the measurement method of the storage elastic modulus before and after the above heating are described in the test examples described below.
(4)水接觸角 (4) Water contact angle
在本實施形態之保護片，係貼合在預定被黏著物且放置在預定條件下之後，將保護片剝離而露出之上述被黏著物的露出面，係以表示如以下說明的水接觸角為佳。 In this embodiment, the protective sheet is attached to a predetermined adherend and placed under predetermined conditions. After the protective sheet is peeled off, the exposed surface of the adherend is preferably expressed as a water contact angle as described below.
首先，保護片之黏著劑層側的面對具備樹脂板及層積在前述樹脂板的一面側的硬塗層之附硬塗層樹脂板之上述硬塗層側的面進行貼合而成的積層體，設為第1積層體。 First, a laminated body is formed by bonding the adhesive layer side of the protective sheet to the hard coating layer side of a hard coating layer-attached resin sheet having a resin sheet and a hard coating layer laminated on one side of the resin sheet, and this is referred to as the first laminated body.
然後，將上述第1積層體放置在23℃、50%RH的環境下24小時後，在將保護片從第1積層體剝離而露出的附硬塗層樹脂板之硬塗層側的面所測定之水接觸角(°)設為W1。 Then, the first laminate was placed in an environment of 23°C and 50% RH for 24 hours, and the water contact angle (°) measured on the hard coating layer side of the hard coating resin board exposed after the protective sheet was peeled off from the first laminate was defined as W 1 .
又，將上述第1積層體在23℃、50%RH的環境下放置24小時，接著在100℃加熱30分鐘，進而在23℃、50%RH的環境下放置30分鐘之後，在將保護片從第1積層體剝離而露出的附硬塗層樹脂板之硬塗層側的面所測定之水接觸角(°)設為W2。 The first laminate was placed in an environment of 23°C and 50% RH for 24 hours, then heated at 100°C for 30 minutes, and then placed in an environment of 23°C and 50% RH for 30 minutes. The protective sheet was peeled off from the first laminate, and the water contact angle (°) measured on the hard coating layer side of the hard coating resin sheet exposed was defined as W 2 .
此時，上述水接觸角W2對上述水接觸角W1之比值(W2/W1)係以0.8以上為佳，以0.88以上為特佳，進而以0.98以上為佳。又，上述比值(W2/W1)係以1.2以下為佳，以1.1以下為特佳，進而以1.05以下為佳。上述比值(W2/W1)為該等範圍時，在本實施形態之黏著劑層係能夠有效地抑制在加熱前後之性狀變化，藉此，即便在將本實施形態的保護片加熱之情況，亦容易對被黏著物兼具優異的密著性與剝離性。 At this time, the ratio of the water contact angle W2 to the water contact angle W1 ( W2 / W1 ) is preferably 0.8 or more, particularly preferably 0.88 or more, and further preferably 0.98 or more. In addition, the ratio ( W2 / W1 ) is preferably 1.2 or less, particularly preferably 1.1 or less, and further preferably 1.05 or less. When the ratio ( W2 / W1 ) is within these ranges, the adhesive layer of the present embodiment can effectively suppress the change in properties before and after heating, thereby, even when the protective sheet of the present embodiment is heated, it is easy to have both excellent adhesion and releasability to the adherend.
又，上述水接觸角W1係以40°以上為佳，以50°以上為較佳，以60°以上為特佳，進而以68°以上為佳。又，上述水接觸角W1係以90°以下為佳，以 80°以下為特佳，進而以72°以下為佳。藉由上述水接觸角W1為該等範圍，容易將比值(W2/W1)調整成為上述的範圍。 Furthermore, the water contact angle W1 is preferably 40° or more, more preferably 50° or more, particularly preferably 60° or more, and further preferably 68° or more. Furthermore, the water contact angle W1 is preferably 90° or less, particularly preferably 80° or less, and further preferably 72° or less. By setting the water contact angle W1 within these ranges, it is easy to adjust the ratio ( W2 / W1 ) to the above range.
而且，上述水接觸角W2係以40°以上為佳，以50°以上為較佳，以60°以上為特佳，進而以70°以上為佳。又，上述水接觸角W2係以95°以下為佳，以85°以下為特佳，進而以75°以下為佳。藉由上述水接觸角W2為該等範圍，容易將比值(W2/W1)調整成為上述的範圍。 Furthermore, the water contact angle W2 is preferably 40° or more, more preferably 50° or more, particularly preferably 60° or more, and further preferably 70° or more. Furthermore, the water contact angle W2 is preferably 95° or less, particularly preferably 85° or less, and further preferably 75° or less. By setting the water contact angle W2 within these ranges, it is easy to adjust the ratio ( W2 / W1 ) to the above range.
其次，將保護片之黏著劑層側的面對玻璃板的一面進行貼合而成之積層體設為第2積層體。 Next, the laminate formed by laminating the adhesive layer side of the protective sheet to the side facing the glass plate is set as the second laminate.
然後，將上述第2積層體在23℃、50%RH的環境下放置在24小時後，在將保護片從第2積層體剝離而露出之玻璃板的露出面所測定之水接觸角(°)設為W3。 Then, the second laminate was left in an environment of 23°C and 50% RH for 24 hours, and the water contact angle (°) measured on the exposed surface of the glass plate after the protective sheet was peeled off from the second laminate was defined as W 3 .
又，將上述第2積層體在23℃、50%RH的環境下放置24小時，接著在100℃加熱30分鐘，進而在23℃、50%RH的環境下放置30分鐘後，在將保護片從第2積層體剝離而露出之玻璃板的露出面所測定之水接觸角(°)設為W4。 The second laminate was placed in an environment of 23°C and 50% RH for 24 hours, then heated at 100°C for 30 minutes, and then placed in an environment of 23°C and 50% RH for 30 minutes. The water contact angle (°) measured on the exposed surface of the glass plate exposed by peeling the protective sheet from the second laminate was set as W 4 .
此時，上述水接觸角W4對上述水接觸角W3之比值(W4/W3)係以1以上為佳，以2以上為特佳，進而以3以上為佳。又，上述比值(W4/W3)係以6以下為佳，以5以下為特佳，進而以4以下為佳。上述比值(W4/W3)為該等範圍時，在本實施形態之黏著劑層，係能夠有效地抑制在加熱前後之性狀變化，藉此，即便本實施形態之保護片被加熱時，亦容易對被黏著物兼具優異的密著性與剝離性。 At this time, the ratio (W 4 /W 3 ) of the water contact angle W 4 to the water contact angle W 3 is preferably 1 or more, particularly preferably 2 or more, and further preferably 3 or more. Furthermore, the ratio (W 4 /W 3 ) is preferably 6 or less, particularly preferably 5 or less, and further preferably 4 or less. When the ratio (W 4 /W 3 ) is within these ranges, the adhesive layer of the present embodiment can effectively suppress the change in properties before and after heating, thereby, even when the protective sheet of the present embodiment is heated, it is easy to have both excellent adhesion and releasability to the adherend.
又，上述水接觸角W3係以5°以上為佳，以10°以上為特佳，進而以15°以上為佳。而且上述水接觸角W3係以60°以下為佳，以50°以下為較佳，以40°以下為特佳，進而以30°以下為佳，以20°以下為最佳。藉由上述水接觸角W3為該等範圍，容易將比值(W4/W3)調整成為上述的範圍。 Furthermore, the water contact angle W3 is preferably 5° or more, particularly 10° or more, and further preferably 15° or more. Furthermore, the water contact angle W3 is preferably 60° or less, more preferably 50° or less, particularly preferably 40° or less, further preferably 30° or less, and most preferably 20° or less. By setting the water contact angle W3 within these ranges, it is easy to adjust the ratio ( W4 / W3 ) to the above range.
而且，上述水接觸角W4係以30°以上為佳，以40°以上為特佳，進而以50°以上為佳。又，上述水接觸角W4係以95°以下為佳，以85°以下為較佳，以75°以下為特佳，進而以60°以下為佳。藉由上述水接觸角W4為該等範圍，容易將比值(W4/W3)調整成為的範圍。 Furthermore, the water contact angle W4 is preferably 30° or more, particularly 40° or more, and further preferably 50° or more. Furthermore, the water contact angle W4 is preferably 95° or less, more preferably 85° or less, particularly 75° or less, and further preferably 60° or less. By setting the water contact angle W4 within these ranges, it is easy to adjust the ratio ( W4 / W3 ) to the range.
又，以上的水接觸角W1、W2、W3及W4的測定方法的詳細，如在後述的試驗例所記載。 The details of the method for measuring the above water contact angles W 1 , W 2 , W 3 , and W 4 are described in the test examples described later.
(5)黏著力 (5) Adhesion
在本實施形態之保護片，對具備樹脂板及層積在該樹脂板的一面側的硬塗層之附硬塗層樹脂板的該硬塗層側的面之黏著力係以0.5N/25mm以上為佳，以0.7N/25mm以上為特佳，進而以0.9N/25mm以上為佳。又，上述黏著力係以10N/25mm以下為佳，以5N/25mm以下為較佳，以2N/25mm以下為特佳，進而以1.5N/25mm以下為佳。藉由上述黏著力為0.5N/25mm以上，保護片容易良好地密著在附硬塗層樹脂板且在步驟中等能夠有效地抑制未蓄意的剝落。又，藉由上述黏著力為10N/25mm以下，更容易將保護片從附硬塗層樹脂板剝離。 In the protective sheet of the present embodiment, the adhesion of the hard-coated resin sheet with a resin sheet and the hard-coated layer layered on one side of the resin sheet to the hard-coated layer side is preferably 0.5N/25mm or more, particularly preferably 0.7N/25mm or more, and further preferably 0.9N/25mm or more. In addition, the above-mentioned adhesion is preferably 10N/25mm or less, more preferably 5N/25mm or less, particularly preferably 2N/25mm or less, and further preferably 1.5N/25mm or less. With the above-mentioned adhesion of 0.5N/25mm or more, the protective sheet can be easily and well adhered to the hard-coated resin sheet and can effectively suppress unintentional peeling during the steps. Furthermore, since the above-mentioned adhesive force is less than 10N/25mm, it is easier to peel the protective sheet from the hard-coated resin board.
又，在本實施形態之保護片，保護片之黏著劑層側的面對具備樹脂板及層積在該樹脂板的一面側的硬塗層之附硬塗層樹脂板的硬塗層側的面進行貼合而成之積層體，在100℃加熱30分鐘之後，保護片對構成該積層體的硬塗層之黏著力係以0.3N/25mm以上為佳，以0.5N/25mm以上為特佳，進而以0.65N/25mm以上為佳。又，上述黏著力係以10N/25mm以下為佳，以5N/25mm以下為特佳，進而以2N/25mm以下為佳。藉由上述黏著力為0.3N/25mm以上，即便加熱後，保護片亦容易良好地密著在附硬塗層樹脂板且在加熱處理後能夠有效地抑制未蓄意的剝落。又，藉由上述黏著力為10N/25mm以下，即便加熱後亦更容易將保護片從附硬塗層樹脂板剝離。 Furthermore, in the protective sheet of the present embodiment, the adhesive layer side of the protective sheet faces the hard coating layer side of the hard coating layer of the resin sheet with the resin sheet and the hard coating layer laminated on one side of the resin sheet, and after heating at 100°C for 30 minutes, the adhesive force of the protective sheet to the hard coating layer constituting the laminate is preferably 0.3N/25mm or more, particularly preferably 0.5N/25mm or more, and further preferably 0.65N/25mm or more. Furthermore, the above-mentioned adhesive force is preferably 10N/25mm or less, particularly preferably 5N/25mm or less, and further preferably 2N/25mm or less. With the above-mentioned adhesive force being 0.3N/25mm or more, the protective sheet can be easily and well adhered to the hard-coated resin sheet even after heating, and can effectively suppress unintentional peeling after heating. In addition, with the above-mentioned adhesive force being 10N/25mm or less, it is easier to peel the protective sheet from the hard-coated resin sheet even after heating.
而且，在本實施形態之保護片，對玻璃板之黏著力以0.1N/25mm 以上為佳，以0.2N/25mm以上為特佳，進而以0.3N/25mm以上為佳。又，上述黏著力係以10N/25mm以下為佳，以5N/25mm以下為較佳，以2N/25mm以下為特佳，進而以0.8N/25mm以下為佳。藉由上述黏著力為0.1N/25mm以上，保護片對玻璃板容易良好地密著且在步驟中等能夠有效地抑制未蓄意的剝落。又，藉上述黏著力為10N/25mm以下，更容易將保護片從玻璃板剝離。 Moreover, in the present embodiment, the adhesion of the protective sheet to the glass plate is preferably 0.1N/25mm or more, particularly preferably 0.2N/25mm or more, and further preferably 0.3N/25mm or more. Furthermore, the above-mentioned adhesion is preferably 10N/25mm or less, preferably 5N/25mm or less, particularly preferably 2N/25mm or less, and further preferably 0.8N/25mm or less. With the above-mentioned adhesion of 0.1N/25mm or more, the protective sheet can be easily well adhered to the glass plate and can effectively suppress unintentional peeling during the steps. Moreover, with the above-mentioned adhesion of 10N/25mm or less, it is easier to peel the protective sheet from the glass plate.
又，在本實施形態之保護片，保護片之黏著劑層側的面對玻璃板的一面進行貼合而成之積層體在100℃加熱30分鐘後，保護片對構成該積層體的玻璃板之黏著力以0.1N/25mm以上為佳，以0.2N/25mm以上為特佳，進而以0.5N/25mm以上為佳。又，上述黏著力以10N/25mm以下為佳，以5N/25mm以下為較佳，以2N/25mm以下為特佳，進而以1N/25mm以下為佳。藉由上述黏著力為0.1N/25mm以上，即便在加熱後，保護片對玻璃板亦容易良好地密著且在加熱處理後能夠有效地抑制未蓄意的剝落。又，藉由上述黏著力為10N/25mm以下，即便加熱後亦更容易將保護片從玻璃板剝離。 Furthermore, in the protective sheet of the present embodiment, after the laminate formed by bonding the side of the protective sheet with the adhesive layer facing the glass plate is heated at 100°C for 30 minutes, the adhesion of the protective sheet to the glass plate constituting the laminate is preferably 0.1N/25mm or more, particularly preferably 0.2N/25mm or more, and further preferably 0.5N/25mm or more. Furthermore, the above-mentioned adhesion is preferably 10N/25mm or less, more preferably 5N/25mm or less, particularly preferably 2N/25mm or less, and further preferably 1N/25mm or less. With the above-mentioned adhesion of 0.1N/25mm or more, the protective sheet can be easily and well adhered to the glass plate even after heating and can effectively suppress unintentional peeling after the heat treatment. Furthermore, since the above-mentioned adhesive force is less than 10N/25mm, it is easier to peel the protective sheet from the glass plate even after heating.
又，以上4種黏著力的測定方法的詳細係如在後述的試驗例所記載。 In addition, the details of the above four methods for measuring adhesion are described in the test examples described below.
(6)被黏著物的總光線透射率的變化率 (6) Change rate of total light transmittance of the adherend
本實施形態之保護片，將保護片對被黏著物進行貼合而成之積層體在23℃、50%RH的環境下放置24小時且在100℃加熱30分鐘，而且藉由在23℃、50%RH的環境下靜置30分鐘靜置而返回至室溫為止之後，設想將保護片從積層體剝離時，相對於對將保護片貼合在被黏著物之前的被黏著物所測定的總光線透射率，進行上述加熱及剝離之後的被黏著物所測定的總光線透射率的變化率以5%以下為佳，以3%以下為較佳，以1%以下為特佳，進而以0%(亦即總光線透射率沒有變化)為佳。藉由上述變化率為5%以下，由本實施形態之保護片保護之被黏著物容易發揮所需要的性能。又，上述總光線透射率的測定方法的詳細係 如在後述的試驗例所記載。 In the protective sheet of this embodiment, the laminate formed by laminating the protective sheet to the adherend is placed in an environment of 23°C and 50%RH for 24 hours and heated at 100°C for 30 minutes. After being left still in the environment of 23°C and 50%RH for 30 minutes and then returned to room temperature, it is assumed that when the protective sheet is peeled off from the laminate, the change rate of the total light transmittance measured for the adherend after the above heating and peeling, relative to the total light transmittance measured for the adherend before the protective sheet is laminating to the adherend, is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, and further preferably 0% (i.e., no change in total light transmittance). By making the above-mentioned change rate less than 5%, the adherend protected by the protective sheet of this embodiment can easily exhibit the required performance. In addition, the details of the above-mentioned total light transmittance measurement method are as described in the test examples described later.
2.構成保護片之各構件 2. Various components that make up the protective sheet
(1)基材 (1) Base material
作為在本實施形態之基材，係只要能夠層積黏著劑層就沒有特別限定，較佳是使用按照本實施形態之保護片的用途之物。例如，在貼合有本實施形態之保護片之狀態下將裝置曝露在高溫環境下時，作為基材，係以對所施加的溫度(例如90~150°)具有耐熱性之物為佳。又，隔著本實施形態之保護片而進行裝置的發光檢査時，作為基材，係以使用對該檢査所使用的波長的光線具有透過性之物為佳。 The substrate in the present embodiment is not particularly limited as long as it can be laminated with an adhesive layer, and it is preferably used in accordance with the purpose of the protective sheet of the present embodiment. For example, when the device is exposed to a high temperature environment with the protective sheet of the present embodiment attached, it is preferable to use a substrate that is heat-resistant to the applied temperature (e.g., 90 to 150°). In addition, when the device is subjected to a luminescence inspection through the protective sheet of the present embodiment, it is preferable to use a substrate that is transparent to the wavelength of light used in the inspection.
作為基材的具體例，係以由聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等的聚酯、二乙醯纖維素、三乙醯纖維素、乙醯基丁酸纖維素等的纖維素、聚乙烯、聚丙烯等的聚烯烴、聚醯亞胺、聚醚醯亞胺、聚碳酸酯、聚甲基戊烯、聚苯硫醚(polyphenylene sulfide)、聚氯乙烯、聚偏二氯乙烯(polyvinylidene chloride)、聚乙烯醇、乙烯-乙酸乙烯酯共聚物、聚苯乙烯、聚碸、聚醚醚酮、聚醚碸、氟樹脂、聚醯胺、丙烯酸樹脂、降莰烯系樹脂、環烯烴樹脂、液晶聚合物等的樹脂所構成之塑膠膜為佳。又，該等塑膠膜可為由單層所構成之薄膜，亦可為將同種或異種的複數層層積而成之薄膜。 Specific examples of the substrate include polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, celluloses such as diacetyl cellulose, triacetyl cellulose, and cellulose acetyl butyrate, polyolefins such as polyethylene and polypropylene, polyimide, polyetherimide, polycarbonate, polymethylpentene, polyphenylene sulfide, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polysulfone, polyetheretherketone, polyethersulfone, fluororesin, polyamide, acrylic resin, norbornene resin, cycloolefin resin, liquid crystal polymer, and the like. Furthermore, the plastic films may be films composed of a single layer or films formed by laminating multiple layers of the same or different types.
在基材，基於提升與黏著劑層的密著性之目的，亦可對層積黏著劑層之面，施行使用氧化法、凹凸化法等之表面處理、或底漆(primer)處理。作為上述氧化法，例如可舉出電暈放電處理、電漿放電處理、鉻氧化處理(濕式)、火焰處理、熱風處理、臭氧、紫外線照射處理等，又，作為凹凸化法，例如可舉出噴砂處理法、熱噴塗處理法等。該等表面處理法係能夠按照基材的種類而適當地選擇。 In order to improve the adhesion with the adhesive layer, the surface of the laminated adhesive layer may be subjected to surface treatment such as oxidation, embossing, or primer treatment. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of the embossing method include sandblasting and thermal spraying. These surface treatment methods can be appropriately selected according to the type of substrate.
基材的厚度係沒有特別限定，以保護片能夠充分地達成保護功能 之厚度為佳。例如，基材的厚度以10μm以上為佳，以25μm以上為特佳，進而以38μm以上為佳。又，基材的厚度係以200μm以下為佳，以175μm以下為特佳，進而以150μm以下為佳。 The thickness of the substrate is not particularly limited, and the thickness is preferably such that the protective sheet can fully achieve the protective function. For example, the thickness of the substrate is preferably 10 μm or more, particularly preferably 25 μm or more, and further preferably 38 μm or more. In addition, the thickness of the substrate is preferably 200 μm or less, particularly preferably 175 μm or less, and further preferably 150 μm or less.
(2)黏著劑層 (2) Adhesive layer
在本實施形態作為構成黏著劑層之黏著劑，係只要滿足前述比值(E2/E1)之同時，在加熱後之損失正切tanδ為前述範圍，而且具有作為保護片的預定密著性及剝離性之物，就沒有特別限定。特別是作為構成黏著劑層之黏著劑，係以丙烯酸系黏著劑、聚矽氧系黏著劑、橡膠系黏著劑及胺甲酸酯系黏著劑等為佳，尤其是從容易滿足上述物性的觀點而言，係以丙烯酸系黏著劑為佳。 In the present embodiment, the adhesive constituting the adhesive layer is not particularly limited as long as it satisfies the aforementioned ratio (E 2 /E 1 ), has a loss tangent tanδ after heating within the aforementioned range, and has predetermined adhesion and releasability as a protective sheet. In particular, the adhesive constituting the adhesive layer is preferably an acrylic adhesive, a silicone adhesive, a rubber adhesive, or a urethane adhesive. In particular, from the viewpoint of easily satisfying the aforementioned physical properties, an acrylic adhesive is preferred.
丙烯酸系黏著劑係以從含(甲基)丙烯酸酯聚合物(A)之黏著性組合物(以下有稱為「黏著性組合物P」之情形)所得到之物為佳。黏著性組合物P係除了(甲基)丙烯酸酯聚合物(A)以外，以亦含有交聯劑(B)為佳。又，在本說明書，所謂(甲基)丙烯酸，係意味著丙烯酸及甲基丙烯酸之雙方。其它類似用語亦同樣。又，「聚合物」亦包含「共聚物」的概念之物。 The acrylic adhesive is preferably obtained from an adhesive composition containing a (meth)acrylate polymer (A) (hereinafter referred to as "adhesive composition P"). The adhesive composition P preferably contains a crosslinking agent (B) in addition to the (meth)acrylate polymer (A). In addition, in this specification, the so-called (meth)acrylic acid means both acrylic acid and methacrylic acid. Other similar terms are the same. In addition, "polymer" also includes the concept of "copolymer".
(2-1)(甲基)丙烯酸酯聚合物(A) (2-1) (Meth)acrylate polymer (A)
(甲基)丙烯酸酯聚合物(A)係以含有(甲基)丙烯酸烷酯作為構成該聚合物之單體單元為佳。藉此，容易顯現良好的黏著性。烷基可為直鏈狀或分枝鏈狀。 The (meth)acrylate polymer (A) preferably contains (meth)acrylate alkyl as a monomer unit constituting the polymer. This makes it easy to exhibit good adhesion. The alkyl group can be a straight chain or a branched chain.
作為(甲基)丙烯酸烷酯，從黏著性的觀點而言，係以具有直鏈狀或分枝鏈狀烷基之同時，該烷基的碳數為1~20之(甲基)丙烯酸烷酯為佳。作為此種烷基的碳數為1~20之(甲基)丙烯酸烷酯，例如可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸棕櫚酯、(甲基)丙烯酸硬脂酸酯等。尤其是從進一步提升黏著性的觀點而言，係以烷 基的碳數為3~8之丙烯酸烷酯為佳，以使用丙烯酸正丁酯及丙烯酸2-乙基己酯的至少一者為特佳。又，該等可單獨使用，亦可組合2種以上而使用。 As the (meth)acrylic acid alkyl ester, from the viewpoint of adhesiveness, it is preferred that the alkyl ester has a linear or branched chain alkyl group and the carbon number of the alkyl group is 1 to 20. Examples of such alkyl esters having an alkyl group having a carbon number of 1 to 20 include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, and stearic (meth)acrylate. In particular, from the viewpoint of further improving adhesiveness, it is preferred that the alkyl ester has an alkyl group having a carbon number of 3 to 8, and it is particularly preferred to use at least one of n-butyl acrylate and 2-ethylhexyl acrylate. Furthermore, these can be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)，係以含有40質量%以上的(甲基)丙烯酸烷酯作為構成該聚合物之單體單元為佳，以含有60質量%以上為佳，以含有80質量%以上為特佳。(甲基)丙烯酸烷酯的含量之下限值為上述時，(甲基)丙烯酸酯聚合物(A)係能夠發揮適合的黏著性。又，(甲基)丙烯酸酯聚合物(A)係以含有99質量%以下的(甲基)丙烯酸烷酯作為構成該聚合物之單體單元為佳，以含有95質量%以下為特佳，進而以含有92質量%以下為佳。(甲基)丙烯酸烷酯的含量之上限值為上述時，容易將適合量之含反應性官能基的單體等的其它單體成分導入至(甲基)丙烯酸酯聚合物(A)中。 The (meth)acrylate polymer (A) preferably contains 40% by mass or more of (meth)acrylate alkyl as a monomer unit constituting the polymer, preferably 60% by mass or more, and particularly preferably 80% by mass or more. When the lower limit of the content of the (meth)acrylate alkyl is as described above, the (meth)acrylate polymer (A) can exhibit suitable adhesion. In addition, the (meth)acrylate polymer (A) preferably contains 99% by mass or less of (meth)acrylate alkyl as a monomer unit constituting the polymer, particularly preferably 95% by mass or less, and further preferably 92% by mass or less. When the upper limit of the content of the (meth)acrylate alkyl is as described above, it is easy to introduce a suitable amount of other monomer components such as a monomer containing a reactive functional group into the (meth)acrylate polymer (A).
(甲基)丙烯酸酯聚合物(A)係以在分子內含有具有能夠與上述交聯劑(B)反應的反應性基之含反應性基單體作為構成該聚合物之單體單元為佳。源自該含反應性基單體的反應性基與交聯劑(B)反應而形成交聯結構(三維網狀結構)且能夠得到具有所需要的凝聚力之黏著劑。 The (meth)acrylate polymer (A) preferably contains a reactive group-containing monomer having a reactive group capable of reacting with the crosslinking agent (B) as a monomer unit constituting the polymer. The reactive group derived from the reactive group-containing monomer reacts with the crosslinking agent (B) to form a crosslinking structure (three-dimensional network structure) and can obtain an adhesive having the required cohesive force.
作為上述含反應性基單體，以可舉出在分子內具有羥基之單體(含羥基單體)、在分子內具有羧基之單體(含羧基單體)、及在分子內具有胺基之單體(含胺基單體)等為佳。該等之中，係以與交聯劑(B)具有優異的反應且對被黏著物的不良影響較少之含羥基單體及含羧基單體的至少一者為特佳。 As the above-mentioned reactive group-containing monomer, monomers having a hydroxyl group in the molecule (hydroxyl-containing monomer), monomers having a carboxyl group in the molecule (carboxyl-containing monomer), and monomers having an amino group in the molecule (amino-containing monomer) are preferred. Among them, at least one of a hydroxyl-containing monomer and a carboxyl-containing monomer that has an excellent reaction with the crosslinking agent (B) and has less adverse effects on the adherend is particularly preferred.
作為含羥基單體，例如可舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等的(甲基)丙烯酸羥基烷酯等。尤其是在所得到的(甲基)丙烯酸酯聚合物(A)之羥基與交聯劑(B)的反應性及與其它單體的共聚合性而言，係以(甲基)丙烯酸2-羥基乙酯為佳、而且從所形成的黏著劑層容易滿足有關前述伸長率之比值(E2/E1)及損失正切tanδ的觀點而言，係以甲基丙 烯酸2-羥基乙酯為佳。該等可單獨使用，亦可組合2種以上而使用。 Examples of the hydroxyl group-containing monomer include hydroxyl alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. In particular, 2-hydroxyethyl (meth)acrylate is preferred from the viewpoint of the reactivity of the hydroxyl group of the obtained (meth)acrylate polymer (A) with the crosslinking agent (B) and the copolymerizability with other monomers. Furthermore, 2-hydroxyethyl methacrylate is preferred from the viewpoint that the formed adhesive layer easily satisfies the above-mentioned elongation ratio (E 2 /E 1 ) and loss tangent tan δ. These monomers may be used alone or in combination of two or more.
作為含羧基單體，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、順丁烯二酸、伊康酸(itaconic acid)、檸康酸等的乙烯性不飽和羧酸。尤其是就在所得到的(甲基)丙烯酸酯聚合物(A)之羧基與交聯劑(B)的反應性及與其它單體的共聚合性而言，係以丙烯酸為佳。該等可單獨使用，亦可組合2種以上而使用。 As carboxyl group-containing monomers, for example, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, succinic acid, itaconic acid, and citric acid can be cited. In particular, acrylic acid is preferred in terms of the reactivity of the carboxyl group of the obtained (meth)acrylate polymer (A) with the crosslinking agent (B) and the copolymerizability with other monomers. These monomers can be used alone or in combination of two or more.
作為含胺基單體，例如可舉出(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸正丁基胺基乙酯等。該等可單獨使用，亦可組合2種以上而使用。 As the amino group-containing monomer, for example, aminoethyl (meth)acrylate, n-butylaminoethyl (meth)acrylate, etc. can be cited. These can be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)係以含有下限值為1質量%以上之含反應性基單體作為構成該聚合物之單體單元為佳，以含有2質量%以上為較佳，以含有4質量%以上為特佳。又，含反應性基單體為含羧基單體時，係以含有8質量%以上為更佳。又，(甲基)丙烯酸酯聚合物(A)係以含有上限值為25質量%以下之含反應性基單體作為構成該聚合物之單體單元為佳，以含有18質量%以下為較佳，以含有12質量%以下為特佳。又，含反應性基單體為含羥基單體時，係以含有8質量%以下為更佳。(甲基)丙烯酸酯聚合物(A)係以上述量含有含反應性基單體作為單體單元時，在所得到的黏著劑能夠形成良好的交聯結構且容易得到所需要的凝聚力。藉此，所形成的黏著劑層係容易滿足有關前述伸長率的比值(E2/E1)及損失正切tanδ。 The (meth)acrylate polymer (A) preferably contains a reactive group-containing monomer having a lower limit of 1% by mass or more as a monomer unit constituting the polymer, preferably contains 2% by mass or more, and particularly preferably contains 4% by mass or more. Furthermore, when the reactive group-containing monomer is a carboxyl group-containing monomer, it is more preferably contained at 8% by mass or more. Furthermore, the (meth)acrylate polymer (A) preferably contains a reactive group-containing monomer having an upper limit of 25% by mass or less as a monomer unit constituting the polymer, preferably contains 18% by mass or less, and particularly preferably contains 12% by mass or less. Furthermore, when the reactive group-containing monomer is a hydroxyl group-containing monomer, it is more preferably contained at 8% by mass or less. When the (meth)acrylate polymer (A) contains the reactive group-containing monomer as a monomer unit in the above amount, the resulting adhesive can form a good cross-linked structure and easily obtain the required cohesive force. Thus, the formed adhesive layer can easily satisfy the above-mentioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
(甲基)丙烯酸酯聚合物(A)係含有在分子內具有脂環式結構之單體(含脂環式結構單體)作為構成該聚合物之單體單元亦佳。因為含脂環式結構單體較大型，藉由使其在聚合物中存在，推定使聚合物彼此之間隔擴大且所得到的黏著劑成為具有預定柔軟性之物。藉此，黏著劑層係容易滿足有關前述伸長率的比值(E2/E1)及損失正切tanδ。 The (meth)acrylate polymer (A) preferably contains a monomer having an alicyclic structure in the molecule (alicyclic structure-containing monomer) as a monomer unit constituting the polymer. Since the alicyclic structure-containing monomer is relatively large, the presence of the monomer in the polymer is expected to increase the spacing between the polymers and provide the adhesive with a predetermined softness. As a result, the adhesive layer is likely to satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
在含脂環式結構單體之脂環式結構的碳環，可為飽和構造之物，亦可為在一部分具有不飽和鍵之物。又，脂環式結構可為單環的脂環式結構， 亦可為二環、三環等多環的脂環式結構。從使所得到的(甲基)丙烯酸酯聚合物(A)之相互間的距離成為適當，且對黏著劑賦予預定的柔軟性的觀點而言，上述脂環式結構係以多環的脂環式結構(多環結構)為佳。而且，考慮(甲基)丙烯酸酯聚合物(A)與其它成分的相溶性，上述多環結構係以二環至四環為特佳。又，與上述同樣地，從賦予預定的柔軟性的觀點而言，脂環式結構的碳數(係指形成環的部分的全部碳數，複數個環獨立地存在時，係指其合計的碳數)係通常以5以上為佳，以7以上為特佳。另一方面，脂環式結構的碳數之上限係沒有特別限制，與上述同樣地從相溶性的觀點而言，以15以下為佳，以10以下為特佳。 The carbon ring of the alicyclic structure of the alicyclic structure-containing monomer may be a saturated structure or may have an unsaturated bond in part. Furthermore, the alicyclic structure may be a monocyclic alicyclic structure or a polycyclic alicyclic structure such as a bicyclic or tricyclic alicyclic structure. From the viewpoint of making the distances between the obtained (meth)acrylate polymers (A) appropriate and imparting a predetermined softness to the adhesive, the alicyclic structure is preferably a polycyclic alicyclic structure (polycyclic structure). Furthermore, considering the compatibility of the (meth)acrylate polymer (A) with other components, the polycyclic structure is particularly preferably a bicyclic to tetracyclic structure. In addition, similarly to the above, from the perspective of imparting a predetermined softness, the carbon number of the alicyclic structure (referring to the total carbon number of the part forming the ring, when multiple rings exist independently, it refers to the total carbon number) is usually preferably 5 or more, and particularly preferably 7 or more. On the other hand, the upper limit of the carbon number of the alicyclic structure is not particularly limited, and similarly to the above, from the perspective of compatibility, it is preferably 15 or less, and particularly preferably 10 or less.
作為上述含脂環式結構單體，具體而言，可舉出(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯等，尤其是以(甲基)丙烯酸異莰酯為佳。該等可單獨使用1種，亦可組合2種以上而使用。 As the above-mentioned lipid-containing cyclic structure monomer, specifically, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. can be cited, and isoborneol (meth)acrylate is particularly preferred. These monomers can be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)係含有含脂環式結構單體作為構成該聚合物之單體單元時，以含有0.5質量%以上之該含脂環式結構單體為佳，以含有1質量%以上為特佳，進而以含有2質量%以上為佳。又，(甲基)丙烯酸酯聚合物(A)係以含有10質量%以下的含脂環式結構單體作為構成該聚合物之單體單元為佳，以含有8質量%以下為特佳，進而以含有5質量%以下為佳。藉由含脂環式結構單體的含量為上述範圍，所得到的黏著劑層更容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。 When the (meth)acrylate polymer (A) contains aliphatic cyclic structure monomers as monomer units constituting the polymer, it is preferred that the content of the aliphatic cyclic structure monomers is 0.5% by mass or more, particularly preferably 1% by mass or more, and further preferably 2% by mass or more. In addition, the (meth)acrylate polymer (A) preferably contains aliphatic cyclic structure monomers as monomer units constituting the polymer in an amount of 10% by mass or less, particularly preferably 8% by mass or less, and further preferably 5% by mass or less. When the content of the aliphatic cyclic structure monomers is within the above range, the obtained adhesive layer is more likely to satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
(甲基)丙烯酸酯聚合物(A)亦可含有上述單體以外的單體作為構成該聚合物之單體單元。作為此種單體，例如可舉出丙烯醯胺、甲基丙烯醯胺等非交聯性的丙烯醯胺、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等的(甲基)丙烯酸烷氧基烷酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯等具有非交聯性的三級胺基之(甲基)丙烯酸酯、乙酸乙烯 酯、苯乙烯等。該等可單獨使用，亦可組合2種以上而使用。 The (meth)acrylate polymer (A) may also contain monomers other than the above-mentioned monomers as monomer units constituting the polymer. Examples of such monomers include non-crosslinking acrylamides such as acrylamide and methacrylamide, (meth)acrylate alkoxyalkyls such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate, (meth)acrylates having non-crosslinking tertiary amino groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate, vinyl acetate, styrene, etc. These monomers may be used alone or in combination of two or more.
上述之中，(甲基)丙烯酸酯聚合物(A)係以含有丙烯醯胺作為構成該聚合物之單體單元為佳，以含有N-(丁氧基甲基)丙烯醯胺為特佳。(甲基)丙烯酸酯聚合物(A)藉由含有丙烯醯胺作為構成該聚合物之單體單元，所得到的黏著劑容易形成所需要的交聯結構而成為具有適合的凝聚力之物。藉此，所得到的黏著劑層係容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。 Among the above, the (meth)acrylate polymer (A) preferably contains acrylamide as a monomer unit constituting the polymer, and particularly preferably contains N-(butoxymethyl)acrylamide. Since the (meth)acrylate polymer (A) contains acrylamide as a monomer unit constituting the polymer, the obtained adhesive can easily form the required cross-linked structure and become a material with suitable cohesive force. Thus, the obtained adhesive layer can easily satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
(甲基)丙烯酸酯聚合物(A)係含有丙烯醯胺作為構成該聚合物之單體單元時，以含有0.5質量%以上的該丙烯醯胺為佳，以含有1質量%以上為特佳，進而以含有1.5質量%以上為佳。又，(甲基)丙烯酸酯聚合物(A)係含有10質量%以下的丙烯醯胺作為構成該聚合物之單體單元為佳，以含有8質量%以下為較佳，以含有5質量%以下為特佳，進而以含有3質量%以下為佳。藉由丙烯醯胺的含量為上述範圍，所得到的黏著劑更容易形成所需要的交聯結構且成為具有適合的凝聚力之物。藉此，所得到的黏著劑層係更容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。 When the (meth)acrylate polymer (A) contains acrylamide as a monomer unit constituting the polymer, it is preferred that the acrylamide is contained in an amount of 0.5% by mass or more, particularly preferably in an amount of 1% by mass or more, and further preferably in an amount of 1.5% by mass or more. Furthermore, it is preferred that the (meth)acrylate polymer (A) contains acrylamide as a monomer unit constituting the polymer in an amount of 10% by mass or less, more preferably in an amount of 8% by mass or less, particularly preferably in an amount of 5% by mass or less, and further preferably in an amount of 3% by mass or less. When the content of acrylamide is within the above range, the obtained adhesive is more likely to form the desired cross-linked structure and have suitable cohesive force. Thereby, the obtained adhesive layer is more likely to satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
(甲基)丙烯酸酯聚合物(A)係以直鏈狀聚合物為佳。藉由直鏈狀聚合物，分子鏈容易產生互相糾纏且容易形成具有所需要的凝聚力之黏著劑。 The (meth)acrylate polymer (A) is preferably a linear polymer. With a linear polymer, the molecular chains are easily entangled with each other and an adhesive with the required cohesive force is easily formed.
又，(甲基)丙烯酸酯聚合物(A)係以使用溶液聚合法而得到的溶液聚合物為佳。藉由溶液聚合物，容易得到高分子量的聚合物且容易形成具有所需要的凝聚力之黏著劑。 In addition, the (meth)acrylate polymer (A) is preferably a solution polymer obtained by solution polymerization. By using solution polymerization, it is easy to obtain a high molecular weight polymer and to form an adhesive with the required cohesive force.
(甲基)丙烯酸酯聚合物(A)的聚合態樣可為無規共聚物，亦可為嵌段共聚物。 The polymerization state of the (meth)acrylate polymer (A) can be a random copolymer or a block copolymer.
(甲基)丙烯酸酯聚合物(A)的重量平均分子量係下限值以2萬以上為佳，以6萬以上為特佳，進而以12萬以上為佳。又，(甲基)丙烯酸酯聚合物(A)的重量平均分子量係上限值以100萬以下為佳，以75萬以下為較佳，以50萬以 下為特佳，進而以25萬以下為佳。藉由(甲基)丙烯酸酯聚合物(A)的重量平均分子量在上述範圍，所形成的黏著劑層係容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。又，在本說明書之重量平均分子量係使用凝膠滲透層析(GPC)法而測定的標準聚苯乙烯換算值。 The weight average molecular weight of the (meth)acrylate polymer (A) is preferably 20,000 or more, particularly preferably 60,000 or more, and further preferably 120,000 or more as the lower limit. The weight average molecular weight of the (meth)acrylate polymer (A) is preferably 1,000,000 or less, more preferably 750,000 or less, particularly preferably 500,000 or less, and further preferably 250,000 or less as the upper limit. When the weight average molecular weight of the (meth)acrylate polymer (A) is within the above range, the adhesive layer formed can easily satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ. The weight average molecular weight in this specification is a standard polystyrene conversion value measured by gel permeation chromatography (GPC).
又，在上述黏著性組合物P，(甲基)丙烯酸酯聚合物(A)可單獨使用1種，亦可組合2種以上而使用。 In addition, in the above-mentioned adhesive composition P, the (meth)acrylate polymer (A) may be used alone or in combination of two or more.
(2-2)交聯劑(B) (2-2) Crosslinking agent (B)
交聯劑(B)係在將黏著性組合物P加熱時將(甲基)丙烯酸酯聚合物(A)進行交聯，因此，能夠在所得到的黏著劑中形成良好的三維網狀結構。藉此，所得到的黏著劑的凝聚力提升且所形成黏著劑層容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。 The crosslinking agent (B) crosslinks the (meth)acrylate polymer (A) when the adhesive composition P is heated, thereby forming a good three-dimensional network structure in the obtained adhesive. As a result, the cohesive force of the obtained adhesive is improved and the formed adhesive layer easily satisfies the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
作為上述交聯劑(B)，與(甲基)丙烯酸酯聚合物(A)所具有的反應性基進行反應之物即可，例如可舉出異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、吖環丙烷系交聯劑、肼系交聯劑、醛系交聯劑、
異氰酸酯系交聯劑係至少含有聚異氰酸酯化合物之物。作為聚異氰酸酯化合物，例如可舉出苯亞甲基二異氰酸酯(tolylene diisocyanate)、二苯基甲烷二異氰酸酯、伸茬基二異氰酸酯(xylylene diisocyanate)等的芳香族聚異氰酸酯、六亞甲基二異氰酸酯等的脂肪族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化 二苯基甲烷二異氰酸酯等的脂環式聚異氰酸酯等、及該等的脲體、異三聚氰酸酯體，進而與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等的低分子活性氫含有化合物的反應物之加成物等。尤其是從與羥基的反應性的觀點而言，係以使用三羥甲基丙烷改性的芳香族聚異氰酸酯、特別是三羥甲基丙烷改性苯亞甲基二異氰酸酯及三羥甲基丙烷改性伸茬基二異氰酸酯的至少一者為佳。 Isocyanate crosslinking agents are those containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and urea and isocyanurate forms thereof, and adducts of reaction products with low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trihydroxymethylpropane, and castor oil. In particular, from the perspective of reactivity with hydroxyl groups, it is preferred to use at least one of trihydroxymethylpropane-modified aromatic polyisocyanate, especially trihydroxymethylpropane-modified benzyl diisocyanate and trihydroxymethylpropane-modified stubby diisocyanate.
作為環氧系交聯劑，例如可舉出1,3-雙(N,N-二環氧丙基胺甲基)環己烷、N,N,N’,N’-四環氧丙基-間苯二甲胺(N,N,N',N'-tetraglycidyl-m-xylylenediamine)、乙二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、三羥甲基丙烷二環氧丙基醚、二環氧丙基苯胺、二環氧丙胺等。尤其是從與羧基反應性的觀點而言，係以1,3-雙(N,N-二環氧丙基胺甲基)環己烷為佳。 Examples of epoxy crosslinking agents include 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-m-xylylenediamine, ethylene glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trihydroxymethylpropane diepoxypropyl ether, diepoxypropylaniline, and diepoxypropylamine. In particular, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane is preferred from the viewpoint of reactivity with carboxyl groups.
在黏著性組合物P中之交聯劑(B)的含量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，以0.1質量份以上為佳，以1質量份以上為特佳，進而以2.5質量份以上為佳。又，該含量係以10質量份以下為佳，以8質量份以下為特佳，進而以5質量份以下為佳。藉由交聯劑(B)的含量在上述範圍，所得到的黏著劑層係更容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。 The content of the crosslinking agent (B) in the adhesive composition P is preferably 0.1 parts by mass or more, particularly 1 part by mass or more, and further preferably 2.5 parts by mass or more, relative to 100 parts by mass of the (meth)acrylate polymer (A). Furthermore, the content is preferably 10 parts by mass or less, particularly 8 parts by mass or less, and further preferably 5 parts by mass or less. When the content of the crosslinking agent (B) is within the above range, the adhesive layer obtained is more likely to satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
(2-3)其它的添加劑 (2-3) Other additives
黏著性組合物P係能夠依照需要而在丙烯酸系黏著劑添加通常使用的各種添加劑，例如矽烷偶合劑、紫外線吸收劑、抗靜電劑、黏著賦予劑、抗氧化劑、光安定劑、軟化劑、填充劑、折射率調整劑、防鏽劑等。又，構成黏著性組合物之添加劑係設為不包含後述的聚合溶劑和稀釋溶劑。 The adhesive composition P can add various commonly used additives to the acrylic adhesive as needed, such as silane coupling agent, ultraviolet absorber, antistatic agent, adhesion agent, antioxidant, light stabilizer, softener, filler, refractive index adjuster, rustproof agent, etc. In addition, the additives constituting the adhesive composition are set not to include the polymerization solvent and dilution solvent described later.
(2-4)黏著性組合物P的調製 (2-4) Preparation of adhesive composition P
黏著性組合物P係能夠藉由製造(甲基)丙烯酸酯聚合物(A)，且將所得到的 (甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及依照需要之其它的添加劑進行混合而製造。 The adhesive composition P can be produced by preparing a (meth)acrylate polymer (A), and mixing the obtained (meth)acrylate polymer (A), a crosslinking agent (B), and other additives as required.
(甲基)丙烯酸酯聚合物(A)係能夠藉由將構成聚合物之單體的混合物使用通常的自由基聚合法進行聚合而製造。(甲基)丙烯酸酯聚合物(A)的聚合係以依照需要而使用聚合起始劑，且使用溶液聚合法而進行為佳。作為聚合溶劑，例如可舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲苯、丙酮、己烷、甲基乙基酮等，亦可併用2種類以上。 The (meth)acrylate polymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer using a conventional free radical polymerization method. The polymerization of the (meth)acrylate polymer (A) is preferably carried out using a polymerization initiator as required and a solution polymerization method. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, etc., and two or more types may be used in combination.
作為聚合起始劑，可舉出偶氮系化合物、有機過氧化物等，亦可併用2種類以上。作為偶氮系化合物，例如可舉出2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷1-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、4,4’-偶氮雙(4-氰基戊酸)、2,2’-偶氮雙(2-羥甲基丙腈)、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。 As polymerization initiators, azo compounds, organic peroxides, etc. can be cited, and two or more types can be used in combination. As azo compounds, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc. can be cited.
作為有機過氧化物，例如可舉出過氧化苯甲醯、過氧化苯甲酸第三丁酯、異丙苯過氧化氫、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、過氧化二碳酸二(2-乙氧基乙基)酯、過氧化新癸酸第三丁酯、過氧化新戊酸第三丁酯、過氧化(3,5,5-三甲基己醯)、過氧化二丙醯、過氧化二乙醯等。 Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, isopropyl hydrogen peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.
又，在上述聚合步驟，藉由調配2-巰基乙醇等的鏈轉移劑，而能夠調節所得到的聚合物的重量平均分子量。 Furthermore, in the above polymerization step, the weight average molecular weight of the obtained polymer can be adjusted by adding a chain transfer agent such as 2-hydroxyethanol.
得到(甲基)丙烯酸酯聚合物(A)之後，能夠藉由在(甲基)丙烯酸酯聚合物(A)的溶液，添加交聯劑(B)、依照需要之其它的添加劑、以及依照需要之稀釋溶劑及添加劑且充分地混合，而得到經溶劑稀釋的黏著性組合物P(塗佈溶液)。又，在上述各成分的任一者係使用固體狀物時、或在未被稀釋的狀態下與其它成分混合時產生析出時，亦可將該成分單獨預先在稀釋溶劑進行溶解或稀 釋之後，與其它成分混合。 After obtaining the (meth)acrylate polymer (A), a crosslinking agent (B), other additives as required, and a diluting solvent and additives as required can be added to the solution of the (meth)acrylate polymer (A) and the mixture is fully mixed to obtain a solvent-diluted adhesive composition P (coating solution). In addition, when any of the above components is used in a solid state or precipitates when mixed with other components in an undiluted state, the component can be dissolved in a diluting solvent alone or diluted before mixing with other components.
作為上述稀釋溶劑，例如能夠使用己烷、庚烷、環己烷等的脂肪族烴、甲苯、二甲苯等的芳香族烴、二氯甲烷、二氯乙烷等的鹵化烴、甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇、丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等的酮、乙酸乙酯、乙酸丁酯等的酯、乙基賽路蘇等的賽路蘇系溶劑等。 As the above-mentioned diluting solvent, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, alcohols such as methanol, ethanol, propanol, butanol, and 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, and thiocyanate-based solvents such as ethylthiocyanate can be used.
作為如此進行而調製的塗佈溶液的濃度．黏度，能夠塗佈的範圍即可而沒有特別限制，能夠按照狀況而適當地選定。例如、黏著性組合物P的濃度以成為10~60質量%，較佳是以成為20~30質量%之方式稀釋。又，得到塗佈溶液時，稀釋溶劑等的添加不是必要條件下，黏著性組合物P為能夠塗佈的黏度等時，亦可不添加稀釋溶劑。此時，黏著性組合物p係將(甲基)丙烯酸酯聚合物(A)的聚合溶劑直接作為稀釋溶劑之塗佈溶液。 The concentration and viscosity of the coating solution prepared in this way are not particularly limited as long as they are within the range that can be coated, and can be appropriately selected according to the situation. For example, the concentration of the adhesive composition P is diluted to 10-60% by mass, preferably 20-30% by mass. In addition, when obtaining the coating solution, the addition of a diluting solvent is not a necessary condition, and when the adhesive composition P is a coating viscosity, no diluting solvent may be added. At this time, the adhesive composition P is a coating solution in which the polymerization solvent of the (meth)acrylate polymer (A) is directly used as a diluting solvent.
(2-5)黏著劑層的物性等 (2-5) Physical properties of adhesive layer, etc.
黏著劑層的凝膠分率係以60%以上為佳，以70%以上為特佳，進而以80%以上為佳。又，黏著劑層的凝膠分率係以100%以下為佳，以98%以下為特佳，進而以95%以下為佳。藉由黏著劑層的凝膠分率為上述範圍，所形成的黏著劑層係容易滿足有關前述的伸長率之比值(E2/E1)及損失正切tanδ。 The gel fraction of the adhesive layer is preferably 60% or more, particularly preferably 70% or more, and further preferably 80% or more. Furthermore, the gel fraction of the adhesive layer is preferably 100% or less, particularly preferably 98% or less, and further preferably 95% or less. When the gel fraction of the adhesive layer is within the above range, the formed adhesive layer is likely to satisfy the aforementioned elongation ratio (E 2 /E 1 ) and loss tangent tanδ.
黏著劑層的厚度係以3μm以上為佳，以8μm以上為特佳，進而以16μm以上為佳。又，黏著劑層的厚度係以50μm以下為佳，以40μm以下為特佳，進而以30μm以下為佳。藉由黏著劑層的厚度在上述範圍，容易將本實施形態之保護片的黏著力調整成為前述範圍之同時，容易成為對被黏著物良好地兼具密著性與剝離性之物。 The thickness of the adhesive layer is preferably 3 μm or more, particularly 8 μm or more, and further preferably 16 μm or more. In addition, the thickness of the adhesive layer is preferably 50 μm or less, particularly 40 μm or less, and further preferably 30 μm or less. By making the thickness of the adhesive layer within the above range, it is easy to adjust the adhesive force of the protective sheet of this embodiment to the above range, and it is easy to become a product with good adhesion and releasability to the adherend.
(3)剝離片 (3) Peeling film
本實施形態之保護片係具備剝離片時，作為該剝離片，只要不對黏著劑層 造成不良影響就沒有特別限定，例如能夠使用聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚胺酯膜、乙烯乙酸乙烯酯膜、離子聚合物樹脂膜、乙烯．(甲基)丙烯酸共聚物膜、乙烯．(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚醯亞胺膜、氟樹脂膜等。又，亦可使用該等的交聯膜。而且，亦可為該等的積層膜。上述之中，以具有優異的操作性之聚對苯二甲酸乙二酯膜為佳。 When the protective sheet of this embodiment is provided with a release sheet, the release sheet is not particularly limited as long as it does not adversely affect the adhesive layer. For example, polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionic polymer resin film, ethylene. (meth) acrylic acid copolymer film, ethylene. (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. can be used. In addition, the crosslinked films thereof can also be used. Moreover, the laminated films thereof can also be used. Among the above, the polyethylene terephthalate film having excellent operability is preferred.
亦可對上述剝離片與黏著劑層接觸之面施行剝離處理。作為使用在剝離處理之剝離劑，例如可舉出氟系、醇酸系、聚矽氧系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。 The surface of the release sheet in contact with the adhesive layer may also be subjected to a release treatment. Examples of the release agent used in the release treatment include fluorine-based, alkyd-based, polysilicone-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
針對剝離片的厚度，係沒有特別限制，通常以15μm以上為佳，以25μm以上為特佳。又，該厚度係通常以100μm以下為佳，以75μm以下為特佳。 There is no particular restriction on the thickness of the peeling sheet, but it is usually preferably 15 μm or more, and particularly preferably 25 μm or more. In addition, the thickness is usually preferably 100 μm or less, and particularly preferably 75 μm or less.
3.保護片的製造方法 3. Manufacturing method of protective film
本實施形態之保護片的製造方法係沒有特別限定，能夠使用常用的方法。例如，首先將黏著性組合物P(或將其使用溶劑稀釋而成之塗佈溶液)，藉由使用模塗佈機(die coater)、簾式塗佈機、噴霧塗佈機、狹縫塗佈機、刮刀塗佈機等塗佈在基材的一面上而形成塗膜。隨後，藉由使該塗膜乾燥而能夠得到將黏著劑層設置在基材上而成之保護片。 The manufacturing method of the protective sheet of this embodiment is not particularly limited, and a common method can be used. For example, first, the adhesive composition P (or a coating solution obtained by diluting it with a solvent) is applied to one side of the substrate using a die coater, a curtain coater, a spray coater, a slit coater, a scraper coater, etc. to form a coating film. Then, by drying the coating film, a protective sheet in which the adhesive layer is disposed on the substrate can be obtained.
黏著性組合物P係含有交聯劑(B)時，為了以所需要的存在密度形成交聯結構，亦可改變上述的乾燥條件(溫度、時間等)、或也可另外設置加熱處理。為了使交聯反應充分地進行，亦可使用上述的方法等將黏著劑層層積在基材之後，將所得到的保護片進行例如在23℃、相對濕度50%的環境下靜置數天之熟化。 When the adhesive composition P contains a crosslinking agent (B), in order to form a crosslinked structure at the required density, the above-mentioned drying conditions (temperature, time, etc.) may be changed, or a heat treatment may be provided separately. In order to allow the crosslinking reaction to proceed sufficiently, the adhesive may be deposited on the substrate layer by layer using the above-mentioned method, and the resulting protective sheet may be aged for several days in an environment of 23°C and a relative humidity of 50%.
作為保護片之另外的製造例，亦可將黏著性組合物P(或將其使用 溶劑稀釋而成之塗佈溶液)塗佈在剝離片之剝離面上而形成塗膜後，藉由使該塗膜乾燥而形成黏著劑層，而且藉由將所形成的黏著劑層轉印在基材的一面上而得到保護片。 As another example of manufacturing the protective sheet, the adhesive composition P (or a coating solution obtained by diluting the adhesive composition P with a solvent) may be applied to the release surface of the release sheet to form a coating film, and then the coating film may be dried to form an adhesive layer, and the formed adhesive layer may be transferred to one side of the substrate to obtain the protective sheet.
4.保護片的用途 4. Purpose of protective film
本實施形態之保護片係能夠為了保護裝置等的對象而使用。此時，在裝置的加工、裝配、檢査等的步驟中，藉由成為將保護片貼合在裝置的預定面之狀態，而能夠防止該面產生損傷等。 The protective sheet of this embodiment can be used to protect an object such as a device. In this case, during the processing, assembly, and inspection of the device, the protective sheet is attached to a predetermined surface of the device, thereby preventing the surface from being damaged.
作為上述裝置，係沒有特別限定，例如可舉出光學構件或電子構件。作為此種光學構件或電子構件的具體例，可舉出具備樹脂板及層積在該樹脂板的一面側的硬塗層之附硬塗層樹脂板、玻璃板等。 The above-mentioned device is not particularly limited, and an optical component or an electronic component can be cited, for example. As a specific example of such an optical component or an electronic component, a hard-coated resin plate having a resin plate and a hard-coated layer laminated on one side of the resin plate, a glass plate, etc. can be cited.
本實施形態之保護片係如前述，即便被加熱時，亦能夠維持黏著劑層的性狀，對被黏著物顯示良好的密著性，同時在剝離時能夠從被黏著物良好地剝離。因此，本實施形態之保護片係以使用在被保護片保護的狀態下受到加熱處理之裝置為佳。 As described above, the protective sheet of this embodiment can maintain the properties of the adhesive layer even when heated, showing good adhesion to the adherend, and can be well peeled off from the adherend when peeling. Therefore, the protective sheet of this embodiment is preferably used in a device that is subjected to heat treatment while being protected by the protective sheet.
又，本實施形態之保護片係如前述，被貼合在存在微細的凹凸之面時，黏著劑層能夠適當地追隨該凹凸，即便加熱後，亦能夠以高水準兼具良好的密著性與剝離性。因此，本實施形態之保護片係以使用在通常多半在表面具有微細的凹凸之附硬塗層樹脂板為佳。 Furthermore, when the protective sheet of this embodiment is attached to a surface with fine unevenness as described above, the adhesive layer can properly follow the unevenness, and even after heating, it can have both good adhesion and peeling properties at a high level. Therefore, the protective sheet of this embodiment is preferably used on a hard-coated resin board that usually has fine unevenness on the surface.
[積層體] [Laminar body]
本實施形態之積層體係具備：具備樹脂板及層積在樹脂板的一面側的硬塗層之附硬塗層樹脂板；及前述的保護片。而且，可成為該保護片之黏著劑層側的面係被層積在上述附硬塗層樹脂板之硬塗層側的面而成之物。 The laminated body of this embodiment comprises: a resin sheet with a hard coating layer having a resin sheet and a hard coating layer laminated on one side of the resin sheet; and the aforementioned protective sheet. Moreover, the surface of the adhesive layer side of the protective sheet may be laminated on the surface of the hard coating layer side of the aforementioned resin sheet with a hard coating layer.
上述保護片係如前述，即便被加熱時亦能夠維持黏著劑層的性狀，雖然對被黏著物顯示良好的密著性，同時在剝離時也能夠從被黏著物良好 地剝離。而且，被貼合在存在微細的凹凸之面時，黏著劑層對該凹凸適當地追隨，即便加熱後亦能夠以高水準兼具良好的密著性與剝離性。 As mentioned above, the protective sheet can maintain the properties of the adhesive layer even when heated, and can be well peeled off from the adherend while showing good adhesion to the adherend. Moreover, when it is attached to a surface with fine unevenness, the adhesive layer appropriately follows the unevenness, and can have both good adhesion and peeling properties at a high level even after heating.
因此，在本實施形態之積層體，係成為保護片適當地密著在附硬塗層樹脂板之硬塗層側的面之積層體，即便該積層體被加熱時，亦能夠抑制保護片從附硬塗層樹脂板未蓄意地剝落。另一方面，在將保護片剝離時，能夠從附硬塗層樹脂板良好地剝離。 Therefore, in the laminate of the present embodiment, the protective sheet is appropriately adhered to the hard coating side of the hard coating resin sheet, and even when the laminate is heated, the protective sheet can be prevented from unintentionally peeling off from the hard coating resin sheet. On the other hand, when the protective sheet is peeled off, it can be peeled off well from the hard coating resin sheet.
以上說明的實施形態，係為了容易理解本發明而記載，不是為了限定本發明而記載。因而，在上述實施形態所揭示的各要素，其宗旨亦包含屬於本發明的技術範圍之全部的設計變更或均等物。 The embodiments described above are recorded for easy understanding of the present invention, not for limiting the present invention. Therefore, the elements disclosed in the above embodiments also include all design changes or equivalents within the technical scope of the present invention.
例如，在保護片之基材與黏著劑層之間，其它層亦可介於其間，在基材之與黏著劑層側為相反側的面亦可層積其它層。 For example, other layers may be interposed between the substrate and the adhesive layer of the protective sheet, and other layers may be stacked on the side of the substrate opposite to the adhesive layer.
[實施例] [Implementation example]
以下，藉由實施例等而更具體地說明本發明，但是本發明的範圍係不被該等實施例等限定。 The present invention is described in more detail below through examples, but the scope of the present invention is not limited by these examples, etc.
[實施例1] [Implementation Example 1]
1.(甲基)丙烯酸酯聚合物的調製 1. Preparation of (meth)acrylate polymers
將丙烯酸正丁酯70質量份、丙烯酸2-乙基己酯20質量份、丙烯酸異莰酯3質量份、甲基丙烯酸2-羥基乙酯5質量份及N-(丁氧基甲基)丙烯醯胺2質量份共聚合而調製(甲基)丙烯酸酯聚合物。使用後述方法測定該(甲基)丙烯酸酯聚合物的重量平均分子量(Mw)時為15萬。 A (meth)acrylate polymer was prepared by copolymerizing 70 parts by mass of n-butyl acrylate, 20 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of isoborneol acrylate, 5 parts by mass of 2-hydroxyethyl methacrylate, and 2 parts by mass of N-(butoxymethyl)acrylamide. The weight average molecular weight (Mw) of the (meth)acrylate polymer was 150,000 when measured by the method described below.
2.黏著性組合物的調製 2. Preparation of adhesive composition
將上述步驟1所得到的(甲基)丙烯酸酯聚合物100質量份(固體成分換算值；以下相同)、及作為異氰酸酯系交聯劑之六亞甲基二異氰酸酯3.5質量份進行混合且充分地攪拌，而且藉由使用甲基乙基酮稀釋而得到固體成分濃度25質量%之黏 著性組合物的塗佈溶液。 100 parts by mass of the (meth)acrylate polymer obtained in step 1 above (solid content conversion value; the same below) and 3.5 parts by mass of hexamethylene diisocyanate as an isocyanate crosslinking agent are mixed and stirred thoroughly, and then diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition with a solid content concentration of 25% by mass.
3.保護片的製造 3. Manufacturing of protective film
將上述步驟2所得到的黏著性組合物的塗佈溶液，使用刮刀塗佈機塗佈在聚對苯二甲酸乙二酯膜(三菱CHEMICAL公司製、製品名「PET38T-100」、厚度：38μm)的一面而形成塗佈層。隨後，將該塗佈層在90℃進行加熱處理1分鐘而形成厚度20μm的黏著劑層。藉此，得到由基材及黏著劑層所構成之保護片。 The coating solution of the adhesive composition obtained in step 2 above is applied to one side of a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Co., Ltd., product name "PET38T-100", thickness: 38μm) using a doctor blade coater to form a coating layer. Subsequently, the coating layer is heat-treated at 90°C for 1 minute to form an adhesive layer with a thickness of 20μm. In this way, a protective sheet consisting of a substrate and an adhesive layer is obtained.
[實施例2~4、比較例1] [Implementation Examples 2~4, Comparative Example 1]
除了將(甲基)丙烯酸酯聚合物的組成、以及交聯劑的種類及含量變更成為如表1所示以外，與實施例1同樣地進行而製造黏著片。 The adhesive sheet was produced in the same manner as in Example 1 except that the composition of the (meth)acrylate polymer and the type and content of the crosslinking agent were changed to those shown in Table 1.
在此，前述的重量平均分子量(Mw)係使用凝膠滲透層析法(GPC)且在以下的條件下測定(GPC測定)之標準聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) mentioned above is the weight average molecular weight converted to standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions (GPC measurement).
<測定條件> <Measurement conditions>
．GPC測定裝置：TOSOH公司製、HLC-8320 ．GPC measuring device: HLC-8320 manufactured by TOSOH
．GPC管柱(依照以下的順序而通過)：TOSOH公司製 ． GPC column (passed in the following order): made by TOSOH
TSK gel superH-H TSK gel superH-H
TSK gel superHM-H TSK gel superHM-H
TSK gel superH2000 TSK gel superH2000
．測定溶劑：四氫呋喃 ． Determination solvent: tetrahydrofuran
．測定溫度：40℃ ．Measurement temperature: 40℃
[試驗例1](凝膠分率的測定) [Test Example 1] (Determination of gel fraction)
將實施例及比較例所得到的保護片裁斷成為80mm×80mm的大小，而且在聚酯製篩網(Tetron Mesh#200)將該黏著劑層包住且使用精密天秤稱量其質量，藉由減去上述篩網單獨的質量來算出只有黏著劑的質量。將此時的質量設為M1。 The protective sheet obtained in the embodiment and the comparative example was cut into a size of 80 mm × 80 mm, and the adhesive layer was wrapped in a polyester mesh (Tetron Mesh #200) and its mass was weighed using a precision balance. The mass of the adhesive alone was calculated by subtracting the mass of the mesh alone. The mass at this time was set as M1.
其次，將被上述聚酯製篩網包住的黏著劑，使其於室溫下(23℃) 在乙酸乙酯浸漬24小時浸漬。隨後，將黏著劑取出且在溫度23℃、相對濕度50%的環境下使其風乾24小時，進而在80℃的烘箱中乾燥12小時。乾燥後，使用精密天秤稱量其質量，藉由減去上述篩網單獨的質量而算出只有黏著劑的質量。將此時的質量設為M2。而且，藉由計算(M2/M1)×100而算出凝膠分率(%)。將結果顯示在表1。 Next, the adhesive wrapped by the polyester mesh was immersed in ethyl acetate at room temperature (23°C) for 24 hours. Then, the adhesive was taken out and air-dried for 24 hours at a temperature of 23°C and a relative humidity of 50%, and then dried in an oven at 80°C for 12 hours. After drying, the mass was weighed using a precision balance, and the mass of the adhesive alone was calculated by subtracting the mass of the mesh alone. The mass at this time was set as M2. In addition, the gel fraction (%) was calculated by calculating (M2/M1)×100. The results are shown in Table 1.
[試驗例2](黏著力的測定) [Test Example 2] (Measurement of Adhesion)
將實施例及比較例所製造的保護片裁斷成為寬度25mm、長度120mm的大小之後，將其黏著劑層側的面貼合在一面具備以聚甲基丙烯酸甲酯作為材料的硬塗層之聚碳酸酯樹脂板(三菱氣體化學公司製、製品名「HMRS52T」、厚度：2.0mm，以下有稱為「附硬塗層樹脂板」之情形)之硬塗層側的面，而且將其作為黏著力測定用試樣。 After cutting the protective sheet produced in the embodiment and the comparative example into a size of 25 mm in width and 120 mm in length, the adhesive layer side of the sheet was attached to the hard coating side of a polycarbonate resin sheet (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "HMRS52T", thickness: 2.0 mm, hereinafter referred to as "resin sheet with hard coating layer") with polymethyl methacrylate as the material, and used as a sample for adhesion measurement.
將上述黏著力測定用試樣在23℃、50%RH的環境下放置24小時之後，使用拉伸試驗機於180°的剝離角度以0.3m/分鐘的剝離速度將保護片剝離來測定黏著力(N/25mm)。將該測定值設為在加熱前之對附硬塗層樹脂板的黏著力。將結果顯示在表2 After placing the above-mentioned adhesion test specimen in an environment of 23°C and 50% RH for 24 hours, the protective sheet was peeled off at a peeling angle of 180° and a peeling speed of 0.3m/min using a tensile tester to measure the adhesion (N/25mm). The measured value was set as the adhesion to the hard-coated resin board before heating. The results are shown in Table 2
又，將與上述同樣地進行而得到的黏著力測定用試樣，在23℃、50%RH的環境下放置24小時之後，在100℃加熱30分鐘，且在23℃、50%RH的環境下靜置30分鐘。針對藉此而溫度返回至室溫為止之黏著力測定用試樣，與上述同樣地測定黏著力。將其結果顯示在表2，作為在加熱後之對附硬塗層樹脂板的黏著力。 Furthermore, the adhesion test sample obtained in the same manner as above was placed in an environment of 23°C and 50% RH for 24 hours, then heated at 100°C for 30 minutes, and then left at 23°C and 50% RH for 30 minutes. The adhesion of the adhesion test sample, which was returned to room temperature, was measured in the same manner as above. The results are shown in Table 2 as the adhesion to the hard-coated resin board after heating.
而且，使用將附硬塗層樹脂板變更成為鈉鈣玻璃而得到的黏著力測定用試樣，與上述同樣地測定在加熱前及加熱後之對玻璃板的黏著力。將該等結果亦顯示在表2。 Furthermore, using a sample for measuring adhesion obtained by changing the hard-coated resin plate to sodium calcium glass, the adhesion to the glass plate before and after heating was measured in the same manner as above. These results are also shown in Table 2.
又，表2中附加「※1」之黏著力的測定結果，係如以下測定的結 果。亦即，該黏著力測定時，在將保護片從黏著力測定用試樣剝離時，黏著劑層從基材分離而只有黏著劑層殘留在玻璃板上。但是只有針對該黏著劑層，以上述的剝離角度及剝離速度進行剝離時，能夠適當地剝離而測定黏著力。因此，附加「※1」之黏著力，以如此方式進行而測定之黏著力。 In addition, the adhesive force measurement results with "※1" in Table 2 are the results of the following measurement. That is, during the adhesive force measurement, when the protective sheet is peeled off from the adhesive force measurement sample, the adhesive layer is separated from the substrate and only the adhesive layer remains on the glass plate. However, only when the adhesive layer is peeled off at the above-mentioned peeling angle and peeling speed can it be properly peeled off and the adhesive force can be measured. Therefore, the adhesive force with "※1" is the adhesive force measured in this way.
[試驗例3](水接觸角的測定) [Test Example 3] (Measurement of water contact angle)
將實施例及比較例所製造的保護片之黏著劑層側的面，貼合在作為附硬塗層樹脂板之在一面具備以聚甲基丙烯酸甲酯作為材料的硬塗層之聚碳酸酯樹脂板(三菱氣體化學公司製、製品名「HM RS52T」，厚度：2.0mm)之硬塗層側的面，而且將其作為水接觸角測定用試樣。 The adhesive layer side of the protective sheet manufactured in the embodiment and the comparative example was bonded to the hard coating side of a polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "HM RS52T", thickness: 2.0 mm) with a hard coating layer made of polymethyl methacrylate on one side as a hard coating resin plate, and used as a sample for water contact angle measurement.
將上述水接觸角測定用試樣在23℃、50%RH的環境下放置24小時之後，針對將保護片剝下而露出的附硬塗層樹脂板之硬塗層側的面，使用全自動式接觸角測定計(協和界面科學公司製、製品名「DM-701」)且在以下的條件下測定水接觸角(°)。將其結果作為在加熱前之對附硬塗層樹脂板的水接觸角W1且顯示在表2。 After the water contact angle measurement sample was placed in an environment of 23°C and 50% RH for 24 hours, the water contact angle (°) was measured on the hard coating side of the hard coating resin board exposed by peeling off the protective sheet using a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name "DM-701") under the following conditions. The result was taken as the water contact angle W1 of the hard coating resin board before heating and is shown in Table 2.
．純化水的液滴量：2ul ． Drop volume of purified water: 2ul
．測定時間：滴下3秒後 ． Measuring time: 3 seconds after dripping
．影像解析法：θ/2法 ． Image analysis method: θ/2 method
又，將與上述同樣地進行而得到的水接觸角測定用試樣，在23℃、50%RH的環境下放置24小時之後，在100℃加熱30分鐘，進而在23℃、50%RH的環境下靜置30分鐘。針對藉此而溫度返回至室溫為止之水接觸角測定用試樣，與上述同樣地測定水接觸角。將其結果作為在加熱後之對附硬塗層樹脂板的水接觸角W2且顯示在表2。而且，算出水接觸角W2對如上述測定的水接觸角W1之比值(W2/W1)。將該結果亦顯示在表2。 Furthermore, the water contact angle measurement sample obtained in the same manner as above was placed in an environment of 23°C and 50% RH for 24 hours, then heated at 100°C for 30 minutes, and then placed in an environment of 23°C and 50% RH for 30 minutes. The water contact angle of the water contact angle measurement sample whose temperature was returned to room temperature was measured in the same manner as above. The result was taken as the water contact angle W 2 of the hard-coated resin board after heating and is shown in Table 2. In addition, the ratio of the water contact angle W 2 to the water contact angle W 1 measured as above was calculated (W 2 /W 1 ). The result is also shown in Table 2.
而且，使用將附硬塗層樹脂板變更成為鈉鈣玻璃而得到的水接觸 角測定用試樣，與上述同樣地測定在加熱前之對玻璃板的水接觸角W3及在加熱後之對玻璃板的水接觸角W4之同時，算出其比值(W4/W3)。將該等結果亦顯示在表2。 Furthermore, using a water contact angle measurement sample obtained by changing the hard-coated resin plate to sodium calcium glass, the water contact angle W3 to the glass plate before heating and the water contact angle W4 to the glass plate after heating were measured in the same manner as above, and their ratio ( W4 / W3 ) was calculated. These results are also shown in Table 2.
又，表2中附加「※2」之水接觸角的測定結果，係如以下測定的結果。亦即，測定該水接觸角時，在將保護片從水接觸角測定用試樣剝離時黏著劑層係從基材分離而只有黏著劑層殘留在玻璃板上。因此，針對藉由只有將該黏著劑層從玻璃板剝離而露出的玻璃板之露出面，如上述測定水接觸角且將其結果附加「※2」而顯示在表2。 In addition, the water contact angle measurement results appended with "※2" in Table 2 are the results of the following measurements. That is, when measuring the water contact angle, the adhesive layer is separated from the substrate when the protective sheet is peeled off from the water contact angle measurement sample, and only the adhesive layer remains on the glass plate. Therefore, for the exposed surface of the glass plate exposed by peeling off only the adhesive layer from the glass plate, the water contact angle is measured as described above and the results are appended with "※2" and displayed in Table 2.
[試驗例4](總光線透射率的測定) [Test Example 4] (Determination of total light transmittance)
使用霧度計(日本電色工業製、製品名「NDH5000」)依據JIS K7361-1：1997而測定作為附硬塗層樹脂板之在一面具備以聚甲基丙烯酸甲酯作為材料的硬塗層之聚碳酸酯樹脂板(三菱氣體化學公司製、製品名「HMRS52T」、厚度：2.0mm)的總光線透射率(%)。將其結果顯示在表2，作為在貼附保護片之前(貼附前)之附硬塗層樹脂板的總光線透射率。 The total light transmittance (%) of a polycarbonate resin sheet (Mitsubishi Gas Chemical Co., Ltd., product name "HMRS52T", thickness: 2.0 mm) having a hard coating layer made of polymethyl methacrylate on one side as a hard coating resin sheet was measured using a mist meter (Nippon Denshoku Industries, product name "NDH5000") in accordance with JIS K7361-1:1997. The results are shown in Table 2 as the total light transmittance of the hard coating resin sheet before the protective sheet was attached (before attachment).
接著，將在實施例及比較例所製造的保護片的黏著劑層側的面貼合在上述附硬塗層樹脂板之硬塗層側的面，且將其作為總光線透射率測定用試樣。將該總光線透射率測定用試樣在23℃、50%RH的環境下放置24小時之後，在100℃加熱30分鐘加熱，進而在23℃、50%RH的環境下靜置30分鐘。針對將保護片從藉此而溫度返回至室溫為止之總光線透射率測定用試樣剝離除去而成之附硬塗層樹脂板，亦與上述同樣地測定總光線透射率(%)。將其結果作為在貼附有保護片的狀態下進行加熱而且將該保護片剝離之後(加熱剝離後)之附硬塗層樹脂板的總光線透射率，且顯示在表2。 Next, the adhesive layer side of the protective sheet produced in the embodiment and the comparative example was attached to the hard coating layer side of the above-mentioned resin board with hard coating, and it was used as a sample for total light transmittance measurement. After the sample for total light transmittance measurement was placed in an environment of 23°C and 50%RH for 24 hours, it was heated at 100°C for 30 minutes, and then left in an environment of 23°C and 50%RH for 30 minutes. The total light transmittance (%) of the resin board with hard coating, which was obtained by peeling off the protective sheet from the sample for total light transmittance measurement until the temperature returned to room temperature, was also measured in the same manner as above. The results are shown in Table 2 as the total light transmittance of the hard-coated resin board after heating with the protective sheet attached and peeling off the protective sheet (after heating and peeling off).
而且，將附硬塗層樹脂板變更為鈉鈣玻璃且與上述同樣地進行總光線透射率(%)的測定，來得到在貼附前之玻璃板的總光線透射率及在加熱剝離 後之玻璃板的總光線透射率。將該等結果亦顯示表2。 Furthermore, the hard-coated resin plate was changed to sodium calcium glass and the total light transmittance (%) was measured in the same manner as above to obtain the total light transmittance of the glass plate before bonding and the total light transmittance of the glass plate after thermal peeling. These results are also shown in Table 2.
[試驗例5](儲存彈性模數及損失正切tanδ的測定) [Test Example 5] (Determination of storage elastic modulus and loss tangent tanδ)
將在實施例及比較例所調製之黏著性組合物的塗佈溶液，使用刮刀塗佈機塗佈在剝離片(LINTEC公司製、製品名「SP-PET381130」、厚度：38μm)的剝離處理面上，該剝離片係在聚對苯二甲酸乙二酯膜的一面使用聚矽氧系剝離劑進行剝離處理而成。藉由將所得到的塗膜在90℃的環境下經過1分鐘來加熱塗膜，而準備複數片在剝離片上層積由各黏著性組合物所形成之厚度40μm的試驗用黏著劑層而成之黏著片。 The coating solution of the adhesive composition prepared in the embodiment and the comparative example was coated on the peeling treatment surface of a peeling sheet (manufactured by LINTEC, product name "SP-PET381130", thickness: 38μm) using a doctor blade coater. The peeling sheet was obtained by peeling treatment on one side of a polyethylene terephthalate film using a polysilicone-based peeling agent. The obtained coating film was heated at 90°C for 1 minute to prepare a plurality of adhesive sheets formed by laminating a 40μm thick test adhesive layer formed by each adhesive composition on the peeling sheet.
使用所得到的黏著片，貼合試驗用的黏著劑層至厚度成為800μm為止，而得到黏著劑層的積層體。將該積層體沖切成為直徑10mm的圓形而得到黏著劑層的黏彈性測定用試樣。將該黏彈性測定用試樣在23℃、50%RH的環境下放置24小時之後，使用黏彈性測定裝置(TA Instruments公司製、製品名「ARES」)對上述黏彈性測定用試樣施加頻率1Hz的應變且在-50~150℃測定儲存彈性模數及損失彈性模數。從該等之值算出在23℃之儲存彈性模數(MPa)及損失正切tanδ。將該等結果作為在加熱前之儲存彈性模數及損失正切tanδ且顯示在表3。 Using the obtained adhesive sheet, the adhesive layer for the test was bonded until the thickness reached 800 μm, thereby obtaining a laminate of the adhesive layer. The laminate was punched into a circle with a diameter of 10 mm to obtain a sample for measuring the viscoelasticity of the adhesive layer. After the sample for measuring the viscoelasticity was placed in an environment of 23°C and 50% RH for 24 hours, a strain of 1 Hz was applied to the sample for measuring the viscoelasticity using a viscoelasticity measuring device (manufactured by TA Instruments, product name "ARES"), and the storage elastic modulus and loss elastic modulus were measured at -50 to 150°C. The storage elastic modulus (MPa) and loss tangent tanδ at 23°C were calculated from these values. These results are taken as the storage elastic modulus and loss tangent tanδ before heating and are shown in Table 3.
又，將與上述同樣地進行而得到的黏彈性測定用試樣，在23℃、50%RH的環境下放置24小時之後，在100℃加熱30分鐘，而且藉由在23℃、50%RH的環境下靜置30分鐘使該試樣的溫度返回至室溫之後，與上述同樣地進行而算出儲存彈性模數(MPa)及損失正切tanδ。將該等結果作為在加熱後之儲存彈性模數及損失正切tanδ且顯示在表3。 In addition, the viscoelasticity measurement sample obtained in the same manner as above was placed in an environment of 23°C and 50% RH for 24 hours, then heated at 100°C for 30 minutes, and then returned to room temperature by standing still in an environment of 23°C and 50% RH for 30 minutes, and then the storage elastic modulus (MPa) and loss tangent tanδ were calculated in the same manner as above. These results are shown in Table 3 as the storage elastic modulus and loss tangent tanδ after heating.
[試驗例6](藉由拉伸試驗之伸長率的測定) [Test Example 6] (Determination of elongation by tensile test)
將在實施例及比較例所調製之黏著性組合物的塗佈溶液，使用刮刀塗佈機塗佈在經使用聚矽氧系剝離劑對聚對苯二甲酸乙二酯膜的一面進行剝離處理之 剝離片(LINTEC公司製、製品名「SP-PET381130」、厚度：38μm)的剝離處理面上。藉由使所得到的塗膜在90℃的環境下經過1分鐘而加熱塗膜，而準備複數片由各黏著性組合物所形成之厚度25μm的試驗用黏著劑層層積在剝離片上而成之黏著片。 The coating solution of the adhesive composition prepared in the embodiment and the comparative example was applied by a doctor blade coater on the peeling-treated surface of a peeling sheet (manufactured by LINTEC, product name "SP-PET381130", thickness: 38μm) on which one side of a polyethylene terephthalate film was peeled using a silicone-based peeling agent. The obtained coating film was heated in an environment of 90°C for 1 minute, and a plurality of test adhesive layers with a thickness of 25μm formed by each adhesive composition were prepared on the peeling sheet.
使用所得到的黏著片，貼合試驗用的黏著劑層至厚度成為500μm為止。又，該貼合時，係邊殘留最表層的剝離片邊重複貼合，藉此，得到由厚度500μm的黏著劑層及1片剝離片所構成之積層體。隨後，將該積層體裁斷成為10mm×75mm的大小而得到伸長率測定用試樣。 Using the obtained adhesive sheet, the adhesive layer for the test was bonded until the thickness reached 500μm. In addition, during the bonding, the bonding was repeated while leaving the peeling sheet on the outermost layer, thereby obtaining a laminate consisting of an adhesive layer with a thickness of 500μm and a peeling sheet. Subsequently, the laminate was cut into a size of 10mm×75mm to obtain a sample for elongation measurement.
將所得到的伸長率測定用試樣在23℃、50%RH的環境下放置24小時之後，以測定部位成為10mm×20mm的大小之方式安裝於拉伸試驗機(ORIENTEC公司製、製品名「TENSILON」)。而且，在23℃、50%RH的環境下以拉伸速度200mm/分鐘使其伸長且測定斷裂伸長率(%)。將其結果作為加熱前的伸長率E1而顯示在表3。 The obtained elongation measurement sample was placed in an environment of 23°C and 50% RH for 24 hours, and then installed in a tensile testing machine (manufactured by ORIENTEC, product name "TENSILON") in a manner such that the measurement portion became 10 mm × 20 mm in size. Furthermore, it was stretched at a tensile speed of 200 mm/min in an environment of 23°C and 50% RH, and the elongation at break (%) was measured. The results are shown in Table 3 as the elongation E1 before heating.
又，將與上述同樣地進行而得到的伸長率測定用試樣在23℃、50%RH的環境下放置24小時之後，在100℃加熱30分鐘，而且在23℃、50%RH的環境下靜置30分鐘使該試樣的溫度返回至室溫為止之後，與上述同樣地進行而測定斷裂伸長率(%)。將其結果作為在加熱後之伸長率E2且顯示在表3。而且，算出如上述測定之伸長率E2對伸長率E1之比值(E2/E1)。該結果亦顯示在表3。 Furthermore, the elongation test sample obtained in the same manner as above was placed in an environment of 23°C and 50%RH for 24 hours, then heated at 100°C for 30 minutes, and then allowed to stand in an environment of 23°C and 50%RH for 30 minutes until the temperature of the sample returned to room temperature, and then the elongation at break (%) was measured in the same manner as above. The result was taken as the elongation after heating E2 and is shown in Table 3. Furthermore, the ratio of the elongation E2 measured as above to the elongation E1 ( E2 / E1 ) was calculated. The result is also shown in Table 3.
[試驗例7](加熱後的密著性之評價) [Test Example 7] (Evaluation of adhesion after heating)
將實施例及比較例所製造之保護片的黏著劑層側的面，貼合在作為附硬塗層樹脂板之在一面具備以聚甲基丙烯酸甲酯作為材料的硬塗層之聚碳酸酯樹脂板(三菱氣體化學公司製、製品名「HM RS52T」，厚度：2.0mm)之硬塗層側的面，而且將其作為密著性評價用試樣。 The adhesive layer side of the protective sheet manufactured in the embodiment and the comparative example was bonded to the hard coating side of a polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "HM RS52T", thickness: 2.0 mm) with a hard coating layer made of polymethyl methacrylate on one side as a resin plate with a hard coating layer, and used as a sample for evaluating adhesion.
將上述密著性評價用試樣在23℃、50%RH的環境下放置24小時 之後，在100℃加熱30分鐘，而且藉由在23℃、50%RH的環境下靜置30分鐘，使黏著力測定用試樣的溫度返回至室溫為止。針對該密著性評價用試樣，目視確認保護片與附硬塗層樹脂板的界面狀況且基於以下的基準而進行評價保護片加熱後的密著性。將結果顯示在表3。 The above-mentioned adhesion evaluation sample was placed in an environment of 23°C and 50% RH for 24 hours. After that, it was heated at 100°C for 30 minutes, and then left at 23°C and 50% RH for 30 minutes until the temperature of the adhesion measurement sample returned to room temperature. For the adhesion evaluation sample, the interface between the protective sheet and the hard-coated resin sheet was visually confirmed and the adhesion of the protective sheet after heating was evaluated based on the following criteria. The results are shown in Table 3.
◎：不產生浮起或氣泡且保護片良好地密著在附硬塗層樹脂板。 ◎: No floating or bubbles are generated and the protective sheet is well adhered to the hard-coated resin board.
○：雖然稍微產生浮起或氣泡，但是保護片充分地密著在附硬塗層樹脂板。 ○: Although some floating or bubbles occur, the protective sheet is well adhered to the hard-coated resin board.
×：全面產生浮起且保護片從附硬塗層樹脂板剝落。 ×: Floating occurs all over the surface and the protective sheet peels off from the hard-coated resin sheet.
而且，使用將附硬塗層樹脂板變更成為鈉鈣玻璃而得到的密著性評價用試樣，與上述同樣地進行評價保護片加熱後的密著性。其結果亦顯示在表3。 Furthermore, the adhesion evaluation sample obtained by changing the hard-coated resin plate to sodium calcium glass was used to evaluate the adhesion of the protective sheet after heating in the same manner as above. The results are also shown in Table 3.
[試驗例8](加熱後的剝離性之評價) [Test Example 8] (Evaluation of peeling properties after heating)
針對在上述試驗例7得到「◎」或「○」的評價之例子(實施例1~4)，將保護片從上述試驗例7之評價後的密著性評價用試樣剝離，針對此時的剝離狀況且基於以下的基準而進行評價保護片加熱後的剝離性。將結果顯示在表3。 For the examples (Examples 1 to 4) that were evaluated as "◎" or "○" in the above-mentioned Test Example 7, the protective sheet was peeled off from the adhesion evaluation sample after the evaluation of the above-mentioned Test Example 7, and the peeling property of the protective sheet after heating was evaluated based on the peeling state at this time and the following criteria. The results are shown in Table 3.
◎：能夠容易地剝離。 ◎: Can be easily peeled off.
○：雖然剝離需要少許力量，但是能夠剝離。 ○: Although it takes a little force to peel off, it can be peeled off.
×：無法剝離。 ×: Cannot be removed.
又，針對表3中附加「※3」之評價結果，意味著在將保護片從密著性評價用試樣剝離時，雖然黏著劑層係從基材分離而只有黏著劑層殘留在玻璃板上，但是隨後能夠只將該黏著劑層從玻璃板剝離。 In addition, the evaluation results with "※3" in Table 3 mean that when the protective sheet was peeled off from the adhesion evaluation sample, although the adhesive layer was separated from the substrate and only the adhesive layer remained on the glass plate, only the adhesive layer could be peeled off from the glass plate afterwards.
而且，表1中的縮寫如以下所示。 Furthermore, the abbreviations in Table 1 are as follows.
[丙烯酸酯聚合物的組成] [Composition of acrylic polymer]
BA：丙烯酸正丁酯 BA: n-butyl acrylate
2EHA：丙烯酸2-乙基己酯 2EHA: 2-ethylhexyl acrylate
IBXA：丙烯酸異莰酯 IBXA: Isoborneol acrylate
HEMA：甲基丙烯酸2-羥基乙酯 HEMA: 2-Hydroxyethyl methacrylate
BMAA：N-(丁氧基甲基)丙烯醯胺 BMAA: N-(Butoxymethyl)acrylamide
AA：丙烯酸 AA: Acrylic acid
HEA：丙烯酸2-羥基乙酯 HEA: 2-Hydroxyethyl acrylate
[交聯劑] [Crosslinking agent]
異氰酸酯系：六亞甲基二異氰酸酯 Isocyanate series: Hexamethylene diisocyanate
環氧系：1,3-雙(N,N’-二環氧丙基胺甲基)環己烷 Epoxy series: 1,3-bis(N,N’-diepoxypropylaminomethyl)cyclohexane
從表2及表3能夠清楚明白，在實施例所製造的保護片係即便受到加熱處理之後，對被黏著物顯示良好的密著性，同時亦具有優異的剝離性。 It can be clearly seen from Tables 2 and 3 that the protective sheet manufactured in the embodiment shows good adhesion to the adherend even after being subjected to heat treatment, and also has excellent peeling properties.
[產業上之可利用性] [Industrial availability]
本發明之保護片係適合作為用以保護光學構件等的表面之保護片。 The protective sheet of the present invention is suitable as a protective sheet for protecting the surface of optical components, etc.
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-241203 | 2018-12-25 | ||
| JP2018241203A JP7219082B2 (en) | 2018-12-25 | 2018-12-25 | protective sheets and laminates |
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| Publication Number | Publication Date |
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| TW202033347A TW202033347A (en) | 2020-09-16 |
| TWI841611B true TWI841611B (en) | 2024-05-11 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256111A (en) | 1998-03-11 | 1999-09-21 | Nitto Denko Corp | Pressure sensitive adhesive for surface-protecting film, and film for surface protection |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256111A (en) | 1998-03-11 | 1999-09-21 | Nitto Denko Corp | Pressure sensitive adhesive for surface-protecting film, and film for surface protection |
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