KR102232802B1 - Adhesive composition and adhesive tape - Google Patents
Adhesive composition and adhesive tape Download PDFInfo
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- KR102232802B1 KR102232802B1 KR1020187017330A KR20187017330A KR102232802B1 KR 102232802 B1 KR102232802 B1 KR 102232802B1 KR 1020187017330 A KR1020187017330 A KR 1020187017330A KR 20187017330 A KR20187017330 A KR 20187017330A KR 102232802 B1 KR102232802 B1 KR 102232802B1
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- sensitive adhesive
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- adhesive composition
- toluene
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 39
- 239000000853 adhesive Substances 0.000 title abstract description 82
- 230000001070 adhesive effect Effects 0.000 title abstract description 82
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 117
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 47
- 230000008961 swelling Effects 0.000 claims abstract description 39
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
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- 229910052697 platinum Inorganic materials 0.000 description 12
- 238000011282 treatment Methods 0.000 description 11
- 238000013006 addition curing Methods 0.000 description 9
- 229920002050 silicone resin Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
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- 229920002799 BoPET Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
가교 실리콘 성분을 포함하고, 겔 분율(톨루엔에 상온에서 1일간 침지했을 때의 불용해분의 비율)이 45% 이상 70% 미만이며, 톨루엔에 대한 팽윤도(1일간 침지했을 때의 톨루엔 흡수에 의한 팽윤 비율)가 290% 이하인 점착제 조성물; 및, 이 점착제 조성물로 이루어지는 점착제층을 가지는 점착 테이프가 개시된다. 이 점착제 조성물 및 점착 테이프는 부품의 고정력이 뛰어나고, 고온 환경하에서 사용해도 점착제 잔여 없이 박리할 수 있으며, 또한 접착-박리를 반복하여도 접착력의 변화가 적다.It contains a crosslinked silicone component, and the gel fraction (the ratio of the insoluble matter when immersed in toluene at room temperature for 1 day) is 45% or more and less than 70%, and the degree of swelling to toluene (by absorption of toluene when immersed for 1 day) A pressure-sensitive adhesive composition having a swelling ratio) of 290% or less; And, the adhesive tape which has the adhesive layer which consists of this adhesive composition is disclosed. This pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape have excellent fixing power of parts, can be peeled off without residual pressure-sensitive adhesive even when used in a high-temperature environment, and there is little change in the adhesive force even if the adhesive-peeling is repeated.
Description
본 발명은, 예를 들면, 전기·전자 부품 등의 제조 공정에서 사용되는 점착 테이프에 있어서, 부품의 고정력이 뛰어나고, 고온 환경하에서 사용해도 점착제 잔여 없이 박리할 수 있으며, 또한 접착-박리를 반복하여도 접착력의 변화가 적은 점착제 조성물 및 점착 테이프에 관한 것이다.The present invention, for example, in the adhesive tape used in the manufacturing process of electric and electronic components, has excellent fixing power of the component, can be peeled off without residual adhesive even when used in a high temperature environment, and also by repeating the adhesion-peeling. It also relates to an adhesive composition and an adhesive tape with little change in adhesive force.
실리콘 점착제 조성물은, 내열성, 내한성, 내후성, 전기 절연성, 내약품성, 각종 피착체에 대한 점착성이 뛰어나다. 또한 실리콘 점착제층을 가지는 점착 테이프는, 특히 고온 환경하에서 사용해도 박리 후에 점착제 잔여물이 남기 어렵다. 따라서, 그러한 점착 테이프는, 전기·전자 부품 등의 각종 부품의 제조 공정에 있어서 부품의 보호, 마스킹, 가고정, 반송용 고정 등의 용도에 넓리 이용되고 있다.The silicone pressure-sensitive adhesive composition is excellent in heat resistance, cold resistance, weather resistance, electrical insulation, chemical resistance, and adhesion to various adherends. In addition, even if the adhesive tape having a silicone adhesive layer is used in a high-temperature environment, it is difficult to leave an adhesive residue after peeling. Therefore, such an adhesive tape is widely used for applications such as protection, masking, temporary fixing, and fixing for conveyance in the manufacturing process of various components such as electric and electronic components.
종래의 점착 테이프는 반복 사용했을 때의 접착성이 안정되지 않고, 약 1회 사용할 때마다 교환할 필요가 있었다. 구체적으로는, 박리를 반복함으로써 점착면이 거칠어져 피착체에 보다 융합되기 쉬워지는 등의 이유에 의해 접착력이 상승하여, 테이프를 박리할 수 없는 경우가 있다. 또한, 박리를 반복함으로써 점착제 중의 저분자 성분이나 접착성의 발현에 기여하는 성분이 피착체로 이행하는 등의 이유로 접착력이 저하한 경우, 부품에 대한 고정력이 부족하여 공정 중에 부품이 벗겨져 떨어지는 경우가 있다. 또한, 고온 환경하에서 반복 사용하는 동안에 점착제가 열화하여, 부품에 점착제 잔여물이 남는 경우도 있다.Conventional adhesive tapes do not have stable adhesiveness when repeatedly used, and need to be replaced about each time they are used. Specifically, by repeating peeling, the adhesive strength may increase due to reasons such as roughening of the adhesive surface, which makes it easier to fuse with the adherend, and thus the tape may not be peeled off. In addition, when peeling is repeated, the low molecular weight component in the pressure-sensitive adhesive or the component contributing to the expression of the adhesive property is lowered due to reasons such as migration to the adherend, the component may be peeled off during the process due to insufficient fixing power to the component. In addition, during repeated use in a high-temperature environment, the pressure-sensitive adhesive may deteriorate, leaving a residual pressure-sensitive adhesive on the part.
종래는, 박리 후에 점착제 잔여물이 남기 어려운 실리콘 점착제 조성물이나 점착 테이프가 많이 연구되어 왔다(예를 들면 특허문헌 1∼4). 그러나, 박리 후의 접착력의 안정성이라는 과제에 관해서는 조금도 검토되고 있지 않다.Conventionally, many studies have been conducted on silicone pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes in which adhesive residues are less likely to remain after peeling (for example,
특허문헌 5에서는, 디스플레이 패널 등의 정보 표시 화면에 투명 보호 커버를 첩착(貼着)하기 위한 양면 점착 테이프로서, 기재 필름의 한쪽 면에 실리콘 수지를 주성분으로 하는 흡착층을 적층하고, 다른 한쪽 면에 아크릴계 점착제로 이루어지는 점착제층을 적층한 점착 테이프가 개시되어 있다. 이 실리콘 흡착층은 다시 붙이는 것을 전제로 한 것이지만, 이 문헌 내에 박리를 반복했을 때의 접착력의 안정성은 물론, 점착력 등의 기본적인 점착 물성에 관하여 언급되어 있지 않다. 또한, 이 흡착층은 어디까지나 실리콘 수지이며, 그 보호 커버 정도의 중량의 것이 디스플레이 패널로부터 벗겨져 떨어지지 않을 정도의 소소한 흡착력을 얻는 것을 목적으로 하고 있기 때문에, 전기·전자 부품 등의 제조 공정에서 사용되는 점착 테이프와 같이, 어떠한 외력이나 다른 부품을 고정하는 힘(즉 고정력)이 가해지는 용도를 목적으로 한 것과는 근본적으로 상이한 것이다.In Patent Document 5, as a double-sided adhesive tape for attaching a transparent protective cover to an information display screen such as a display panel, an adsorption layer containing a silicone resin as a main component is laminated on one side of a base film, and the other side A pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive is laminated is disclosed. This silicone adsorption layer is made on the premise that it is reattached, but in this document, not only the stability of the adhesive force when peeling is repeated, nor the basic adhesive properties such as adhesive force are mentioned. In addition, this adsorption layer is a silicone resin to the last, and it is used in the manufacturing process of electric and electronic parts, because it aims to obtain a small adsorption force that does not peel off and fall off the weight of the protective cover from the display panel. Like an adhesive tape, it is fundamentally different from that intended for use in which any external force or force (ie, a clamping force) is applied.
특허문헌 6∼8에서는, 판체로 이루어지는 지그(jig) 베이스에 약(弱)점착성 수지를 도포한 프린트 배선 기판의 유지 반송용의 지그에 관하여 개시되어 있다. 이들 특허문헌에도 박리를 반복했을 때의 접착력의 안정성은 물론, 점착력 등의 기본적인 점착 물성에 관하여 언급되어 있지 않고, 충분한 검증이 이루어졌다고는 말할 수 없다. 특허문헌 내에서는 약점착성의 점착제가 사용되고 있으나, 약점착성이라면 반드시 박리를 반복했을 때의 접착력이 안정되는 것은 아니다. 또한 부품에 대한 고정력이나 점착제 잔여성도 검증되어 있지 않다.In Patent Documents 6 to 8, a jig for holding and transporting a printed wiring board in which a weakly adhesive resin is applied to a jig base made of a plate body is disclosed. In these patent documents, as well as the stability of adhesive force when peeling is repeated, basic adhesive physical properties such as adhesive force are not mentioned, and it cannot be said that sufficient verification has been made. In the patent literature, a weakly-adhesive pressure-sensitive adhesive is used, but if it is weakly-adhesive, the adhesive strength when repeated peeling is not necessarily stable. In addition, the fixation power or residual adhesiveness to the parts has not been verified.
본 발명자들은, 박리 후의 접착력의 안정성이라는 과제에 주목하여, 전기·전자 부품 등의 각종 부품의 제조 공정에서의 코스트 삭감을 목적으로 하여 반복 사용이 가능한 점착 테이프에 관해서 개발을 실시했다. 즉 본 발명의 목적은, 부품의 고정력이 뛰어나고, 고온 환경하에서 사용해도 점착제 잔여 없이 박리할 수 있으며, 또한 접착-박리를 반복하여도 접착력의 변화가 적은 점착제 조성물 및 점착 테이프를 제공하는 것에 있다.The present inventors paid attention to the problem of stability of adhesive force after peeling, and developed an adhesive tape that can be repeatedly used for the purpose of reducing the cost in the manufacturing process of various parts such as electric and electronic parts. That is, an object of the present invention is to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that has excellent fixing power of parts, can be peeled off without residual pressure-sensitive adhesive even when used in a high-temperature environment, and also exhibit little change in adhesive force even after repeated adhesion-peeling.
본 발명자들은 상기 목적을 달성하기 위하여 예의 검토한 결과, 실리콘 점착제층의 겔 분율과 팽윤도의 밸런스가, 반복 사용했을 때의 접착력의 변화 및 그 밖의 제성능과 관계되어 있는 것을 발견하여, 본 발명을 완성하기에 이르렀다.The inventors of the present invention found that the balance between the gel fraction and the degree of swelling of the silicone pressure-sensitive adhesive layer is related to the change in adhesive force and other performances when repeatedly used as a result of intensive study in order to achieve the above object. It came to completion.
즉 본 발명은, 가교된 실리콘 구조를 포함하고, 하기 방법에 의해 측정되는 겔 분율이 45% 이상 70% 미만이며, 또한 하기 방법에 의해 측정되는 톨루엔에 대한 팽윤도가 290% 이하인 것을 특징으로 하는 실리콘계 점착제 조성물이다.That is, the present invention includes a crosslinked silicone structure, a gel fraction measured by the following method is 45% or more and less than 70%, and a swelling degree for toluene measured by the following method is 290% or less. It is an adhesive composition.
(겔 분율)(Gel fraction)
톨루엔에 실리콘계 점착제 조성물을 상온에서 1일간 침지했을 때의 불용해분의 비율인, 하기식에 의해 겔 분율을 얻는다.The gel fraction is obtained by the following formula, which is the ratio of the insoluble matter when the silicone pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
겔 분율(%)=(C/A)×100Gel fraction (%) = (C/A) × 100
A: 실리콘계 점착제 조성물의 초기 질량 A: Initial mass of the silicone pressure-sensitive adhesive composition
C: 톨루엔 침지 후의 실리콘계 점착제 조성물의 건조 질량(건조 조건: 130℃, 2시간) C: Dry mass of the silicone pressure-sensitive adhesive composition after toluene immersion (drying conditions: 130°C, 2 hours)
(팽윤도)(Swelling degree)
톨루엔에 실리콘계 점착제 조성물을 상온에서 1일간 침지했을 때의 톨루엔 흡수에 의한 팽윤 비율인, 하기식에 의해 팽윤도를 얻는다.The degree of swelling is obtained by the following formula, which is the swelling ratio due to toluene absorption when the silicone pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
팽윤도(%)=((B-A)/A)×100% Swelling degree (%)=((B-A)/A)×100%
A: 실리콘계 점착제 조성물의 초기 질량 A: Initial mass of the silicone pressure-sensitive adhesive composition
B: 톨루엔 침지 후의 실리콘계 점착제 조성물의 팽윤 질량 B: Swelling mass of the silicone pressure-sensitive adhesive composition after toluene immersion
또한 본 발명은, 기재의 적어도 편면(片面)에 상기 점착제 조성물로 이루어지는 점착제층을 가지는 점착 테이프이다.Further, the present invention is an adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition on at least one side of a substrate.
본 발명에 의하면, 부품의 고정력이 뛰어나고, 고온 환경하에서 사용해도 점착제 잔여 없이 박리할 수 있고, 또한 접착-박리를 반복하여도 접착력의 변화가 적은 점착제 조성물 및 점착 테이프가 제공된다. 특히, 본 발명의 점착 테이프는 상기 특정의 점착제층을 가지므로, 예를 들면 고온하에서의 전기·전자 부품 등의 각종 부품의 제조 공정에 있어서, 공정 중에서 부품이 벗겨져 떨어지는 경우가 없고, 박리 후에 점착제 잔여물이 남기 어렵고, 또한 접착-박리를 반복하여도 접착력의 변화가 적기 때문에 반복 사용이 가능하며, 코스트 삭감의 점에서 매우 유용하다.Advantageous Effects of Invention According to the present invention, there are provided an adhesive composition and an adhesive tape that have excellent fixing power of parts, can be peeled off without residual adhesive even when used in a high-temperature environment, and have little change in adhesive force even when the adhesive-peeling is repeated. In particular, since the adhesive tape of the present invention has the specific adhesive layer, for example, in the manufacturing process of various components such as electric and electronic components under high temperature, the component does not peel off during the process, and the adhesive remains after peeling. Since water is difficult to remain and the change in adhesion is small even after repeated adhesion-peeling, it can be used repeatedly, and is very useful in terms of cost reduction.
[도 1] 실시예 및 비교예의 종합 평가를, 겔 분율과 팽윤도의 상관관계에 있어서 정리한 그래프이다.
[도 2] 실시예 및 비교예에 있어서의 고정력 시험을 설명하기 위한 모식도이다.[Fig. 1] It is a graph which put together the general evaluation of an Example and a comparative example in the correlation between a gel fraction and swelling degree.
It is a schematic diagram for demonstrating the fixing force test in an Example and a comparative example.
<점착제 조성물><Adhesive composition>
본 발명의 점착제 조성물은, 실리콘계 점착제를 주성분으로서 포함하는 점착제 조성물이다. 본 발명의 점착제 조성물의 겔 분율은 45% 이상 70% 미만이며, 바람직하게는 48∼65%, 보다 바람직하게는 50∼60%이다. 또한, 본 발명의 점착제 조성물의 톨루엔에 대한 팽윤도는 290% 이하이며, 바람직하게는 260% 이하, 보다 바람직하게는 230% 이하이다. 겔 분율 및 팽윤도의 구체적인 측정 방법은, 후술하는 실시예란에 기재한다. 일반적으로, 팽윤도는 점착제 조성물의 가교 밀도에 의존한다. 가교 밀도가 높은 경우는 톨루엔에 침지해도 점착제를 구성하는 삼차원으로 가교된 폴리머쇄가 넓어지기 어렵고, 팽윤도는 낮아진다. 한편, 가교 밀도가 낮은 경우는 폴리머쇄가 넓어지기 쉽고 팽윤도는 높아진다.The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a silicone pressure-sensitive adhesive as a main component. The gel fraction of the pressure-sensitive adhesive composition of the present invention is 45% or more and less than 70%, preferably 48 to 65%, and more preferably 50 to 60%. In addition, the degree of swelling of the pressure-sensitive adhesive composition of the present invention with respect to toluene is 290% or less, preferably 260% or less, and more preferably 230% or less. The specific measuring method of the gel fraction and the degree of swelling is described in the Examples section described later. In general, the degree of swelling depends on the crosslinking density of the pressure-sensitive adhesive composition. When the crosslinking density is high, even if immersed in toluene, the three-dimensionally crosslinked polymer chain constituting the pressure-sensitive adhesive is difficult to widen, and the degree of swelling is lowered. On the other hand, when the crosslinking density is low, the polymer chain tends to become wider and the degree of swelling increases.
겔 분율과 팽윤도가 본 발명의 특정의 범위이면, 충분한 고정력과 점착제 잔여 방지성, 반복 사용했을 때의 접착력의 안정성을 얻을 수 있다. 겔 분율이 45% 미만이면, 고정력은 보다 강고하게 되는 반면, 응집력 부족에 의한 점착제 잔여가 발생하기 쉬워져, 반복 사용했을 때의 접착력은 안정되지 않는다. 한편, 겔 분율이 70%를 넘으면, 충분한 고정력을 얻을 수 없다. 또한, 겔 분율이 45% 이상 70% 미만의 범위 내여도, 팽윤도가 290%를 초과하면, 가교 밀도가 낮은 것에 기인한 응집력 부족에 의한 점착제 잔여가 발생하기 쉬워져, 반복 사용했을 때의 접착력은 안정되지 않는다.If the gel fraction and the degree of swelling are within the specific ranges of the present invention, sufficient fixing power, adhesive residual prevention property, and stability of adhesive force when repeatedly used can be obtained. When the gel fraction is less than 45%, the fixing force becomes stronger, whereas the adhesive residue due to insufficient cohesive force tends to occur, and the adhesive force when repeatedly used is not stable. On the other hand, when the gel fraction exceeds 70%, sufficient fixing force cannot be obtained. In addition, even if the gel fraction is in the range of 45% or more and less than 70%, if the swelling degree exceeds 290%, residual adhesive due to insufficient cohesive strength due to low crosslinking density is likely to occur, and the adhesive strength when repeatedly used Not stable.
본 발명에 사용하는 실리콘계 점착제의 구체예로서는, 주로 실리콘 생고무(D단위[(CH3)2SiO]로 이루어지는 폴리디메틸실록산의 장쇄의 중합체)와 MQ레진(M단위[(CH3)3SiO1 /2]와 Q단위[SiO2]로 이루어지는 3차원 구조의 실리콘 레진의 중합체)로 이루어지는 점착제를 들 수 있다. 이러한 실리콘 생고무와 MQ레진으로 이루어지는 점착제는, 실리콘 생고무 단체와 비교하여 점착성이 뛰어나다. 또한, 점착제 중의 실리콘 생고무와 MQ레진의 비율을 바꿈으로써 점착력·유지력·턱(tuck) 등의 기본적인 점착 물성을 컨트롤할 수 있다. 실리콘계 점착제로서는, 그 경화 기구(機構)에 의해, 부가 경화형, 과산화물 경화형으로 대별(大別)된다. 부가 경화형 실리콘 점착제는, 알케닐기를 함유하는 실리콘 생고무로 이루어지는 주제(主劑)와 SiH기를 함유하는 폴리오가노실록산으로 이루어지는 가교제를 예를 들면 백금 촉매하에서 가열하여 가교 반응시키는 것에 의해 경화한다. 이때 가교제의 양을 적절히 조정함으로써 가교 밀도를 바꾸는 것이 가능하다. 또한, 과산화물 경화형 실리콘 점착제는, 경화제로서 과산화벤조일 등의 과산화물을 첨가하여, 용매를 제거한 후, 예를 들면 고온으로 가열함으로써 경화한다. 이때, 첨가하는 과산화물의 양을 적절히 조정함으로써 점착제의 가교 밀도를 바꾸는 것이 가능하다. 실리콘계 점착제는 2종 이상을 조합하여 사용해도 된다. 특히, 본 발명의 점착제 조성물은 가교 경화된 부가 경화형 실리콘 점착제를 포함하는 것이 바람직하다.As a specific example of the silicone adhesive used in the present invention, mainly raw silicone rubber ( a long-chain polymer of polydimethylsiloxane consisting of D units [(CH 3 ) 2 SiO]) and MQ resin (M units [(CH 3 ) 3 SiO 1 / 2 ] and a pressure-sensitive adhesive made of a polymer of a silicone resin having a three-dimensional structure consisting of a Q unit [SiO 2 ]. The adhesive made of such a raw silicone rubber and an MQ resin has excellent adhesiveness compared to that of the raw silicone rubber alone. In addition, by changing the ratio of the raw silicone rubber and the MQ resin in the adhesive, basic adhesive properties such as adhesion, retention, and tuck can be controlled. As a silicone pressure-sensitive adhesive, it is roughly classified into an addition curing type and a peroxide curing type by its curing mechanism. The addition-curable silicone pressure-sensitive adhesive is cured by heating a crosslinking agent composed of a base material composed of a silicone raw rubber containing an alkenyl group and a polyorganosiloxane containing a SiH group, for example, by heating under a platinum catalyst for crosslinking reaction. At this time, it is possible to change the crosslinking density by appropriately adjusting the amount of the crosslinking agent. In addition, the peroxide-curable silicone pressure-sensitive adhesive is cured by adding a peroxide such as benzoyl peroxide as a curing agent, removing the solvent, and heating, for example, at a high temperature. At this time, it is possible to change the crosslinking density of the pressure-sensitive adhesive by appropriately adjusting the amount of peroxide to be added. Silicone adhesives may be used in combination of two or more. In particular, it is preferable that the pressure-sensitive adhesive composition of the present invention includes a crosslinked curable addition-curable silicone pressure-sensitive adhesive.
본 발명의 점착제 조성물은, 시판품을 사용하여 얻을 수 있다. 예를 들면, 시판의 실리콘계 점착제를 가교 경화시키는 것에 의해 원하는 물성의 점착제 조성물을 얻을 수 있다. 구체적으로는, 먼저 예시한 실리콘계 점착제를 가교 경화시키는 것에 의해, 가교된 실리콘 구조를 포함하는 본 발명의 점착제 조성물을 얻을 수 있다. 가교 경화 반응은 통상은 가열에 의해 실시하지만, 점착제나 경화제의 종류에 따라서는 축합 반응이나 자외선 조사로도 가교 경화가 가능하다.The pressure-sensitive adhesive composition of the present invention can be obtained using a commercial item. For example, by crosslinking and curing a commercially available silicone pressure-sensitive adhesive, a pressure-sensitive adhesive composition with desired physical properties can be obtained. Specifically, the pressure-sensitive adhesive composition of the present invention containing a crosslinked silicone structure can be obtained by crosslinking and curing the silicone pressure-sensitive adhesive exemplified above. The crosslinking curing reaction is usually carried out by heating, but depending on the type of pressure-sensitive adhesive or curing agent, crosslinking curing can also be performed by condensation reaction or ultraviolet irradiation.
본 발명의 특정의 겔 분율 및 팽윤도를 가지는 점착제 조성물은, 예를 들면, 2종 이상의 시판 실리콘계 점착제의 혼합물을 사용해 얻을 수 있다. 구체적으로는, 예를 들면 겔 분율 및 팽윤도가 비교적 높은 실리콘계 점착제와, 겔 분율 및 팽윤도가 비교적 낮은 실리콘계 점착제를 적당한 비율로 혼합하여 가교 경화하는 것에 의해, 겔 분율 및 팽윤도가 본 발명의 범위 내가 되는 점착제 조성물을 얻을 수 있다. 단 본 발명의 점착제 조성물은, 이러한 방법으로 얻은 것에 한정되는 것은 아니다.The pressure-sensitive adhesive composition having a specific gel fraction and swelling degree of the present invention can be obtained, for example, using a mixture of two or more commercially available silicone-based pressure-sensitive adhesives. Specifically, for example, by mixing a silicone-based adhesive having a relatively high gel fraction and swelling degree and a silicone-based adhesive having a relatively low gel fraction and swelling degree in an appropriate ratio and crosslinking and curing, the gel fraction and swelling degree are within the scope of the present invention. A pressure-sensitive adhesive composition can be obtained. However, the pressure-sensitive adhesive composition of the present invention is not limited to those obtained by such a method.
본 발명의 점착제 조성물에는, 각종 특성의 향상을 목적으로 하여 첨가제를 첨가해도 된다. 첨가제의 구체예로서는, 카본블랙, 실리카 등의 무기 충전제; 실리콘레진, 폴리디메틸실록산, 폴리디메틸페닐실록산 등의 폴리오가노실록산; 페놀계 산화 방지제, 아민계 산화 방지제 등의 산화 방지제; 실란커플링제를 들 수 있다. 단 첨가제의 종류나 양은, 발명의 효과가 손상되지 않도록 적절히 선정할 필요가 있다.Additives may be added to the pressure-sensitive adhesive composition of the present invention for the purpose of improving various properties. Specific examples of the additive include inorganic fillers such as carbon black and silica; Polyorganosiloxanes such as silicone resin, polydimethylsiloxane, and polydimethylphenylsiloxane; Antioxidants such as phenolic antioxidants and amine antioxidants; Silane coupling agents are mentioned. However, the type or amount of the additive needs to be appropriately selected so that the effect of the invention is not impaired.
<점착 테이프><Adhesive tape>
본 발명의 점착 테이프는, 기재의 적어도 편면에 이상 설명한 본 발명의 점착제 조성물로 이루어지는 점착제층을 가지는 점착 테이프이며, 대표적으로는, 기재 필름의 편면 또는 양면에 그 점착제층을 가지는 점착 테이프이다. 점착제층의 두께는 특별히 한정되지 않지만, 바람직하게는 2∼150μm, 보다 바람직하게는 5∼100μm, 특히 바람직하게는 10∼75μm이다.The adhesive tape of the present invention is an adhesive tape having an adhesive layer made of the adhesive composition of the present invention described above on at least one side of a base material, and is typically an adhesive tape having the adhesive layer on one side or both sides of a base film. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 2 to 150 µm, more preferably 5 to 100 µm, and particularly preferably 10 to 75 µm.
점착제층은, 점착제 조성물을 가교 경화 반응시키는 것에 의해 형성할 수 있다. 예를 들면, 점착제 조성물을 기재상에 도포하고, 가열 또는 축합 반응이나 자외선 조사에 의해 가교 경화시켜 기재상에 점착제층을 형성할 수 있다. 또한, 점착제 조성물을 이형지 또는 그 밖의 필름상에 도포하고, 가열 또는 축합 반응이나 자외선 조사에 의해 가교 경화시켜 점착제층을 형성하고, 이 점착제층을 기재의 편면 또는 양면에 첩합할 수도 있다.The pressure-sensitive adhesive layer can be formed by subjecting the pressure-sensitive adhesive composition to a crosslinking curing reaction. For example, a pressure-sensitive adhesive composition may be applied on a substrate and crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the substrate. Further, the pressure-sensitive adhesive composition may be applied onto a release paper or other film, crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer may be bonded to one or both sides of the substrate.
도포시의 점착제 조성물의 점도를 낮추기 위해, 용제를 첨가해도 된다. 용제의 구체예로서는, 톨루엔, 자일렌 등의 방향족계 용제; 헥산, 옥탄, 이소파라핀 등의 지방족계 용제; 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤계 용제; 아세트산에틸, 아세트산이소부틸 등의 에스테르계 용제; 디이소프로필에테르, 1,4-디옥산 등의 에테르계 용제를 들 수 있다.In order to lower the viscosity of the pressure-sensitive adhesive composition at the time of application, a solvent may be added. Specific examples of the solvent include aromatic solvents such as toluene and xylene; Aliphatic solvents such as hexane, octane, and isoparaffin; Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Ester solvents such as ethyl acetate and isobutyl acetate; Ether solvents, such as diisopropyl ether and 1,4-dioxane, are mentioned.
도공 방법은 특별히 한정되지 않으며, 공지의 방법을 이용하면 된다. 그 구체예로서는, 콤마코터, 립코터, 롤코터, 다이코터, 나이프코터, 브레이드코터, 로드코터, 키스 코터 또는 그라비아코터를 사용한 도공; 스크린 도공; 침지 도공; 캐스트 도공을 들 수 있다.The coating method is not particularly limited, and a known method may be used. As a specific example, coating using a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a braid coater, a rod coater, a kiss coater or a gravure coater; Screen coating; Immersion coating; Cast potters are mentioned.
기재는 특별히 한정되지 않지만, 필름상(狀)의 기재가 바람직하다. 특히, 고온하에서 처리 가능한 내열성이 높은 수지 필름이 바람직하다. 그 구체예로서는 예를 들면, 폴리이미드(PI), 폴리에테르에테르케톤(PEEK), 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈레이트(PEN), 폴리페닐렌설파이드(PPS), 폴리아미드이미드(PAI), 폴리에테르술폰(PES), 폴리테트라플루오로에틸렌(PTFE) 등의 수지 필름을 들 수 있다. 이들 필름을 단층, 또는 2층 이상의 적층 필름으로서 사용할 수 있다. 그 중에서도, 폴리이미드필름이 바람직하다. 기재의 두께는 특별히 한정되지 않지만, 바람직하게는 2∼180μm, 보다 바람직하게는 5∼100μm, 특히 바람직하게는 12∼75μm이다.The substrate is not particularly limited, but a film-like substrate is preferable. In particular, a resin film with high heat resistance that can be treated under high temperature is preferable. Specific examples thereof include, for example, polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamideimide (PAI), And resin films such as polyethersulfone (PES) and polytetrafluoroethylene (PTFE). These films can be used as a single layer or as a laminated film of two or more layers. Among them, a polyimide film is preferable. The thickness of the substrate is not particularly limited, but is preferably 2 to 180 µm, more preferably 5 to 100 µm, and particularly preferably 12 to 75 µm.
또한, 기재의 점착제층을 설치하는 면에는, 필요에 따라 이(易)접착 처리를 실시해도 된다. 이접착 처리로서는, 예를 들면, 프라이머 처리, 코로나 처리, 에칭 처리, 플라스마 처리, 샌드블레스트 처리 등을 들 수 있다.In addition, on the surface on which the pressure-sensitive adhesive layer of the substrate is provided, an easily bonding treatment may be performed as necessary. Examples of the easy adhesion treatment include primer treatment, corona treatment, etching treatment, plasma treatment, and sandblast treatment.
본 발명의 점착 테이프에는 박리 라이너를 설치해도 된다. 박리 라이너란, 점착 테이프의 점착제층을 보호하기 위한 것이며, 첩부기 직전에 박리하여, 점착제를 노출시켜 피착체에 점착 테이프를 첩부한다. 박리 라이너의 종류는 특별히 한정되지 않고, 공지의 박리 라이너를 사용할 수 있다. 그 구체예로서는, 상질지(上質紙), 그라신지(紙), 합성 수지 필름 등의 기재의 표면에 이형제 처리를 실시한 것을 들 수 있다. 이형제 처리에는, 예를 들면 불소 치환 알킬 변성 실리콘 수지 등에 의한 이형제를 사용하면 된다. 특히, 실리콘계 점착제층에 적층하는 박리 라이너로서는, 폴리에틸렌테레프탈레이트 필름의 표면을 불소 치환 알킬 변성 실리콘 수지로 이형 처리한 것이 바람직하다.You may provide a release liner to the adhesive tape of this invention. The release liner is for protecting the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, and is peeled immediately before the sticking machine to expose the pressure-sensitive adhesive, and the pressure-sensitive adhesive tape is affixed to the adherend. The kind of release liner is not particularly limited, and a known release liner can be used. As a specific example, the thing which performed the releasing agent treatment on the surface of a base material, such as high-quality paper, glassine paper, and synthetic resin film, is mentioned. For the releasing agent treatment, for example, a releasing agent made of a fluorine-substituted alkyl-modified silicone resin or the like may be used. In particular, as a release liner laminated on the silicone pressure-sensitive adhesive layer, it is preferable that the surface of a polyethylene terephthalate film is subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin.
실시예Example
이하, 실시예에 의해 본 발명을 더 상세하게 설명한다. 단, 본 발명은 이들 실시예에 한정되는 것은 아니다. 이하의 기재에 있어서 「부(部)」는 「질량부」를 의미한다.Hereinafter, the present invention will be described in more detail by examples. However, the present invention is not limited to these Examples. In the following description, "part" means "mass part".
<실시예 1><Example 1>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4560, 도레이·다우코닝가부시키가이샤제) 70부, 고형분 농도 40질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4587L, 도레이·다우코닝가부시키가이샤제) 30부, 희석 용제로서 톨루엔 54부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(1)을 얻었다.Addition-curable silicone adhesive stock solution with a solid content of 60% by mass (brand name SD-4560, manufactured by Toray Dow Corning Co., Ltd.), 70 parts, addition-curable silicone adhesive stock solution with a solid content concentration of 40% by mass (brand name SD-4587L, Toray-Dow Corning Co., Ltd.) (Manufactured by Bushiki Corporation) 30 parts, 54 parts of toluene as a diluting solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain a pressure-sensitive adhesive solution (1).
다음으로, 프라이머 처리한 두께 25μm의 폴리이미드(PI) 필름의 편면에, 점착제액(1)을 건조 후의 점착제층의 두께가 30μm가 되도록 도포하고, 건조로 내에서 130℃, 2분에서 경화·건조하여 점착제층을 형성했다. 그리고 박리 라이너(불소 치환 알킬 변성 실리콘 수지로 이형 처리를 실시한 두께 50μm의 PET 필름)를 점착제층에 첩합하여, 점착 테이프를 얻었다.Next, on one side of a 25 μm-thick polyimide (PI) film treated with a primer, the pressure-sensitive adhesive solution (1) was applied so that the thickness of the pressure-sensitive adhesive layer after drying was 30 μm, and cured in a drying furnace at 130° C. for 2 minutes. It dried to form a pressure-sensitive adhesive layer. Then, a release liner (a 50 μm-thick PET film subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin) was bonded to the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.
<실시예 2><Example 2>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4560, 도레이·다우코닝가부시키가이샤제) 50부, 고형분 농도 40질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4587L, 도레이·다우코닝가부시키가이샤제) 50부, 희석 용제로서 톨루엔 43부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(2)을 얻었다. 그리고, 점착제액(2)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning, Inc.) 50 parts, solid content concentration of 60% by mass (trade name SD-4587L, Toray Dow Corning Co., Ltd.) 50 parts (manufactured by Bushiki Co., Ltd.), 43 parts of toluene as a diluting solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain a pressure-sensitive adhesive liquid (2). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (2).
<실시예 3><Example 3>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4560, 도레이·다우코닝가부시키가이샤제) 20부, 고형분 농도 40질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4587L, 도레이·다우코닝가부시키가이샤제) 80부, 희석 용제로서 톨루엔 26부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(3)을 얻었다. 그리고, 점착제액(3)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curable silicone adhesive stock solution (brand name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) with a solid content concentration of 60% by mass (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) 80 parts (manufactured by Bushiki Co., Ltd.), 26 parts of toluene as a diluting solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toray Dow Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain a pressure-sensitive adhesive solution (3). And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (3).
<비교예 1><Comparative Example 1>
고형분 농도 40질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4587L, 도레이·다우코닝가부시키가이샤제) 100부, 희석 용제로서 톨루엔 33부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(4)을 얻었다. 그리고, 점착제액(4)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution having a solid content of 40% by mass (trade name SD-4587L, manufactured by Toray Dow Corning Co., Ltd.)100 parts, toluene 33 parts as a diluent solvent, platinum catalyst as a curing catalyst (trade name NC-25, Toray Dow Corning Co., Ltd.) Corning Co., Ltd.) 0.3 parts were mixed uniformly, and the adhesive liquid (4) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (4).
<비교예 2><Comparative Example 2>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4580, 도레이·다우코닝가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(5)을 얻었다. 그리고, 점착제액(5)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4580, manufactured by Toray Dow Corning Co., Ltd.) 100 parts of
<비교예 3><Comparative Example 3>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4584, 도레이·다우코닝가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(6)을 얻었다. 그리고, 점착제액(6)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4584, manufactured by Toray Dow Corning Co., Ltd.)100 parts of
<비교예 4><Comparative Example 4>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4560, 도레이·다우코닝가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(7)을 얻었다. 그리고, 점착제액(7)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution with a solid content of 60% by mass (brand name SD-4560, manufactured by Toray Dow Corning Co., Ltd.)100 parts, toluene 71 parts as a dilution solvent, platinum catalyst as a curing catalyst (brand name NC-25, Toray Dow Corning Co., Ltd.) Corning Co., Ltd.) 0.3 part was uniformly mixed, and the adhesive liquid (7) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (7).
<비교예 5><Comparative Example 5>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 SD-4570, 도레이·다우코닝가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 NC-25, 도레이·다우코닝가부시키가이샤제) 0.3부를 균일하게 혼합하여, 점착제액(8)을 얻었다. 그리고, 점착제액(8)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4570, manufactured by Toray Dow Corning, Inc.)100 parts of
<비교예 6><Comparative Example 6>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 KR-3700, 신에츠가가쿠고교가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 CAT-PL-50T, 신에츠가가쿠고교가부시키가이샤제) 0.5부를 균일하게 혼합하여, 점착제액(9)을 얻었다. 그리고, 점착제액(9)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution (trade name KR-3700, manufactured by Shin-Etsu Chemical Co., Ltd.)100 parts of
<비교예 7><Comparative Example 7>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 KR-3701, 신에츠가가쿠고교가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 CAT-PL-50T, 신에츠가가쿠고교가부시키가이샤제) 0.5부를 균일하게 혼합하여, 점착제액(10)을 얻었다. 그리고, 점착제액(10)을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution having a solid content of 60% by mass (trade name KR-3701, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)100 parts, toluene 71 parts as a diluent solvent, platinum catalyst as a curing catalyst (trade name CAT-PL-50T, Shin-Etsu Chemical Co., Ltd.) 0.5 part was uniformly mixed, and the adhesive liquid (10) was obtained. And the adhesive tape was obtained by the method similar to Example 1 except having used the adhesive liquid (10).
<비교예 8><Comparative Example 8>
고형분 농도 60질량%의 부가 경화형 실리콘 점착제 원액(상품명 KR-3704, 신에츠가가쿠고교가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화 촉매로서 백금 촉매(상품명 CAT-PL-50T, 신에츠가가쿠고교가부시키가이샤제) 0.5부를 균일하게 혼합하여, 점착제액(11)을 얻었다. 그리고, 점착제액(11)을 이용한 것과, 박리 라이너로서 두께 38μm의 미처리의 PET 필름을 사용한 것 이외는 실시예 1과 동일한 방법으로, 점착 테이프를 얻었다.Addition-curing silicone pressure-sensitive adhesive stock solution having a solid content of 60% by mass (trade name KR-3704, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)100 parts, toluene 71 parts as a diluting solvent, platinum catalyst as a curing catalyst (trade name CAT-PL-50T, Shin-Etsu Chemical Co., Ltd.) 0.5 part was uniformly mixed, and the adhesive liquid (11) was obtained. And an adhesive tape was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive liquid 11 was used and an untreated PET film having a thickness of 38 μm was used as a release liner.
<비교예 9><Comparative Example 9>
고형분 농도 60질량%의 과산화물 경화형 실리콘 점착제 원액(상품명 SH-4280, 도레이·다우코닝가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화제(상품명 나이퍼(등록상표) BMT-40, 니치유가부시키가이샤제) 3.0부를 균일하게 혼합하여, 점착제액(12)을 얻었다.100 parts of peroxide curable silicone adhesive stock solution (trade name SH-4280, manufactured by Toray Dow Corning Co., Ltd.) with a solid content concentration of 60% by mass, 71 parts of toluene as a dilution solvent, curing agent (brand name Niper (registered trademark) BMT-40, Nichiyuga) (Manufactured by Bukki Co.) 3.0 parts were uniformly mixed to obtain a pressure-sensitive adhesive solution (12).
다음으로, 프라이머 처리한 두께 25μm의 폴리이미드(PI) 필름의 편면에, 점착제액(12)을 건조 후의 점착제층의 두께가 30μm가 되도록 도포했다. 이것을 건조로 내에서 60℃, 1분에서 용매를 제거하고, 또한 180℃, 2분에서 경화·건조하여 점착제층을 형성했다. 그리고 박리 라이너(불소 치환 알킬 변성 실리콘 수지로 이형 처리를 실시한 두께 50μm의 PET 필름)를 점착제층에 첩합하여, 점착 테이프를 얻었다.Next, the pressure-sensitive adhesive solution 12 was applied to one side of a 25 μm-thick polyimide (PI) film subjected to the primer treatment so that the thickness of the pressure-sensitive adhesive layer after drying was 30 μm. The solvent was removed in a drying furnace at 60 DEG C for 1 minute, and cured and dried at 180 DEG C for 2 minutes to form a pressure-sensitive adhesive layer. Then, a release liner (a 50 μm-thick PET film subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin) was bonded to the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.
<비교예 10><Comparative Example 10>
고형분 농도 60질량%의 과산화물 경화형 실리콘 점착제 원액(상품명 KR-100, 신에츠가가쿠고교가부시키가이샤제) 100부, 희석 용제로서 톨루엔 71부, 경화제(상품명 나이퍼(등록상표) BMT-40, 니치유가부시키가이샤제) 3.0부를 균일하게 혼합하여, 점착제액(13)을 얻었다. 그리고, 점착제액(13)을 사용한 것 이외는 비교예 9와 동일한 방법으로, 점착 테이프를 얻었다.100 parts of peroxide-curable silicone pressure-sensitive adhesive stock solution (trade name KR-100, manufactured by Shin-Etsu Chemical Co., Ltd.) with a solid content concentration of 60% by mass, 71 parts of toluene as a diluent solvent, curing agent (trade name Niper (registered trademark) BMT-40, Nichi (Made by Yu Co., Ltd.) 3.0 parts were mixed uniformly, and the adhesive liquid (13) was obtained. And the adhesive tape was obtained by the method similar to Comparative Example 9 except having used the adhesive liquid (13).
<점착제 조성물의 겔 분율 및 팽윤도><Gel fraction and swelling degree of adhesive composition>
실시예 및 비교예에서 얻은 점착제액 (1)∼(13)을, 박리 라이너상에 건조 후의 두께가 50∼200μm가 되도록 도포했다. 이어서, 건조로에서 가열하여 경화·건조하여 점착제 조성물로 하고, 이것을 샘플로 했다. 이때의 가열 온도는 각 실시예 및 비교예와 동일한 온도로 했다. 즉, 점착제액 (1)∼(11)의 경우는 130℃, 2분, 점착제액 (12) 및 (13)의 경우는 60℃, 1분 및 180℃, 2분으로 했다.The pressure-sensitive adhesive solutions (1) to (13) obtained in Examples and Comparative Examples were applied onto a release liner so that the thickness after drying was 50 to 200 μm. Subsequently, it was heated in a drying furnace, cured and dried to obtain an adhesive composition, and this was used as a sample. The heating temperature at this time was set to the same temperature as in each example and comparative example. That is, in the case of the pressure-sensitive adhesive solutions (1) to (11), it was set to 130°C for 2 minutes, and in the case of the pressure-sensitive adhesive solutions (12) and (13), it was set to 60°C, 1 minute and 180°C, 2 minutes.
얻어진 샘플을 50mm×50mm으로 단재(斷裁)하여, 박리 라이너를 박리하고, 시트상의 점착제 조성물로 이루어지는 측정용 샘플을 얻었다. 이 측정용 샘플의 초기 질량(A)(=팽윤 전의 점착제 조성물의 질량)을 측정했다. 그리고 이 측정용 샘플을, 초기 질량(A)의 250배 양 이상의 톨루엔에 상온(23℃)에서 1일간 침지하여 팽윤시켰다. 침지 후에 측정용 샘플을 꺼내어 팽윤 질량(B)(=톨루엔으로 팽윤한 점착제 조성물의 질량)을 측정했다. 나아가 이 측정용 샘플을, 130℃의 건조기에서 2시간 건조시켜 흡수한 용매를 제거하고, 건조 질량(C)(=건조한 점착제 조성물의 질량)을 측정했다. 점착제 조성물의 겔 분율 및 팽윤도를 하기식에 의해 얻었다.The obtained sample was cut into 50 mm x 50 mm, the release liner was peeled off, and a sample for measurement comprising a sheet-shaped pressure-sensitive adhesive composition was obtained. The initial mass (A) (=the mass of the pressure-sensitive adhesive composition before swelling) of this sample for measurement was measured. Then, this sample for measurement was swelled by immersing in
겔 분율(%)=(C/A)×100Gel fraction (%) = (C/A) × 100
팽윤도(%)=((B-A)/A)×100%Swelling degree (%)=((B-A)/A)×100%
<상온(23℃)의 대(對)SUS 점착력><Adhesion to SUS at room temperature (23℃)>
20mm 폭으로 재단한 점착 테이프를 연마한 SUS판에 첩부하여, 무게 2kg의 고무층으로 피복된 롤러로 1 왕복시켜 압착하고, 23℃ 환경하에서 20∼40분 방치했다. 그 후, 인장 시험기를 사용하여 300mm/분의 속도에서 180°의 각도로 테이프를 박리하는데 필요로 하는 힘을 측정했다.The adhesive tape cut to a width of 20 mm was affixed to the polished SUS plate, pressed by reciprocating one by a roller coated with a rubber layer having a weight of 2 kg, and allowed to stand for 20 to 40 minutes in an environment at 23°C. Thereafter, the force required to peel the tape was measured at an angle of 180° at a speed of 300 mm/min using a tensile tester.
<가열(200℃ 및 230℃) 후의 반복 대SUS 점착·점착제 잔여성><Repetitive SUS adhesion·adhesive residuals after heating (200℃ and 230℃)>
20mm 폭으로 재단한 점착 테이프를 연마한 SUS판에 첩부하여, 무게 2kg의 고무층으로 피복된 롤러로 1 왕복시켜 압착하고, 200℃ 및 230℃의 건조기 중에 30분 방치했다. 이것을 꺼내어 실온에서 방랭(放冷)했다. 그 후, 인장 시험기를 사용하여 300mm/분의 속도로 180°의 각도로 테이프를 박리하는데 필요로 하는 힘(첫 번째의 가열 후 점착력)을 측정했다. 이 박리 후의 점착 테이프를 다시 연마한 SUS판에 첩부하고, 첫 번째와 동일하게 하여 두 번째의 가열 후 점착력을 측정했다. 이후, 10번째의 가열 후 점착력까지 반복 측정했다. 또한, 각 회에 있어서의 박리했을 때의 점착제 잔여성을 목시(目視)로 확인하고, 이하의 기준으로 평가했다.The adhesive tape cut to a width of 20 mm was affixed to the polished SUS plate, pressed by reciprocating one by a roller coated with a rubber layer having a weight of 2 kg, and allowed to stand in a dryer at 200°C and 230°C for 30 minutes. This was taken out and left to cool at room temperature. Thereafter, the force required to peel the tape at an angle of 180° at a speed of 300 mm/min (adhesive force after the first heating) was measured using a tensile tester. The adhesive tape after the peeling was again affixed to the polished SUS plate, and the adhesive strength after the second heating was measured in the same manner as in the first. Thereafter, it was repeatedly measured until the adhesive force after the tenth heating. Moreover, the adhesive residual property at the time of peeling in each time was confirmed visually, and evaluated by the following criteria.
○: 점착제 잔여 없음○: No residual adhesive
×: 점착제 잔여 있음×: There is residual adhesive
<접착력의 변화율><Change rate of adhesion>
가열 후 점착력을 10회 반복 측정했을 때, 이하의 식에 따라 접착력의 변화율을 산출하고(표 1 및 2), 최대·최소 변화율을 기재했다(표 3).When the adhesive force was repeatedly measured 10 times after heating, the rate of change of the adhesive force was calculated according to the following equation (Tables 1 and 2), and the maximum and minimum rate of change were described (Table 3).
변화율(%)=각 회의 가열 후 점착력/첫 번째의 가열 후 점착력×100%Rate of change (%) = Adhesion after heating each time / Adhesion after first heating × 100%
<고정력 시험><Fixed power test>
도 2에 나타내는 바와 같이, 양단(兩端)을 고정한 점착 테이프(1)의 점착층(1b) 측(하측)에 75g의 추(2)를 첩부하고(첩부 면적 20mm×25mm), 200℃의 건조기 중에서 1시간 방치하여, 추(2)의 낙하 유무를 확인하여, 이하의 기준으로 고정력을 평가했다.As shown in Fig. 2, a 75
○: 추가 낙하하지 않았다○: No additional fall
×: 추가 낙하했다×: additionally fell
이상의 각 측정의 결과를 표 1∼3에 나타낸다. 또한, 실시예 및 비교예의 종합 평가를 겔 분율과 팽윤도의 상관관계에 있어서 정리한 그래프를 도 1에 나타낸다.The results of each of the above measurements are shown in Tables 1-3. In addition, a graph in which the general evaluation of Examples and Comparative Examples is summarized in the correlation between the gel fraction and the swelling degree is shown in FIG. 1.
<평가 결과><Evaluation result>
표 3에 나타내듯이, 실시예 1∼3에서는 200℃ 및 230℃에서 10회 반복 사용해도, 가열 후의 점착력의 변화는 초기의 ±15% 이내에 그치며, 반복 사용했을 때의 접착력은 매우 안정되어 있었다. 또한 점착제 잔여도 없고 부품의 고정력도 충분했다.As shown in Table 3, in Examples 1 to 3, even when repeatedly used at 200°C and 230°
비교예 1에서는, 겔 분율은 낮지 않지만 팽윤도가 높으므로(즉 가교 밀도가 낮으므로), 점착제 잔여는 없었지만, 230℃에서 반복 사용하면 현저하게 점착력이 상승하고, 반복 사용했을 때의 접착력은 불안정했다.In Comparative Example 1, the gel fraction was not low, but the swelling degree was high (i.e., because the crosslinking density was low), so there was no residual adhesive, but when repeatedly used at 230°C, the adhesive strength remarkably increased, and the adhesive strength when repeatedly used was unstable. .
비교예 2∼3 및 비교예 6∼7에서는, 겔 분율이 낮고 또한 팽윤도가 높으므로, 230℃에서 반복 사용하면 점착제 잔여가 발생했다. 또한 반복 사용했을 때의 접착력의 변화가 컸다.In Comparative Examples 2 to 3 and Comparative Examples 6 to 7, since the gel fraction was low and the degree of swelling was high, residual pressure-sensitive adhesive occurred when repeatedly used at 230°C. In addition, there was a large change in adhesive strength when repeatedly used.
비교예 4∼5에서는, 팽윤도는 높지 않으므로 점착제 잔여는 없었지만, 겔 분율이 낮으므로 반복 사용했을 때의 접착력의 안정성이 떨어졌다.In Comparative Examples 4 to 5, since the swelling degree was not high, there was no residual adhesive, but the gel fraction was low, so the stability of the adhesive strength when repeatedly used was inferior.
비교예 8(약점착성 점착제)에서는, 겔 분율이 높고 또한 팽윤도가 높으므로, 점착제 잔여가 발생하기 쉽고, 반복 사용했을 때의 접착력의 안정성이 떨어졌다. 또한, 겔 분율이 높은 것에 기인하여, 부품의 고정력도 떨어졌다.In Comparative Example 8 (weak-adhesive pressure-sensitive adhesive), since the gel fraction was high and the swelling degree was high, residual pressure-sensitive adhesive was likely to occur, and the stability of the adhesive strength when repeatedly used was inferior. Further, due to the high gel fraction, the fixing force of the parts was also inferior.
비교예 9∼10(과산화물 경화형 점착제)에서는, 겔 분율이 낮고 또한 팽윤도가 높으므로, 점착제 잔여가 발생하기 쉽고, 반복 사용했을 때의 접착력의 안정성이 떨어졌다.In Comparative Examples 9 to 10 (peroxide-curable pressure-sensitive adhesive), since the gel fraction was low and the degree of swelling was high, residual pressure-sensitive adhesive was likely to occur, and the stability of the adhesive strength when repeatedly used was inferior.
산업상의 이용 가능성 Industrial availability
본 발명의 점착제 조성물은, 예를 들면 점착 테이프의 점착제층을 형성하기 위한 재료로서 특히 유용하다. 본 발명의 점착 테이프는, 예를 들면 전기·전자 부품 등의 각종 부품의 제조 공정에 있어서, 부품의 보호, 마스킹, 가고정, 반송용 고정 등의 용도에 매우 유용하다.The adhesive composition of the present invention is particularly useful as, for example, a material for forming an adhesive layer of an adhesive tape. The adhesive tape of the present invention is very useful for applications such as protection, masking, temporary fixing, and fixing for conveyance in the manufacturing process of various components such as electric and electronic components, for example.
1 점착 테이프
1a 기재
1b 점착제층
2 추1 adhesive tape
1a description
1b adhesive layer
2 pendulum
Claims (7)
(겔 분율)
톨루엔에 실리콘계 점착제 조성물을 상온에서 1일간 침지했을 때의 불용해분의 비율인, 하기식에 의해 겔 분율을 얻는다.
겔 분율(%)=(C/A)×100
A: 실리콘계 점착제 조성물의 초기 질량
C: 톨루엔 침지 후의 실리콘계 점착제 조성물의 건조 질량(건조 조건: 130℃, 2시간)
(팽윤도)
톨루엔에 실리콘계 점착제 조성물을 상온에서 1일간 침지했을 때의 톨루엔 흡수에 의한 팽윤 비율인, 하기식에 의해 팽윤도를 얻는다.
팽윤도(%)=((B-A)/A)×100%
A: 실리콘계 점착제 조성물의 초기 질량
B: 톨루엔 침지 후의 실리콘계 점착제 조성물의 팽윤 질량A silicone-based pressure-sensitive adhesive composition comprising a crosslinked silicone structure, wherein a gel fraction measured by the following method is 45% or more and less than 70%, and a swelling degree for toluene measured by the following method is 290% or less.
(Gel fraction)
The gel fraction is obtained by the following formula, which is the ratio of the insoluble matter when the silicone pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
Gel fraction (%) = (C/A) × 100
A: Initial mass of the silicone pressure-sensitive adhesive composition
C: Dry mass of the silicone pressure-sensitive adhesive composition after toluene immersion (drying condition: 130°C, 2 hours)
(Swelling degree)
The degree of swelling is obtained by the following formula, which is the swelling ratio due to toluene absorption when the silicone pressure-sensitive adhesive composition is immersed in toluene for 1 day at room temperature.
Swelling degree (%) = ((BA)/A) × 100%
A: Initial mass of the silicone pressure-sensitive adhesive composition
B: Swelling mass of the silicone pressure-sensitive adhesive composition after toluene immersion
겔 분율이 48∼65%인 실리콘계 점착제 조성물.The method according to claim 1,
A silicone pressure-sensitive adhesive composition having a gel fraction of 48 to 65%.
팽윤도가 260% 이하인 실리콘계 점착제 조성물.The method according to claim 1,
A silicone pressure-sensitive adhesive composition having a swelling degree of 260% or less.
가교 경화된 부가 경화형 실리콘 점착제를 포함하는 실리콘계 점착제 조성물.The method according to claim 1,
A silicone pressure-sensitive adhesive composition comprising a crosslinked cured addition-curable silicone pressure-sensitive adhesive.
기재가 수지 필름인 점착 테이프.The method of claim 5,
Adhesive tape in which the base material is a resin film.
수지 필름이 폴리이미드필름인 점착 테이프.The method of claim 6,
Adhesive tape in which the resin film is a polyimide film.
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TW202319233A (en) * | 2021-07-20 | 2023-05-16 | 日商東洋紡股份有限公司 | laminate volume |
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JP2004091703A (en) * | 2002-09-02 | 2004-03-25 | Shin Etsu Chem Co Ltd | Conductive silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
KR100740926B1 (en) | 2005-12-30 | 2007-07-19 | 주식회사 케이씨씨 | Non-Adhesive Silicone Pressure Sensitive Adhesive Composition |
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JP3328248B2 (en) | 1999-11-15 | 2002-09-24 | 株式会社 大昌電子 | Jig for mounting printed wiring board and method for mounting printed wiring board |
JP3751186B2 (en) * | 2000-06-14 | 2006-03-01 | 信越化学工業株式会社 | Silicone adhesive composition |
JP4809988B2 (en) * | 2001-03-21 | 2011-11-09 | 日東電工株式会社 | Silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using the same |
JP4060585B2 (en) | 2001-12-25 | 2008-03-12 | 日東電工株式会社 | Masking adhesive tape and method of using the same |
JP3435157B1 (en) | 2002-05-13 | 2003-08-11 | 株式会社 大昌電子 | Holding and conveying jig and holding and conveying method |
JP4204835B2 (en) * | 2002-09-30 | 2009-01-07 | 日東電工株式会社 | Adhesive tape and method of using adhesive tape |
JP4180353B2 (en) | 2002-11-18 | 2008-11-12 | 信越化学工業株式会社 | Silicone adhesive composition and adhesive tape |
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US8933187B2 (en) * | 2011-12-08 | 2015-01-13 | Momentive Performance Material Inc. | Self-crosslinking silicone pressure sensitive adhesive compositions, process for making and articles made thereof |
JP6251111B2 (en) | 2014-04-10 | 2017-12-20 | フジコピアン株式会社 | Double-sided adhesive film and protective member for information display screen using the same |
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JP2004091703A (en) * | 2002-09-02 | 2004-03-25 | Shin Etsu Chem Co Ltd | Conductive silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape |
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