TWI554580B - 耐久性優秀的橡膠類黏結劑組合物 - Google Patents
耐久性優秀的橡膠類黏結劑組合物 Download PDFInfo
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- TWI554580B TWI554580B TW103128910A TW103128910A TWI554580B TW I554580 B TWI554580 B TW I554580B TW 103128910 A TW103128910 A TW 103128910A TW 103128910 A TW103128910 A TW 103128910A TW I554580 B TWI554580 B TW I554580B
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- Prior art keywords
- butyl rubber
- rosin
- resin
- tackifier
- weight
- Prior art date
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
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- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
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- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- GZKMGAXTHYGXEO-UHFFFAOYSA-M ruthenium(1+);triphenylphosphane;chloride Chemical compound [Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 GZKMGAXTHYGXEO-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
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
- C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/02—Copolymers of mineral oil hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
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- 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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C09J123/283—Halogenated homo- or copolymers of iso-olefines
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Description
本發明涉及耐久性優秀的橡膠類黏結劑組合物。
眾所周知,包含多種封裝的電子器件或透明導電膜等的觸控材料為了突出的工作或者維持規定的儲存壽命而需要防止濕氣。進而,最近關注用於增加有機發光二極體(OLED,Organic Light-Emitting Diode)或者觸控式螢幕之類的新一代裝置的耐久性的黏結劑組合物的開發。
然而,只是持續進行對包含丙烯酸類樹脂的黏結劑的發明,丁基類橡膠樹脂由於根據重鍵(multiple bond),其耐久性降低,因此並不好用作黏結劑組合物。韓國公開公報第10-2011-0064714號中,記載有改善可加工性及成形性的丁基橡膠組合物,但並沒有公開使丁基橡膠硫化來使用,且耐久性優秀的作用及效果,因此,對於使用丁基類橡膠作為黏結劑組合物的方面,依然難以解決上述問題。
本發明的一實施例透過導入具有規定軟化點的增黏劑,從而提供能夠對熱穩定性進行調節的黏結劑組合物。
本發明的另一實施例透過使用丁基類橡膠,使透濕度降低,並使化學交聯密度增加,由此提供耐久性優秀的黏結劑組合物。
在本發明的一實施例,提供包含丁基類橡膠及軟化點為90。℃以上的增黏劑的黏結劑組合物。
上述丁基類橡膠可包含選自包含丁基橡膠、溴化丁基橡膠及氯化丁基橡膠的組中的一種以上。
上述丁基類橡膠的重均分子量可以為約5萬至200萬。
上述丁基類橡膠可由總單體100莫耳%中包含約1莫耳%至約5莫耳%的異戊二烯的混合物聚合而成。
相對於上述黏結劑組合物的總重量可包含約50重量%至約90重量%的上述丁基類橡膠。
上述增黏劑可以為松香類樹脂、松香酯類樹脂、線性烴類樹脂或加氫的環狀烯烴類樹脂。
上述增黏劑可以為重均分子量為約500至約2000的樹脂。
相對於上述黏結劑組合物的總重量可包含約5重量%至約40重量%的上述增黏劑。
本發明還可包含選自包含紫外線固化劑、紫外線穩定劑、光引發劑、熱引發劑、抗氧化劑、填充劑及增塑劑的組中的一種以上。
在溫度為38℃、相對濕度為90%的條件下,上述黏結劑組合物的透濕度可以為約10g/m2.24小時以下。
上述黏結劑組合物能夠對熱穩定性進行調節,並且耐久性優秀,可靠性高,因此,即使在高溫高濕的外部環境下,也不產生氣泡。
上述黏結劑組合物能夠適用於觸控材料或電子器件,從而可增加觸控面板、有機發光二極體(OLED)之類的新一代裝置的壽命及耐久性。
以下,詳細說明本發明的實例。但這僅僅是作為例示而提出的,本發明並不局限於此,應根據要後述的發明要求保護範圍的範疇而定義。
在本發明的一實例,提供包含丁基類橡膠及軟化點為90℃以上的增黏劑的黏結劑組合物。
上述黏結劑組合物為了適用於觸控面板、有機發光二極體之類的新一代裝置,其透濕度應低,化學交聯密度高,耐久性優秀。並且,即使長時間暴露在高溫高濕的外部環境下,也不得產生氣泡。此時,上述黏結劑組合物的基礎樹脂嚴重纏結的橡膠(highly entangled rubber),即當上述橡膠為丁基類橡膠時,在使用限制軟化點的增黏劑作為添加劑的情況下,隨著纏結的程度增加且熱膨脹係數降低,能夠延遲因高溫及高濕的外部環境而產生的氣泡產生時間。
上述丁基類橡膠也被稱為異丁烯-異戊二烯(Isobutylene-Isoprene)橡膠,是指含有大部分的異丁烯和少量的異戊二烯的共聚物。借助少量的異戊二烯存在少量的雙鍵,由於飽和度高,且無水
分性,因此,具有與其他黏附劑等難以進行附著及剝離的性質。
為了克服由於無水分性而與其他黏附劑等難以進行附著及剝離的上述丁基類橡膠的缺點,能夠在丁基類橡膠導入增黏劑(Tackifier)。上述增黏劑是為了提高橡膠和塑膠表面的黏結性而添加的配合材料,例如,能夠在接合配合橡膠之間時使用。
上述黏結劑組合物可包含含有規定的軟化點的增黏劑。透過限定上述增黏劑的軟化點,改變以丁基類橡膠為基本的黏結劑的性質,從而能夠提供化學交聯密度增加而耐久性優秀的黏結劑組合物。
具體地,上述增黏劑的軟化點可以為約90℃以上,具體地,可以為約95℃至約160℃。軟化點是指,通常借助加熱,使物質開始發生變形、軟化的溫度,上述增黏劑可在約90℃的條件下,開始進行增黏劑的變形及軟化。
更具體地,在以約90℃以上維持上述增黏劑的軟化點的情況下,在高溫可靠性條件下,由於增黏劑維持玻璃狀態(glassy state),因此在熱變形率降低的方面存在優勢,且能夠容易確保高溫可靠性。
相反,在上述增黏劑的軟化點小於90℃的情況下,在高溫條件下增黏劑開始進行軟化而帶來耐久性降低的問題。例如,在上述增黏劑的軟化點為約160℃以上的情況下,在常溫下,黏結劑的增黏作用有可能甚微。
上述丁基類橡膠可包含選自包含丁基橡膠(Isobutylene-isoprene Rubber,IIR)、溴化丁基橡膠(Bromo Isobutylene-isoprene Rubber,BIIR)及氯化丁基橡膠(Chloro
Isobutylene-isoprene Rubber,CIIR)的組中的一種以上。
上述溴化丁基橡膠及氯化丁基橡膠為鹵化丁基橡膠,在己烷之類的輕脂肪族烴中溶化丁基橡膠的狀態下,透過使溴和氯原子反應而製備。上述溴化丁基橡膠通常含有約1.9重量%至約2.1重量%的溴,上述氯化丁基橡膠含有約1.1重量%至約1.3重量%的氯。並且,上述溴化丁基橡膠及氯化丁基橡膠由於鹵素含量非常少,因此不屬於極性橡膠,且均具有沒有被變形的丁基橡膠的獨特的特性。
上述丁基類橡膠的重均分子量可以為約5萬至約200萬。重均分子量是指,以重量分率(weight fraction),對具有分子量分佈的高分子化合物的成分分子種類的分子量進行平均來得到的平均分子量,在上述丁基類橡膠的重均分子量小於約5萬的情況下,由於物理纏結區域(physical entanglement site)少,而能夠引起耐久性方面的問題,在上述丁基類橡膠的重均分子量大於約200萬的情況下,黏結劑組合物的黏度急劇上升,存在工序條件的相容性方面發生問題的憂慮。
上述丁基類橡膠由總單體100莫耳%中含有1莫耳%至5莫耳%的異戊二烯的混合物聚合而成。在總單體100莫耳%中,異戊二烯超過上述範圍聚合來形成丁基類橡膠的情況下,丁基類橡膠包含低的雙鍵,在固化時有可能使黏結劑組合物的耐久性降低,含有高的異戊二烯的丁基類橡膠在作為黏結劑組合物而商用化的方面存在困難。
相對於上述黏結劑組合物的總重量,可包含約50重量%至約90重量%的上述丁基類橡膠,相對於上述黏結劑組合物的總重量,包含上述範圍內的上述丁基類橡膠,從而有利於維持丁基類橡膠的水分阻隔性並
能夠透過添加劑來確保耐久性。
上述增黏劑可以為松香類樹脂、松香酯類樹脂、線性烴類樹脂或者加氫的環狀烯烴類樹脂。使用松香類樹脂、松香酯類樹脂、線性烴類樹脂或者加氫的環狀烯烴類樹脂作為上述增黏劑,從而能夠增加與丁基橡膠類之間的相容性,進而能夠提供耐久性突出的黏結劑組合物。上述松香類樹脂不受特別限制,例如,可使用能夠作為增黏樹脂來使用的松香類樹脂、線性烴類樹脂或者加氫的環狀類樹脂。
具體地,能夠使用脂松香、木松香、浮油松香等的未改性松香(生松香)或借助聚合、不均化、加氫化等,使這些的未改性松香發生改性的改性松香(聚合松香、穩定化松香、不均化松香、完全加氫松香、部分加氫松香或其他化學修飾的松香等)作為上述松香類樹脂之外,還可使用適當地選自各種松香衍生物等的公知的松香類樹脂中作為上述松香類樹脂。
例如,作為上述松香衍生物可舉出借助醇類對未改性松香進行酯化的松香的酯化合物(未改性松香酯)或借助醇類對聚合松香、穩定化松香、不均化松香、完全加氫松香、部分加氫松香等的改性松香進行酯化的改性松香的酯化合物(聚合松香酯、穩定化松香酯、不均化松香酯、完全加氫松香酯、部分加氫松香酯等)等的松香酯類樹脂;以不飽和脂肪酸使未改性松香或改性松香(聚合松香、穩定化松香、不均化松香、完全加氫松香、部分加氫松香等)改性的不飽和脂肪酸改性松香類樹脂;以不飽和脂肪酸使松香酯類樹脂改性的不飽和脂肪酸改性松香酯類樹脂;還原處理未改性松香、改性松香(聚合松香、穩定化松香、不均化松香、完全
加氫松香、部分加氫松香等)、不飽和脂肪酸改性松香類樹脂或不飽和脂肪酸改性松香酯類樹脂中的羧基的松香醇類樹脂;未改性松香、改性松香或各種松香衍生物等的松香類樹脂(尤其,松香酯類樹脂)的金屬鹽等。上述松香類樹脂可單獨使用或者透過組合兩種以上來使用。
另一方面,例如,作為當製備上述松香酯類樹脂時所使用的醇類,適當地使用乙二醇、二乙二醇、丙二醇、新戊二醇、三亞甲基乙二醇、四亞甲基乙二醇、1,3-丁二醇、1,6-己二醇等的二元醇類;丙三醇、三甲醇乙烷、三甲醇丙烷、三乙醇乙烷等的三元醇類;季戊四醇、雙甘油等的四元醇類;雙季戊四醇等的六元醇類等的多元醇類,但可以為甲醇、乙醇等的一元醇類。並且,還可使用三乙醇胺、三丙醇胺、三異丙醇胺、N-異丁基二乙醇胺、N-n-丁基二乙醇胺等的氨基醇類作為醇類。
並且,作為製備不飽和脂肪酸改性松香類樹脂或不飽和脂肪酸改性松香酯類樹脂時所使用的不飽和脂肪酸,例如,可舉出富馬酸、馬來酸或者其酐、衣康酸、檸康酸或者其酐、丙烯酸、甲基丙烯酸等的α,β-不飽和羧酸等。
上述線性烴類樹脂可使用C5類樹脂、C9類樹脂、C5類/C9類混合樹脂、環戊二烯類樹脂、乙烯基置換芳香族聚合物樹脂、烯烴/乙烯基置換芳香族共聚物樹脂、環戊二烯/乙烯基置換芳香族共聚物樹脂、這些的加氫物等,但並不局限於此。
作為上述線性烴類樹脂的具體例,可舉出埃克森美孚化工(ExxonMobil Chemical)公司的Escorez、可隆(Kolon)公司的SUKOREZ或者HIKOREZ、出光興產(Idemitsu)公司的I-MARV、日本石油化學的Neo
polymer、荒川(Arakawa)公司的Arkon、東邦化學(Toho Chemical)公司的High resin、安原(Yasuhara)公司的YS Polyester或者Crealon等的產品,但並不局限於此。
較佳地,上述加氫的環狀烯烴類樹脂並不需要必須加氫,根據其用途,能夠直接使用透過聚合所獲得的烯烴類樹脂,但透過考慮增黏劑的軟化點和黏結力增進效果、加熱著色等來決定是否加氫。
用於將氫添加到分子中的烯烴性不飽和鍵的氫化反應,能夠在結束開環聚合之後,使用其共聚物溶液來執行上述氫化反應,還能夠使用以在進行催化劑殘留物或未反應單體的除去處理之後,將開環共聚物溶解於適當的溶劑的方式製備的共聚物溶液來執行上述氫化反應。
通常以氫壓為1.0至15MPa、溫度為50℃至200℃的條件而執行氫化反應。可使用在選自二氧化矽、二氧化鋁、沸石、矽藻土、氧化鎂、碳、碳酸鈣等中的載體中負載有選自鈀、白金、鉑、銠、銥、釕、鎳中的金屬的不均勻系催化劑、或者辛酸鎳/三乙基鋁、環烷酸鎳/三乙基鋁、辛酸鈷/三乙基鋁、辛酸鈷/n-丁基鋰、雙環戊二烯基二氯化鈦二氯二乙基鋁氯化物、乙酸鈀/三乙基鋁、三(三苯基膦)氯化銠、三(三苯基膦)氫化物.羰基.氯.釕、三(三甲苯基膦)氫化物.羰基.氯.釕、三(磷酸三二甲苯酯)氫化物.羰基.氯.釕、三(三環己基膦)氫化物.羰基.氯.釕、三(三苯基膦)二氫.羰基.釕、雙(三苯基膦)二氯釕等的均勻系催化劑作為氫化催化劑。
通常針對開環共聚物,以過渡金屬原子換算使用10至1000ppm範圍的氫化催化劑。上述加氫的環狀烯烴類樹脂其分子中的烯烴性不飽和鍵的氫化率越高,具有優秀的熱穩定性。其結果,能夠抑制在去溶
劑工序、微粒化工序、產品的成形加工工序等中的因加熱引起的熱退化或因氧引起的退化等。
可在上述加氫的環狀烯烴類樹脂中添加公知的抗氧化劑,例如2,6-二叔丁基、4-甲基苯酚、4,4'-巰基雙-(6-叔丁基-3-甲基苯酚)、1,1-雙(4-羥基苯基)環己烷、2,2'-亞甲基雙(4-乙基-6-叔丁基苯酚)、2,5-二叔丁基對苯二酚、四[β-(3,5-二叔丁基-4-羥基苯基)丙酸]季戊四醇酯等的苯酚類或者對苯二酚類抗氧化劑。並且,調配三(4-甲氧基-3,5-二苯基)亞磷酸、三(壬基酚)亞磷酸、三(2,4-二叔丁基苯基)亞磷酸、二(2,4-二叔丁基-4-二苯基)季戊四醇二亞磷酸、二(2,4-二叔丁基苯基)季戊四醇二亞磷酸等的磷類抗氧化劑,從而能夠增強氧化穩定性。
上述增黏劑可以為重均分子量為約500至約2000的樹脂。在上述增黏劑的重均分子量小於約500的情況下,能夠賦予優秀的黏結力,在上述增黏劑的重均分子量大於約2000的情況下,因未參與交聯的分子,存在發生耐久性被減少的問題的隱患。
相對於上述黏結劑組合物的總重量,可包含約5重量%至約40重量%的上述增黏劑。相對於上述黏結劑組合物的總重量,包含上述範圍內的上述增黏劑,從而能夠賦予適當的黏結力,而有利於實現耐久性,進而能夠容易地製備穩定的組合物。
並且,上述黏結劑組合物除了丁基類橡膠及增黏劑之外,還可包含選自包含紫外線固化劑、紫外線穩定劑、光引發劑、熱引發劑、抗氧化劑、填充劑及增塑劑的組中的一種以上。在不阻礙黏結劑組合物的物性的範圍內,能夠適當地調節上述添加劑,還可包含顏料、紫外線穩定劑、
分散劑、消泡劑、增稠劑、增塑劑、增黏樹脂、矽烷結合劑、亮光劑等的添加劑。
上述紫外線固化劑可包含與丁基類橡膠的相容性好的紫外線(UV)固化型樹脂。例如,可選自丙烯酸酯樹脂、甲基丙烯酸酯樹脂、異氰酸酯樹脂、三聚氰胺樹脂、氨基甲酸乙酯樹脂、環氧樹脂、酸酐、聚胺樹脂及含羧基聚合物中。較佳地,相對於整體組合物,添加約5重量%至約20重量%的上述紫外線固化劑。
作為上述光引發劑的例子,可舉出選自包含安息香甲醚、2,4,6-三甲基苯甲醯二苯氧膦、雙(2,4,6-三甲基苯甲醯基)苯氧膦、α,α-甲氧基-α-羥基苯乙酮、2-苯甲醯-2-(二甲氨基)-1-[4-(4-嗎啉基)苯基]-1-丁酮及2,2-二甲氧基-2-苯基苯乙酮的組中的一種以上。優選地,相對於整體組合物包含約0.01重量%至約1重量%的上述光引發劑。
上述黏結劑組合物可包含熱引發劑,透過一同包含光引發劑及熱引發劑,能夠使黏結劑組合物構成為雙重固化型。例如,上述熱引發劑因光引發劑的分解產生的熱而被活性化,由此能夠參與黏結劑組合物的固化反應,上述光引發劑的分解因如紫外線等的照射而所產生。
此時,作為熱引發劑,可舉出選自包含偶氮類化合物、叔戊基類化合物、過氧乙酸叔丁酯、過乙酸及磷酸鉀的組中的一種以上,優選地,相對於整體組合物,添加約0.01重量%至約10重量%的上述熱引發劑。
較佳地,可使用苯酚型、磷化物型、硫醚型或者胺型抗氧化劑作為上述抗氧化劑。並且,為了增強物性或者流動性而能夠使用填充劑,上述填充劑並不局限於以下,但可包含石英粉、熔融二氧化矽、非晶質二
氧化矽、滑石、玻璃珠、石墨、炭黑、氧化鋁、黏土、雲母、氮化鋁及氮化硼。作為黏結劑組合物用途而適合的填充劑的形態及量包含於相關技術領域的普通技術人員的專業知識。
通常,相對於整體組合物包含約1重量%至約10重量%範圍量的這種填充劑。
上述增塑劑並沒有被限制,例如,可舉出液體石蠟、固化油、固化蓖麻油、辛基十二烷醇等的高級醇;角鯊烷、角鯊烯、蓖麻油、液狀橡膠(聚丁烯)、肉豆蔻酸異丙基等的脂肪酸酯等。較佳地,相對於上述整體組合物,上述增塑劑的含量為約1重量%至約10重量%。
在溫度為38℃、相對濕度為90%的條件下,上述黏結劑組合物的透濕度可以為約10g/m2.24小時以下。上述的透濕度(Water Vapor Transmission Rate,WATR)是指水分的每單位面積時間滲透的量,是指在38℃、90%RH條件下滲透的量/單位面積/單位時間。
上述透濕度為約10g/m2.24hr以下,具體地,可以為約5g/m2.24hr以下。並且,與使用包含丁基類橡膠的以往的黏結劑組合物時相比,在丁基類橡膠導入軟化點為約90℃以上的增黏劑的黏結劑組合物,其透濕度增加數十倍以上,上述黏結劑組合物不僅確保了低的透濕度,還確保了初始黏結力、剝離力及耐久性等,因而能夠具有功能性。
因此,上述黏結劑組合物包含丁基類橡膠及軟化點為90℃以上的增黏劑,由此能夠調節熱穩定性,並且耐久性優秀、可靠性高,而能夠在高溫高濕的外部環境下不產生氣泡。並且,使上述黏結劑組合物適用於觸控材料或電子器件,由此能夠增加觸控面板、有機發光二極體之類的
新一代裝置的耐久性。
並且,能夠透過固化上述黏結劑組合物來形成黏結劑層,能夠使其厚度為約10μm至約70μm而使用。使上述黏結劑層的厚度維持上述範圍,從而能夠確保充分的黏結力,並能夠穩定地維持製程條件。
以下提示本發明的具體實施例。但以下所記載的僅僅是為了具體的例示或說明本發明,本發明並不局限於此。
實施例及比較例
下清單1示出了黏結劑組合物的實施例及比較例。
HDDA:hexanediol diacrylate,1,6-己二醇二丙烯酸酯
實驗例-黏結劑組合物的物理特性
透過使上述實施例及比較例的黏結劑組合物固化,形成了厚度為50μm的黏結劑層。
1)透濕度:在溫度為38℃、相對濕度為90%的條件下,在燒杯中放入規定量的水之後,在其上面負載(loading)上述黏結劑層來進行覆蓋(capping)之後,利用蒸發24小時而消失的水的重量,來透過Labthink TSY-T3測定了透濕度(WVTR)。
2)剝離力:以1英寸長度10cm的大小切斷上述黏結劑層,並以2kg輥在作為被黏附劑的玻璃基材面往復附著5次,經過30分鐘之後,透過萬能試驗機(UTM,Universal Testing Machine),並以300mm/min的剝離速度測定了剝離力。
3)耐久性測試:透過對玻璃基材的上部依次層疊上述實施例及比較例的黏結劑層及阻隔膜來製備膜。透過將上述膜放入壓熱器(autoclave),並在溫度為85℃、相對濕度為85%的條件下,經過一天、三天之後,確認了在上述玻璃基材和上述黏結劑層之間是否產生氣泡及在上述黏結劑層和阻隔膜之間是否產生氣泡。
以包含丁基類橡膠及軟化點為90℃以上的增黏劑的黏結劑組合物構成實施例1至實施例3,以不包含增黏劑的黏結劑組合物構成比較例1,以包含軟化點小於90℃的增黏劑的黏結劑組合物構成比較例2,可知實施例1至實施例3的情況與比較例1及比較例2的情況相比具有更優秀的透濕度和高溫高濕可靠性。
並且,在實施例及比較例的情況下,可知維持規定水準以上的剝離力,但實施例1至實施例3的剝離力更優秀,發揮了使用於有機發光二極體或光電器件等之後,沒有殘留殘留物的剝離性能,在實施例1至實施例3的情況下,確認了在高溫高濕的環境下,沒有使氣泡產生在黏結劑組合
物和黏結的玻璃基材及阻隔膜之間,其可靠性與比較例相比更優秀。
就丁基類橡膠的含量與實施例1不同的實施例4及實施例5、增黏劑的分子量與實施例1不同的實施例6及實施例7而言,可知與實施例1至實施例3相比,其水分透濕度略高且剝離力略低,但與比較例相比,其水分透濕度及剝離力更優秀,並未產生氣泡,使得增黏劑的軟化點對黏結劑組合物的耐久性產生很大的影響。
Claims (6)
- 一種黏結劑組合物,包含丁基類橡膠及軟化點為90℃以上的增黏劑,其中該丁基類橡膠包含選自包含丁基橡膠(butyl rubber)、溴化丁基橡膠(Brominated butyl rubber)及氯化丁基橡膠(chlorinated butyl rubber)的群組中的一種以上,該增黏劑為松香類樹脂、松香酯類樹脂、線性烴類樹脂或加氫的環狀烯烴類樹脂,其中相對於上述黏結劑組合物的總重量,包含70重量%至90重量%的該丁基類橡膠以及5重量%至20重量%的該增黏劑。
- 如請求項1所述的黏結劑組合物,其中該丁基類橡膠的重均分子量為5萬至200萬。
- 如請求項1所述的黏結劑組合物,其中該丁基類橡膠由總單體100莫耳%中包含1莫耳%至5莫耳%的異戊二烯(isoprene)的混合物聚合而成。
- 如請求項1所述的黏結劑組合物,其中該增黏劑為重均分子量為500至2000的樹脂。
- 如請求項1所述的黏結劑組合物,其中還包含選自包含紫外線固化劑、紫外線穩定劑、光引發劑、熱引發劑、抗氧化劑、填充劑及增塑劑的群組中的一種以上。
- 如請求項1所述的黏結劑組合物,其中在溫度為38℃、相對濕度為90%的條件下,該黏結劑組合物的透濕度為10g/m2.24小時以下。
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