JPWO2008090815A1 - Adhesive composition and optical film with adhesive - Google Patents
Adhesive composition and optical film with adhesive Download PDFInfo
- Publication number
- JPWO2008090815A1 JPWO2008090815A1 JP2008555035A JP2008555035A JPWO2008090815A1 JP WO2008090815 A1 JPWO2008090815 A1 JP WO2008090815A1 JP 2008555035 A JP2008555035 A JP 2008555035A JP 2008555035 A JP2008555035 A JP 2008555035A JP WO2008090815 A1 JPWO2008090815 A1 JP WO2008090815A1
- Authority
- JP
- Japan
- Prior art keywords
- group
- organopolysiloxane
- pressure
- sensitive adhesive
- optical film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000012788 optical film Substances 0.000 title claims abstract description 70
- 239000000853 adhesive Substances 0.000 title claims abstract description 52
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 52
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 106
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 94
- 125000000524 functional group Chemical group 0.000 claims abstract description 61
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- -1 acryloyloxy group Chemical group 0.000 claims description 156
- 239000010408 film Substances 0.000 claims description 97
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004593 Epoxy Chemical group 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 claims description 6
- 229940081735 acetylcellulose Drugs 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 abstract description 36
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 25
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract description 24
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 24
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 abstract description 7
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 abstract description 7
- 239000011521 glass Substances 0.000 description 45
- 239000010410 layer Substances 0.000 description 34
- 239000000178 monomer Substances 0.000 description 33
- 239000000758 substrate Substances 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 238000006460 hydrolysis reaction Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 230000007062 hydrolysis Effects 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 230000009257 reactivity Effects 0.000 description 21
- 229910000077 silane Inorganic materials 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 210000002858 crystal cell Anatomy 0.000 description 11
- 238000006068 polycondensation reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005187 foaming Methods 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000011698 potassium fluoride Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012719 thermal polymerization Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 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 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000519995 Stachys sylvatica Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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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- 125000000623 heterocyclic group Chemical group 0.000 description 3
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 235000003270 potassium fluoride Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
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- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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Abstract
(A)アクリル樹脂、(B)架橋剤、(C)官能基とともに、メトキシ基及び/又はエトキシ基を一分子内に含有する第一のオルガノポリシロキサン、及び(D)官能基並びにメトキシ基及び/又はエトキシ基に加えて、更にプロポキシ基やブトキシ基等の炭素原子数3及び/又は4のアルコキシ基を一分子内に含有する第二のオルガノポリシロキサンを含有することを特徴とする粘着剤組成物。本発明の粘着剤組成物は、それを光学フィルムに貼着し、粘着剤付き光学フィルムとした状態で、長期間性能が安定しており、また大型化してもリワーク性が良好であるとともに、耐久性にも優れる。従ってこの粘着剤付き光学フィルムは、液晶表示装置に好適に用いられる。(A) acrylic resin, (B) cross-linking agent, (C) first organopolysiloxane containing methoxy group and / or ethoxy group in one molecule together with functional group, and (D) functional group and methoxy group and In addition to the ethoxy group, the pressure-sensitive adhesive further comprises a second organopolysiloxane containing, in one molecule, an alkoxy group having 3 and / or 4 carbon atoms such as a propoxy group or a butoxy group. Composition. The pressure-sensitive adhesive composition of the present invention is a state in which the performance is stable for a long time in a state in which it is adhered to an optical film and made into an optical film with a pressure-sensitive adhesive, and reworkability is good even when the size is increased, Excellent durability. Therefore, this optical film with an adhesive is suitably used for a liquid crystal display device.
Description
本発明は、粘着剤組成物、及び特に液晶表示用ガラスセルに貼合して用いられる粘着剤付き光学フィルムに関するものである。 The present invention relates to a pressure-sensitive adhesive composition and, in particular, an optical film with a pressure-sensitive adhesive that is used by being bonded to a glass cell for liquid crystal display.
TN(Twisted Nematic)、STN(Super Twisted Nematic)等の液晶表示装置に一般に用いられている液晶セルは、液晶成分が二枚のガラス基板間に挟持された構造を有している。そして、それぞれのガラス基板の表面には、アクリル樹脂を主成分とする粘着剤を介して、偏光フィルム、位相差フィルム等の光学フィルムが積層されている。そこで光学フィルムは通常、その少なくとも片面に粘着剤層が形成された粘着剤付き光学フィルムの形で流通しており、液晶セルを組み立てる段階で、その粘着剤側をガラス基板に貼り合わせる形態が、一般に採用されている。 A liquid crystal cell generally used in a liquid crystal display device such as TN (Twisted Nematic) or STN (Super Twisted Nematic) has a structure in which a liquid crystal component is sandwiched between two glass substrates. And the optical film, such as a polarizing film and retardation film, is laminated | stacked on the surface of each glass substrate through the adhesive which has an acrylic resin as a main component. Therefore, the optical film is usually distributed in the form of an optical film with an adhesive having an adhesive layer formed on at least one side thereof, and in the stage of assembling the liquid crystal cell, the form in which the adhesive side is bonded to the glass substrate, Generally adopted.
このような粘着剤付き光学フィルムは、熱又は湿熱条件下では伸縮による寸法変化が大きいため、ガラス基板に貼り合わせた光学積層体の状態では、粘着剤層内で発泡したり、粘着剤層とガラス基板との間に浮きや剥れ等が発生したりするという問題があった。更に最近では、カーナビゲーションシステム等の車載用としても液晶表示装置が用いられているが、車載用途においては、高温・高湿条件下でも発泡や浮き、剥れ等が生じないという耐久性も必要となってきている。 Since such an optical film with an adhesive has a large dimensional change due to expansion and contraction under heat or wet heat conditions, in the state of the optical laminate bonded to the glass substrate, foaming in the adhesive layer, There has been a problem that floating or peeling occurs between the glass substrate and the like. More recently, liquid crystal display devices are also used for in-car applications such as car navigation systems, but in-vehicle applications also require durability that does not cause foaming, floating, or peeling even under high temperature and high humidity conditions. It has become.
また、粘着剤付き光学フィルムを液晶表示用ガラスセルに貼合する際、不備があった場合には、その光学フィルムを剥がしてから、再度貼り直すことになるが、その剥離のときに粘着剤層が光学フィルムに伴って引き剥がされ、ガラス基板上に粘着剤層が残らず、曇り等も生じないような、いわゆるリワーク性も求められる。最近ではテレビ用途等の大型化に伴い、光学フィルムの面積も大きくなる中で、従来よりも一層優れたリワーク性が求められるようになってきた。 In addition, when there is a deficiency when the optical film with pressure-sensitive adhesive is bonded to the glass cell for liquid crystal display, the optical film is peeled off and then re-attached. So-called reworkability is also required such that the layer is peeled off along with the optical film, the pressure-sensitive adhesive layer does not remain on the glass substrate, and no fogging occurs. Recently, with the increase in the size of optical films and the like, the area of optical films has become larger, and reworkability superior to that in the past has been demanded.
かかる問題を解消するために、アクリル樹脂を主成分とする粘着剤について各種の提案がなされている。例えば、特許第3022993号公報(特許文献1)には、エポキシ基をもつシラン化合物を含有するアクリル樹脂粘着剤層を偏光フィルムの表面に設けることが記載されている。また特許第3487940号公報(特許文献2)には、アクリル樹脂中に、硬化剤と特定のシリケートオリゴマーを配合した粘着剤組成物が記載され、その粘着剤組成物を偏光フィルム等の光学フィルムに適用することも記載されている。 In order to solve such a problem, various proposals have been made on pressure-sensitive adhesives mainly composed of acrylic resin. For example, Japanese Patent No. 3022993 (Patent Document 1) describes that an acrylic resin pressure-sensitive adhesive layer containing a silane compound having an epoxy group is provided on the surface of a polarizing film. Japanese Patent No. 3487940 (Patent Document 2) describes an adhesive composition in which a curing agent and a specific silicate oligomer are blended in an acrylic resin, and the adhesive composition is applied to an optical film such as a polarizing film. Application is also described.
しかしながら、本発明者らが検討したところ、従来から知られている粘着剤を設けた光学フィルムは、粘着剤塗工後3ヶ月程度であれば、その粘着剤層を介してガラス基板に貼合した後のリワーク性や粘着耐久性において比較的良好であるものの、塗工後半年とか1年とかの長期間を経た場合には、その粘着剤層を介してガラス基板に貼合した後の粘着耐久性やリワーク性が低下する場合もあることが明らかになってきた。 However, when the present inventors examined, the optical film provided with the conventionally known adhesive was bonded to the glass substrate through the adhesive layer if it was about 3 months after the adhesive was applied. Although it is relatively good in terms of reworkability and adhesion durability after being applied, when it has passed for a long period of time, such as the second half of the coating or one year, the adhesive after being bonded to the glass substrate via the adhesive layer It has become clear that durability and reworkability may decrease.
そこで、本発明の目的は、リワーク性が良好であるとともに、ガラス基板に貼り合わせたときに、ガラス基板と粘着剤層との間の浮きや剥れ、また粘着剤層内での発泡を抑制することができ、粘着剤塗工後、半年とか1年とかの長期間を経た後も、このような浮きや剥れ、発泡、曇り等が生じにくく、耐久性及びリワーク性に優れ、従って光学フィルムの粘着剤として好適な粘着剤組成物、及びそれを用いた粘着剤付き光学フィルムを提供することにある。 Therefore, the object of the present invention is that reworkability is good, and when bonded to a glass substrate, floating and peeling between the glass substrate and the pressure-sensitive adhesive layer, and foaming in the pressure-sensitive adhesive layer are suppressed. Even after a long period of time, such as half a year or a year after the application of the adhesive, such floating, peeling, foaming, fogging, etc. are unlikely to occur, and the durability and reworkability are excellent. It is providing the adhesive composition suitable as an adhesive of a film, and an optical film with an adhesive using the same.
本発明者らは、かかる課題を解決すべく鋭意研究を行った結果、メルカプト基等の官能基とともに、メトキシ基及び/又はエトキシ基を一分子内に含有するオルガノポリシロキサンと、同じくメルカプト基等の官能基並びにメトキシ基及び/又はエトキシ基に加えて、更にプロポキシ基やブトキシ基等の炭素原子数3及び/又は4のアルコキシ基を一分子内に含有するオルガノポリシロキサンとを接着剤成分に配合するのが有効であることを見出した。
即ち、従来から粘着剤分野で用いられているシラン化合物乃至オルガノポリシロキサンは、分子内にメトキシ基及び/又はエトキシ基を有するものが多かったが、この場合は、その加水分解性が十分にコントロールできず、保存安定性に問題があった。特にアクリル系粘着剤には、水分が含まれるため、シラン化合物を含む粘着剤を長期間、粘着剤としての性質を安定させることは困難であった。そこで、加水分解反応性の高いメトキシ基やエトキシ基を含有するポリオルガノシロキサンと、加水分解反応性の低いプロポキシ基やブトキシ基等の炭素原子数3及び/又は4のアルコキシ基を含有するポリオルガノシロキサンを併用することによって、シラン化合物の加水分解反応性を任意に変化させることができることを見出した。従って、かかる2種類のオルガノポリシロキサンをアクリル樹脂及び架橋剤とともに配合した粘着剤組成物は、加水分解するアルコキシ基の量が長期にわたり一定に保たれるため、性能が安定している。
また、粘着剤において、その層が設けられる光学フィルムの種類、使用条件等によって、その中に配合されるシラン化合物の加水分解反応性は異なることがあるが、それぞれの目的に応じてアルコキシ基の種類と含有量を変えた単一製品を提供することには限界がある。そこで、加水分解反応性が異なる少なくとも2種類のオルガノポリシロキサンを用意し、要求レベルに応じてそれらの混合比率を変えた組成物とすることで、対応可能な範囲が拡大する。
更に、上記のオルガノポリシロキサンは、シランカップリング剤としての効果があり、ガラス及びアクリル樹脂との親和性が高いため、それを配合した粘着剤組成物から形成される粘着剤層が設けられた粘着剤付き光学フィルムは、その粘着剤層側でガラス基板に貼り合わせたときに、粘着剤層とガラス基板との間の浮きや剥れ等が抑制される。更にこのオルガノポリシロキサンは、シリコーン系剥離剤としての効果も発現するため、それを配合した粘着剤組成物から形成された粘着剤層が設けられた粘着剤付き光学フィルムは、リワーク性にも優れるものとなることを知見し、本発明をなすに至った。As a result of diligent research to solve such problems, the present inventors have found that organopolysiloxanes containing methoxy groups and / or ethoxy groups in one molecule together with functional groups such as mercapto groups, and mercapto groups, etc. In addition to the functional group and methoxy group and / or ethoxy group, an organopolysiloxane containing an alkoxy group having 3 and / or 4 carbon atoms such as propoxy group or butoxy group in one molecule is used as an adhesive component. It has been found that blending is effective.
That is, silane compounds or organopolysiloxanes conventionally used in the field of pressure-sensitive adhesives have many methoxy groups and / or ethoxy groups in the molecule, but in this case, their hydrolyzability is sufficiently controlled. There was a problem in storage stability. In particular, since acrylic pressure-sensitive adhesive contains moisture, it has been difficult to stabilize the properties of the pressure-sensitive adhesive containing a silane compound for a long period of time. Therefore, a polyorganosiloxane containing a methoxy group or ethoxy group having a high hydrolysis reactivity and a polyorganosiloxane containing an alkoxy group having 3 and / or 4 carbon atoms such as a propoxy group or a butoxy group having a low hydrolysis reactivity. It has been found that the hydrolysis reactivity of the silane compound can be arbitrarily changed by using siloxane together. Therefore, the pressure-sensitive adhesive composition obtained by blending these two types of organopolysiloxane together with the acrylic resin and the crosslinking agent has a stable performance because the amount of the alkoxy group to be hydrolyzed is kept constant over a long period of time.
In addition, in the pressure-sensitive adhesive, the hydrolysis reactivity of the silane compound blended therein may vary depending on the type of optical film provided with the layer, the use conditions, etc. There is a limit to providing a single product with different types and contents. Therefore, by preparing at least two types of organopolysiloxanes having different hydrolytic reactivities and changing the mixing ratio according to the required level, the applicable range is expanded.
Furthermore, the above-mentioned organopolysiloxane has an effect as a silane coupling agent, and since it has high affinity with glass and acrylic resin, a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing the same is provided. When an optical film with an adhesive is bonded to a glass substrate on the adhesive layer side, floating or peeling between the adhesive layer and the glass substrate is suppressed. Furthermore, since this organopolysiloxane also exhibits an effect as a silicone release agent, an optical film with an adhesive provided with an adhesive layer formed from an adhesive composition containing the organopolysiloxane is excellent in reworkability. As a result, the present inventors have made the present invention.
従って、本発明は、下記粘着剤組成物及び粘着剤付き光学フィルムを提供する。
(1)(A)アクリル樹脂、
(B)架橋剤、
(C)下記平均組成式(I)
YaR1 bSi(OCH3)c(OC2H5)d(OH)eO(4-a-b-c-d-e)/2 …(I)
(式中、Yはメルカプト基、エポキシ基、(メタ)アクリロイロキシ基、アルケニル基、
ハロアルキル基及びアミノ基から選ばれる少なくとも1種を有する有機基を表し;
R1は、少なくとも1種の脂肪族不飽和結合を有さない炭素原子数1〜8の非置換の一価炭化水素基を表し;
a、b、c、d及びeは、0.01≦a≦1、0≦b<2、0≦c≦2、0≦d≦2、0≦e≦1であって、かつ0.1≦c+d≦2.5及び2≦a+b+c+d+e≦3を満たす数である。)
で表される第一のオルガノポリシロキサン、及び
(D)下記平均組成式(II)
YfR1 gSi(OCH3)h(OC2H5)i(OR2)j(OH)kO(4-f-g-h-i-j-k)/2
…(II)
(式中、Y及びR1は、上記と同じ意味を表し;
R2は、炭素原子数3及び/又は4のアルキル基あるいはメトキシプロピル基を表し;
f、g、h、i、j及びkは、0.01≦f≦1、0≦g<2、0≦h≦2、0≦i≦2、0<j≦2、0≦k≦1であって、hとiが同時に0となることはなく、かつ0.1≦h+i+j≦2.5及び2≦f+g+h+i+j+k≦3を満たす数である。)
で表される第二のオルガノポリシロキサン
を含有することを特徴とする粘着剤組成物。
(2)アクリル樹脂(A)は、(メタ)アクリル酸アルキルエステルに由来する構造単位を主成分とし、極性官能基を有する(メタ)アクリル酸系化合物に由来する構造単位を含むアクリル樹脂を含有する(1)に記載の粘着剤組成物。
(3)極性官能基は、遊離カルボキシル基、水酸基、アミノ基及びエポキシ環から選ばれるものである(2)に記載の粘着剤組成物。
(4)架橋剤(B)は、イソシアネート系化合物を含む(1)〜(3)のいずれかに記載の粘着剤組成物。
(5)第一のオルガノポリシロキサン(C)を表す前記平均組成式(I)及び第二のオルガノポリシロキサン(D)を表す前記平均組成式(II)において、Yがメルカプト基又はエポキシ基を有する有機基である(1)〜(4)のいずれかに記載の粘着剤組成物。
(6)第一のオルガノポリシロキサン(C)を表す前記平均組成式(I)及び第二のオルガノポリシロキサン(D)を表す前記平均組成式(II)において、b及びgが正数で、R1がメチル基であり、R2がプロピル基又はイソプロピル基である(1)〜(5)のいずれかに記載の粘着剤組成物。
(7)第一のオルガノポリシロキサン(C)を表す前記平均組成式(I)において、c及びdがともに正数であり、第二のオルガノポリシロキサン(D)を表す前記平均組成式(II)において、h及びiがともに正数である(1)〜(6)のいずれかに記載の粘着剤組成物。
(8)第一のオルガノポリシロキサン(C)及び第二のオルガノポリシロキサン(D)は、それぞれ平均重合度が3〜100である(1)〜(7)のいずれかに記載の粘着剤組成物。
(9)光学フィルムの少なくとも一方の面に、(1)〜(8)のいずれかに記載の粘着剤組成物から形成される粘着剤層が設けられていることを特徴とする粘着剤付き光学フィルム。
(10)光学フィルムは、偏光フィルム及び位相差フィルムから選ばれる(9)に記載の粘着剤付き光学フィルム。
(11)光学フィルムは、偏光子の少なくとも一方の面にアセチルセルロース系樹脂又は非晶性環状ポリオレフィン系樹脂からなる保護フィルムが貼着された偏光フィルムを含む(10)に記載の粘着剤付き光学フィルム。Therefore, this invention provides the following adhesive composition and an optical film with an adhesive.
(1) (A) acrylic resin,
(B) a crosslinking agent,
(C) The following average composition formula (I)
Y a R 1 b Si (OCH 3 ) c (OC 2 H 5 ) d (OH) e O (4-abcde) / 2 (I)
Wherein Y is a mercapto group, an epoxy group, a (meth) acryloyloxy group, an alkenyl group,
Represents an organic group having at least one selected from a haloalkyl group and an amino group;
R 1 represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond;
a, b, c, d and e are 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 ≦ c ≦ 2, 0 ≦ d ≦ 2, 0 ≦ e ≦ 1, and 0.1 ≦ c + d ≦ 2.5 and 2 ≦ a + b + c + d + e ≦ 3. )
And (D) the following average composition formula (II)
Y f R 1 g Si (OCH 3 ) h (OC 2 H 5 ) i (OR 2 ) j (OH) k O (4-fghijk) / 2
... (II)
Wherein Y and R 1 represent the same meaning as above;
R 2 represents an alkyl group having 3 and / or 4 carbon atoms or a methoxypropyl group;
f, g, h, i, j and k are 0.01 ≦ f ≦ 1, 0 ≦ g <2, 0 ≦ h ≦ 2, 0 ≦ i ≦ 2, 0 <j ≦ 2, 0 ≦ k ≦ 1. In this case, h and i are not 0 at the same time, and are numbers satisfying 0.1 ≦ h + i + j ≦ 2.5 and 2 ≦ f + g + h + i + j + k ≦ 3. )
A pressure-sensitive adhesive composition comprising a second organopolysiloxane represented by the formula:
(2) The acrylic resin (A) contains an acrylic resin containing a structural unit derived from a (meth) acrylic acid-based compound having a polar functional group as a main component and derived from a (meth) acrylic acid alkyl ester. The pressure-sensitive adhesive composition according to (1).
(3) The pressure-sensitive adhesive composition according to (2), wherein the polar functional group is selected from a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring.
(4) The pressure-sensitive adhesive composition according to any one of (1) to (3), wherein the crosslinking agent (B) includes an isocyanate compound.
(5) In the average composition formula (I) representing the first organopolysiloxane (C) and the average composition formula (II) representing the second organopolysiloxane (D), Y represents a mercapto group or an epoxy group. The pressure-sensitive adhesive composition according to any one of (1) to (4), which is an organic group.
(6) In the average composition formula (I) representing the first organopolysiloxane (C) and the average composition formula (II) representing the second organopolysiloxane (D), b and g are positive numbers, The pressure-sensitive adhesive composition according to any one of (1) to (5), wherein R 1 is a methyl group, and R 2 is a propyl group or an isopropyl group.
(7) In the average composition formula (I) representing the first organopolysiloxane (C), both c and d are positive numbers, and the average composition formula (II) representing the second organopolysiloxane (D) ), The pressure-sensitive adhesive composition according to any one of (1) to (6), wherein h and i are both positive numbers.
(8) The pressure-sensitive adhesive composition according to any one of (1) to (7), wherein the first organopolysiloxane (C) and the second organopolysiloxane (D) each have an average degree of polymerization of 3 to 100. object.
(9) A pressure-sensitive adhesive optical, wherein a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of (1) to (8) is provided on at least one surface of the optical film. the film.
(10) The optical film with an adhesive according to (9), wherein the optical film is selected from a polarizing film and a retardation film.
(11) The optical film includes a polarizing film in which a protective film made of an acetylcellulose-based resin or an amorphous cyclic polyolefin-based resin is attached to at least one surface of a polarizer. the film.
本発明の粘着剤組成物は、それを光学フィルムに貼着し、粘着剤付き光学フィルムとした状態で、長期間性能が安定しており、また大型化してもリワーク性が良好であるとともに、耐久性にも優れる。従ってこの粘着剤付き光学フィルムは、液晶表示装置に好適に用いられる。 The pressure-sensitive adhesive composition of the present invention is a state in which the performance is stable for a long time in a state in which it is adhered to an optical film and made into an optical film with a pressure-sensitive adhesive, and reworkability is good even when the size is increased, Excellent durability. Therefore, this optical film with an adhesive is suitably used for a liquid crystal display device.
以下、本発明の実施の形態を詳しく説明する。本発明の粘着剤組成物は、(A)アクリル樹脂、(B)架橋剤、(C)前記平均組成式(I)で表され、メルカプト基等の官能基とメトキシ基及び/又はエトキシ基とを一分子内に含有する第一のオルガノポリシロキサン、並びに(D)前記平均組成式(II)で表され、メルカプト基等の官能基とメトキシ基及び/又はエトキシ基と炭素原子数3及び/又は4のアルコキシ基とを一分子内に含有する第二のオルガノポリシロキサンを必須に含有するものである。まず、これらの成分について説明する。 Hereinafter, embodiments of the present invention will be described in detail. The pressure-sensitive adhesive composition of the present invention is represented by (A) an acrylic resin, (B) a crosslinking agent, (C) the average composition formula (I), a functional group such as a mercapto group, a methoxy group, and / or an ethoxy group. And (D) a functional group such as a mercapto group, a methoxy group, and / or an ethoxy group, and a carbon atom number of 3 and / or Or the 2nd organopolysiloxane which contains 4 alkoxy groups in 1 molecule is contained essentially. First, these components will be described.
[アクリル樹脂]
本発明に用いられるアクリル樹脂は、具体的には(メタ)アクリル酸アルキルエステルに由来する構造単位を主成分とし、遊離カルボキシル基、水酸基、アミノ基、エポキシ環をはじめとする複素環基等の極性官能基を有するモノマー、好ましくは極性官能基を有する(メタ)アクリル酸系化合物に由来する構造単位を含むアクリル樹脂(A−1)であることが好ましい。ここで、(メタ)アクリル酸とは、アクリル酸又はメタクリル酸のいずれでもよいことを意味し、他に、(メタ)アクリレート等というときの「(メタ)」も同様の趣旨である。また、ここでのアルキル基は脂環式構造を有するアルキル基(シクロアルキル基)は含まない。[acrylic resin]
Specifically, the acrylic resin used in the present invention is mainly composed of a structural unit derived from (meth) acrylic acid alkyl ester, and includes a free carboxyl group, a hydroxyl group, an amino group, a heterocyclic group including an epoxy ring, and the like. A monomer having a polar functional group, preferably an acrylic resin (A-1) containing a structural unit derived from a (meth) acrylic acid compound having a polar functional group is preferred. Here, (meth) acrylic acid means that either acrylic acid or methacrylic acid may be used, and “(meth)” when referred to as (meth) acrylate or the like has the same meaning. Further, the alkyl group here does not include an alkyl group (cycloalkyl group) having an alicyclic structure.
(メタ)アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸2−エチルヘキシル、アクリル酸オクチル、アクリル酸イソオクチル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸ベンジル、アクリル酸メトキシエチル、アクリル酸エトキシメチルの如き、アクリル酸アルキルエステルや、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸2−エチルヘキシル、メタクリル酸オクチル、メタクリル酸イソオクチル、メタクリル酸ラウリル、メタクリル酸ステアリル、メタクリル酸ベンジル、メタクリル酸メトキシエチル、メタクリル酸エトキシメチルの如き、メタクリル酸アルキルエステルが挙げられる。これらの(メタ)アクリル酸アルキルエステルは、それぞれ単独で用いることができるほか、異なる複数のものを用いて共重合させてもよい。 (Meth) acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate Alkyl acrylates such as benzyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Octyl acid, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate Can, methacrylic acid alkyl esters. These (meth) acrylic acid alkyl esters can be used alone or in combination with a plurality of different ones.
極性官能基を有するモノマーの例としては、アクリル酸、メタクリル酸、β−カルボキシエチルアクリレートの如き、遊離カルボキシル基を有するモノマー;(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸2−又は3−クロロ−2−ヒドロキシプロピル、ジエチレングリコールモノ(メタ)アクリレートの如き、水酸基を有するモノマー;アクリロイルモルホリン、ビニルカプロラクタム、N−ビニル−2−ピロリドン、テトラヒドロフルフリル(メタ)アクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、3,4−エポキシシクロヘキシルメチル(メタ)アクリレート、グリシジル(メタ)アクリレート、2,5−ジヒドロフランの如き、複素環基を有するモノマー;N,N−ジメチルアミノエチル(メタ)アクリレートの如き、複素環とは異なるアミノ基を有するモノマー等を挙げることができる。これらの極性官能基を有するモノマーは、それぞれ単独で用いることができるほか、異なる複数のものを用いてもよい。 Examples of the monomer having a polar functional group include monomers having a free carboxyl group such as acrylic acid, methacrylic acid, and β-carboxyethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Monomers having a hydroxyl group such as propyl, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate; acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl Has a heterocyclic group such as (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2,5-dihydrofuran That monomers; N, such as N- dimethylaminoethyl (meth) acrylate, and monomers having different amino group and heterocyclic. These monomers having polar functional groups can be used alone or in combination with a plurality of different monomers.
粘着剤組成物におけるアクリル樹脂(A−1)は、その100質量部中、(メタ)アクリル酸アルキルエステルに由来する構造単位を、通常は60〜99.9質量部、好ましくは80〜99.6質量部の割合で含有しており、また極性官能基を有するモノマーに由来する構造単位を、通常は0.1〜20質量部、好ましくは0.4〜10質量部の割合で含有している。 In 100 parts by mass of the acrylic resin (A-1) in the pressure-sensitive adhesive composition, the structural unit derived from (meth) acrylic acid alkyl ester is usually 60-99.9 parts by mass, preferably 80-99. It is contained at a ratio of 6 parts by mass, and the structural unit derived from the monomer having a polar functional group is usually contained at a ratio of 0.1 to 20 parts by mass, preferably 0.4 to 10 parts by mass. Yes.
本発明で使用されるアクリル樹脂(A−1)は、上記で説明した(メタ)アクリル酸アルキルエステル及び極性官能基を有するモノマー以外のモノマーに由来する構造単位を含有していてもよい。これらの例としては、分子内に脂環式構造を有する(メタ)アクリル酸エステルに由来する構造単位、スチレン系モノマーに由来する構造単位、ビニル系モノマーに由来する構造単位、分子内に複数の(メタ)アクリロイル基を有するモノマーに由来する構造単位等を挙げることができる。 The acrylic resin (A-1) used in the present invention may contain a structural unit derived from a monomer other than the (meth) acrylic acid alkyl ester described above and a monomer having a polar functional group. Examples of these include structural units derived from (meth) acrylic acid esters having an alicyclic structure in the molecule, structural units derived from styrene monomers, structural units derived from vinyl monomers, and a plurality of structural units in the molecule. Examples include structural units derived from monomers having a (meth) acryloyl group.
脂環式構造とは、通常、炭素数5以上、好ましくは炭素数5〜7程度のシクロパラフィン構造である。脂環式構造を有するアクリル酸エステルの具体例としては、アクリル酸イソボルニル、アクリル酸シクロヘキシル、アクリル酸ジシクロペンタニル、アクリル酸シクロドデシル、アクリル酸メチルシクロヘキシル、アクリル酸トリメチルシクロヘキシル、アクリル酸tert−ブチルシクロヘキシル、α−エトキシアクリル酸シクロヘキシル、アクリル酸シクロヘキシルフェニル等が挙げられ、脂環式構造を有するメタクリル酸エステルの具体例としては、メタクリル酸イソボルニル、メタクリル酸シクロヘキシル、メタクリル酸ジシクロペンタニル、メタクリル酸シクロドデシル、メタクリル酸メチルシクロヘキシル、メタクリル酸トリメチルシクロヘキシル、メタクリル酸tert−ブチルシクロヘキシル、メタクリル酸シクロヘキシルフェニル等が挙げられる。 The alicyclic structure is usually a cycloparaffin structure having 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Specific examples of the acrylate ester having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methyl cyclohexyl acrylate, trimethyl cyclohexyl acrylate, and tert-butyl acrylate. Specific examples of methacrylic acid esters having an alicyclic structure include cyclohexyl, α-ethoxyacrylate cyclohexyl, cyclohexyl phenyl acrylate, etc. Specific examples of methacrylic acid esters having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, methacrylic acid. Cyclododecyl, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, tert-butyl cyclohexyl methacrylate, cyclohexyl methacrylate Eniru, and the like.
スチレン系モノマーの例としては、スチレンのほか、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、トリエチルスチレン、プロピルスチレン、ブチルスチレン、ヘキシルスチレン、ヘプチルスチレン、オクチルスチレンの如きアルキルスチレン;フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレンの如きハロゲン化スチレン;更に、ニトロスチレン、アセチルスチレン、メトキシスチレン、ジビニルベンゼン等を挙げることができる。 Examples of styrenic monomers include styrene, alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; Halogenated styrene such as styrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; and nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene and the like.
ビニル系モノマーの例としては、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、2−エチルヘキサン酸ビニル、ラウリン酸ビニルの如き脂肪酸ビニルエステル;塩化ビニルや臭化ビニルの如きハロゲン化ビニル;塩化ビニリデンの如きハロゲン化ビニリデン;ビニルピリジン、ビニルピロリドン、ビニルカルバゾールの如き含窒素芳香族ビニル;ブタジエン、イソプレン、クロロプレンの如き共役ジエンモノマー;更には、アクリロニトリル、メタクリロニトリル等を挙げることができる。 Examples of vinyl-based monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate such as vinyl esters; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride and the like. Examples thereof include vinylidene halides; nitrogen-containing aromatic vinyls such as vinyl pyridine, vinyl pyrrolidone and vinyl carbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; and acrylonitrile and methacrylonitrile.
分子内に複数の(メタ)アクリロイル基を有するモノマーの例としては、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレートの如き、分子内に2個の(メタ)アクリロイル基を有するモノマー;トリメチロールプロパントリ(メタ)アクリレートの如き、分子内に3個の(メタ)アクリロイル基を有するモノマー等を挙げることができる。 Examples of monomers having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( 2 (meth) acryloyl groups in the molecule such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate And a monomer having three (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate.
(メタ)アクリル酸エステル及び極性官能基を有するモノマー以外のモノマーは、それぞれ単独で、又は2種以上組み合わせて使用することができる。粘着剤組成物を構成するアクリル樹脂(A−1)において、(メタ)アクリル酸エステル及び極性官能基を有するモノマー以外のモノマーに由来する構造単位は、アクリル樹脂(A−1)100質量部中、通常0〜20質量部、好ましくは0〜10質量部の割合で含有される。 Monomers other than (meth) acrylic acid esters and monomers having a polar functional group can be used alone or in combination of two or more. In the acrylic resin (A-1) constituting the pressure-sensitive adhesive composition, the structural unit derived from the monomer other than the (meth) acrylic acid ester and the monomer having a polar functional group is 100 parts by mass of the acrylic resin (A-1). The content is usually 0 to 20 parts by mass, preferably 0 to 10 parts by mass.
粘着剤組成物の有効成分は、以上のような、(メタ)アクリル酸アルキルエステルに由来する構造単位を主成分とし、極性官能基を有するモノマーに由来する構造単位を含むアクリル樹脂(A−1)を2種類以上含むものであってもよい。更に、前記アクリル樹脂(A−1)に、それとは異なるアクリル樹脂(A−2)、具体的には例えば、(メタ)アクリル酸アルキルエステルに由来する構造単位を有し、極性官能基を含まないアクリル樹脂等を混合したものであってもよいが、(メタ)アクリル酸アルキルエステルに由来する構造単位を主成分とし、極性官能基を有するモノマーに由来する構造単位を含むアクリル樹脂(A−1)は、全アクリル樹脂の60〜100質量%、特に80〜100質量%であることが好ましい。 The active ingredient of the pressure-sensitive adhesive composition includes an acrylic resin (A-1) containing a structural unit derived from a monomer having a polar functional group, the main component being a structural unit derived from (meth) acrylic acid alkyl ester as described above. ) May be included. Furthermore, the acrylic resin (A-1) has a structural unit derived from an acrylic resin (A-2) different from the acrylic resin (A-2), specifically (meth) acrylic acid alkyl ester, and includes a polar functional group. Acrylic resin (A-) containing a structural unit derived from a monomer having a polar functional group, the main component being a structural unit derived from (meth) acrylic acid alkyl ester. 1) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, based on the total acrylic resin.
(メタ)アクリル酸アルキルエステルに由来する構造単位を主成分とし、極性官能基を有するモノマーに由来する構造単位を含有するアクリル樹脂(A−1)は、ゲルパーミエーションクロマトグラフィー(GPC)による標準ポリスチレン換算の重量平均分子量(Mw)が、1,000,000〜2,000,000の範囲にあることが好ましい。標準ポリスチレン換算の重量平均分子量が1,000,000以上であると、高温高湿下での接着性が向上し、ガラス基板と粘着剤層との間に浮きや剥れの発生する可能性が低くなる傾向にあり、しかもリワーク性が向上する傾向にあることから好ましい。またこの重量平均分子量が2,000,000以下であると、その粘着剤層に貼着された光学フィルムの寸法が変化しても、その寸法変化に粘着剤層が追随して変動するので、液晶セルの周縁部の明るさと中心部の明るさとの間に差がなくなり、白抜けや色ムラが抑制される傾向にあることから好ましい。重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)で表される分子量分布は、通常2〜10程度の範囲にある。 The acrylic resin (A-1) containing a structural unit derived from a monomer having a polar functional group as a main component derived from a (meth) acrylic acid alkyl ester is a standard by gel permeation chromatography (GPC). The polystyrene-equivalent weight average molecular weight (Mw) is preferably in the range of 1,000,000 to 2,000,000. When the weight average molecular weight in terms of standard polystyrene is 1,000,000 or more, the adhesiveness under high temperature and high humidity is improved, and there is a possibility that floating or peeling occurs between the glass substrate and the pressure-sensitive adhesive layer. This is preferable because it tends to be low and reworkability tends to improve. In addition, when the weight average molecular weight is 2,000,000 or less, even if the dimension of the optical film attached to the pressure-sensitive adhesive layer changes, the pressure-sensitive adhesive layer changes following the dimensional change. This is preferable because there is no difference between the brightness at the peripheral edge and the brightness at the center of the liquid crystal cell, and white spots and color unevenness tend to be suppressed. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is usually in the range of about 2 to 10.
アクリル樹脂(2種類以上を組み合わせる場合は両者の混合物)は、それを酢酸エチルに溶かして不揮発分濃度20質量%に調整した溶液が、25℃において20Pa・s以下、更には0.1〜7Pa・sの粘度を示すことが好ましい。このときの粘度が20Pa・s以下であると、高温高湿下での接着性が向上し、ガラス基板と粘着剤層との間に浮きや剥れの発生する可能性が低くなる傾向にあり、しかもリワーク性が向上する傾向にあることから好ましい。粘度は、例えばブルックフィールド粘度計によって測定することができる。 Acrylic resin (a mixture of both when two or more types are combined) is a solution prepared by dissolving it in ethyl acetate to a non-volatile content of 20% by mass at 25 ° C., 20 Pa · s or less, and further 0.1 to 7 Pa. -It is preferable to show the viscosity of s. If the viscosity at this time is 20 Pa · s or less, the adhesiveness under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer tends to be reduced. Moreover, it is preferable because reworkability tends to be improved. The viscosity can be measured by, for example, a Brookfield viscometer.
粘着剤組成物を構成するアクリル樹脂(A−1)は、例えば、溶液重合法、乳化重合法、塊状重合法、懸濁重合法等、公知の各種方法によって製造することができる。このアクリル樹脂の製造においては、通常、重合開始剤が用いられる。重合開始剤は、アクリル樹脂の製造に用いられる全てのモノマーの合計100質量部に対して、0.001〜5質量部程度使用される。 The acrylic resin (A-1) constituting the pressure-sensitive adhesive composition can be produced by various known methods such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method. In the production of this acrylic resin, a polymerization initiator is usually used. A polymerization initiator is used about 0.001-5 mass parts with respect to a total of 100 mass parts of all the monomers used for manufacture of an acrylic resin.
重合開始剤としては、熱重合開始剤や光重合開始剤等が用いられる。光重合開始剤として、例えば、4−(2−ヒドロキシエトキシ)フェニル(2−ヒドロキシ−2−プロピル)ケトン等を挙げることができる。熱重合開始剤として、例えば、2,2′−アゾビスイソブチロニトリル、2,2′−アゾビス(2−メチルブチロニトリル)、1,1′−アゾビス(シクロヘキサン−1−カルボニトリル)、2,2′−アゾビス(2,4−ジメチルバレロニトリル)、2,2′−アゾビス(2,4−ジメチル−4−メトキシバレロニトリル)、ジメチル−2,2′−アゾビス(2−メチルプロピオネート)、2,2′−アゾビス(2−ヒドロキシメチルプロピオニトリル)の如きアゾ系化合物;ラウリルパーオキサイド、tert−ブチルハイドロパーオキサイド、過酸化ベンゾイル、tert−ブチルパーオキシベンゾエート、クメンハイドロパーオキサイド、ジイソプロピルパーオキシジカーボネート、ジプロピルパーオキシジカーボネート、tert−ブチルパーオキシネオデカノエート、tert−ブチルパーオキシピバレート、(3,5,5−トリメチルヘキサノイル)パーオキサイドの如き有機過酸化物;過硫酸カリウム、過硫酸アンモニウム、過酸化水素の如き無機過酸化物等を挙げることができる。また、過酸化物と還元剤を併用したレドックス系開始剤等も、重合開始剤として使用し得る。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Examples of the thermal polymerization initiator include 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-methylpropio) Azo) compounds such as 2,2'-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide , Diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert Organic peroxides such as butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide An oxide etc. can be mentioned. A redox initiator or the like using a peroxide and a reducing agent in combination can also be used as the polymerization initiator.
アクリル樹脂(A−1)の製造方法としては、上記に示した方法のなかでも、溶液重合法が好ましい。溶液重合法の具体例を挙げて説明すると、所望のモノマー及び有機溶媒を混合し、窒素雰囲気下にて、熱重合開始剤を添加して、40〜90℃程度、好ましくは60〜80℃程度にて3〜10時間程度撹拌する方法等を挙げることができる。また、反応を制御するために、モノマーや熱重合開始剤を重合中に連続的又は間歇的に添加したり、有機溶媒に溶解した状態で添加したりしてもよい。ここで、有機溶媒としては、例えば、トルエン、キシレンの如き芳香族炭化水素類;酢酸エチル、酢酸ブチルの如きエステル類;プロピルアルコール、イソプロピルアルコールの如き脂肪族アルコール類;メチルエチルケトン、メチルイソブチルケトンの如きケトン類等を用いることができる。 As a manufacturing method of an acrylic resin (A-1), a solution polymerization method is preferable among the methods shown above. A specific example of the solution polymerization method will be described. A desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added under a nitrogen atmosphere, and is about 40 to 90 ° C, preferably about 60 to 80 ° C. And a method of stirring for about 3 to 10 hours. Moreover, in order to control reaction, you may add a monomer and a thermal-polymerization initiator continuously or intermittently during superposition | polymerization, or may be added in the state melt | dissolved in the organic solvent. Here, examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; methyl ethyl ketone and methyl isobutyl ketone. Ketones can be used.
[架橋剤]
本発明の粘着剤組成物においては、以上のようなアクリル樹脂に、更に架橋剤を配合する。架橋剤は、極性官能基と架橋し得る官能基を分子内に少なくとも2個有する化合物であって、具体的には例えば、イソシアネート系化合物、エポキシ系化合物、金属キレート化合物、アジリジン系化合物等を挙げることができる。[Crosslinking agent]
In the pressure-sensitive adhesive composition of the present invention, a crosslinking agent is further added to the acrylic resin as described above. The crosslinking agent is a compound having at least two functional groups capable of crosslinking with polar functional groups in the molecule, and specific examples include isocyanate compounds, epoxy compounds, metal chelate compounds, aziridine compounds, and the like. be able to.
イソシアネート系化合物は、分子内に少なくとも2個のイソシアナト基(−NCO)を有する化合物であり、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等が挙げられる。また、これらのイソシアネート化合物に、グリセロールやトリメチロールプロパン等のポリオールを反応せしめたアダクト体や、イソシアネート化合物を2量体、3量体等にしたものも、粘着剤組成物に用いられる架橋剤となり得る。更に、2種類以上のイソシアネート系化合物を混合して用いることもできる。 Isocyanate compounds are compounds having at least two isocyanato groups (-NCO) in the molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, Examples include hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. In addition, adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylolpropane, and those obtained by converting isocyanate compounds into dimers, trimers, etc., also serve as crosslinking agents for the pressure-sensitive adhesive composition. obtain. Further, two or more kinds of isocyanate compounds can be mixed and used.
エポキシ系化合物は、分子内に少なくとも2個のエポキシ基を有する化合物であり、例えば、ビスフェノールA型のエポキシ樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、N,N−ジグリシジルアニリン、N,N,N′,N′−テトラグリシジル−m−キシレンジアミン、1,3−ビス(N,N′−ジグリシジルアミノメチル)シクロヘキサン等が挙げられる。2種類以上のエポキシ系化合物を混合して用いてもよい。 The epoxy compound is a compound having at least two epoxy groups in the molecule, for example, bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis ( N, N'-diglycidylaminomethyl) cyclohexane and the like. Two or more types of epoxy compounds may be mixed and used.
金属キレート化合物としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム及びジルコニウム等の多価金属に、アセチルアセトンやアセト酢酸エチルが配位した化合物等が挙げられる。 Examples of the metal chelate compound include compounds in which acetylacetone or ethyl acetoacetate is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. Can be mentioned.
アジリジン系化合物は、エチレンイミンとも呼ばれる1個の窒素原子と2個の炭素原子からなる3員環の骨格を分子内に少なくとも2個有する化合物であり、例えば、ジフェニルメタン−4,4′−ビス(1−アジリジンカルボキサミド)、トルエン−2,4−ビス(1−アジリジンカルボキサミド)、トリエチレンメラミン、イソフタロイルビス−1−(2−メチルアジリジン)、トリス−1−アジリジニルホスフィンオキサイド、ヘキサメチレン−1,6−ビス(1−アジリジンカルボキサミド)、トリメチロールプロパン−トリ−β−アジリジニルプロピオネート、テトラメチロールメタン−トリ−β−アジリジニルプロピオネート等が挙げられる。 An aziridine-based compound is a compound having at least two skeletons of a three-membered ring composed of one nitrogen atom and two carbon atoms, also called ethyleneimine, for example, diphenylmethane-4,4′-bis ( 1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2-methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene -1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and the like.
これらの架橋剤のなかでも、イソシアネート系化合物が好ましく用いられる。また、イソシアネート系化合物とアジリジン系化合物を併用するのも有効である。 Of these crosslinking agents, isocyanate compounds are preferably used. It is also effective to use an isocyanate compound and an aziridine compound in combination.
[オルガノポリシロキサン]
本発明では更に、有機官能基とメトキシ基及び/又はエトキシ基とを一分子内に含有し、下記平均組成式(I)で表される第一のオルガノポリシロキサン、並びに、有機官能基と、メトキシ基及び/又はエトキシ基と、プロポキシ基やブトキシ基等の炭素原子数が3及び/又は4のアルコキシ基とを一分子内に同時に含有し、下記平均組成式(II)で表される第二のオルガノポリシロキサンを配合する。
YaR1 bSi(OCH3)c(OC2H5)d(OH)eO(4-a-b-c-d-e)/2 …(I)
YfR1 gSi(OCH3)h(OC2H5)i(OR2)j(OH)kO(4-f-g-h-i-j-k)/2
…(II)[Organopolysiloxane]
In the present invention, an organic functional group, a methoxy group and / or an ethoxy group are contained in one molecule, the first organopolysiloxane represented by the following average composition formula (I), and the organic functional group: A methoxy group and / or an ethoxy group and an alkoxy group having 3 and / or 4 carbon atoms such as a propoxy group and a butoxy group are simultaneously contained in one molecule, and are represented by the following average composition formula (II): Two organopolysiloxanes are blended.
Y a R 1 b Si (OCH 3 ) c (OC 2 H 5 ) d (OH) e O (4-abcde) / 2 (I)
Y f R 1 g Si (OCH 3 ) h (OC 2 H 5 ) i (OR 2 ) j (OH) k O (4-fghijk) / 2
... (II)
前記式(I)及び(II)において、Yは、メルカプト基、エポキシ基、(メタ)アクリロイロキシ基、アルケニル基、ハロアルキル基及びアミノ基から選ばれる官能基を有する有機基である。これらの官能基のうち、メルカプト基、エポキシ基、(メタ)アクリロイロキシ基及びアミノ基は、通常、連結基を介してケイ素原子に結合し、かかる連結基としては、エーテル結合(−O−)、イミノ基(−NH−)等のヘテロ原子を介在してもよい炭素数1〜12のアルキレン基、アルキレン−アリーレン−アルキレン基等の2価の炭化水素基が挙げられ、例えば、メチレン、エチレン、トリメチレン、ヘキサメチレン、デカメチレン等を包含するアルキレン、メチルフェニルエチル等を包含する芳香族環を間に有する2価の炭化水素基、メトキシメチル、メトキシエチル、メトキシプロピル等を包含する酸素原子を間に有する2価の脂肪族基等を挙げることができる。アルケニル基やハロアルキル基は、上記連結基を介してケイ素原子に結合してもよいし、直接ケイ素原子に結合してもよい。 In the formulas (I) and (II), Y is an organic group having a functional group selected from a mercapto group, an epoxy group, a (meth) acryloyloxy group, an alkenyl group, a haloalkyl group, and an amino group. Among these functional groups, a mercapto group, an epoxy group, a (meth) acryloyloxy group, and an amino group are usually bonded to a silicon atom via a linking group. Examples of the linking group include an ether bond (—O—), Examples thereof include divalent hydrocarbon groups such as an alkylene group having 1 to 12 carbon atoms and an alkylene-arylene-alkylene group which may have a hetero atom such as an imino group (—NH—), for example, methylene, ethylene, Divalent hydrocarbon group having an aromatic ring including trimethylene, hexamethylene, decamethylene, etc., including methylphenylethyl, oxygen atoms including methoxymethyl, methoxyethyl, methoxypropyl, etc. Examples thereof include a divalent aliphatic group. The alkenyl group or haloalkyl group may be bonded to the silicon atom via the above linking group, or may be directly bonded to the silicon atom.
Yで表される官能基を有する有機基(以下、Yで表される基を「有機官能基」と呼ぶことがある)の具体例を挙げると、メルカプト基を有する有機基として、メルカプトメチル基、3−メルカプトプロピル基、6−メルカプトヘキシル基、10−メルカプトデシル基、2−(4−メルカプトメチルフェニル)エチル基等が例示され、エポキシ基を有する有機基として、グリシドキシメチル基、3−グリシドキシプロピル基、5,6−エポキシヘキシル基、9,10−エポキシデシル基、2−(3,4−エポキシシクロヘキシル)エチル基、2−(3,4−エポキシ−4−メチルシクロヘキシル)プロピル基等が例示され、(メタ)アクリロイロキシ基を有する有機基として、アクリロイロキシメチル基、3−アクリロイロキシプロピル基、6−アクリロイロキシヘキシル基、10−アクリロイロキシデシル基、メタクリロイロキシメチル基、3−メタクリロイロキシプロピル基、6−メタクリロイロキシヘキシル基、10−メタクリロイロキシデシル基等が例示され、アルケニル基を有する有機基として、ビニル基、アリル基、5−ヘキセニル基、9−デセニル基、3−ビニルオキシプロピル基、p−スチリル基、シクロヘキセニルエチル基等が例示され、ハロアルキル基を有する有機基として、クロロメチル基、3−クロロプロピル基、6−クロロヘキシル基、10−クロロデシル基、ブロモメチル基、3−ブロモプロピル基等が例示され、アミノ基を有する有機基として、アミノメチル基、3−アミノプロピル基、6−アミノプロピル基、N−メチル−3−アミノプロピル基、N,N−ジメチル−3−アミノプロピル基、N−フェニル−3−アミノプロピル基、N−(2−アミノエチル)−3−アミノプロピル基、N−(6−アミノヘキシル)−3−アミノプロピル基、N−(ビニルベンジル)−2−アミノエチル−3−アミノプロピル基等が例示される。 Specific examples of the organic group having a functional group represented by Y (hereinafter, the group represented by Y may be referred to as “organic functional group”) are as follows. As an organic group having a mercapto group, a mercaptomethyl group , 3-mercaptopropyl group, 6-mercaptohexyl group, 10-mercaptodecyl group, 2- (4-mercaptomethylphenyl) ethyl group and the like, and the organic group having an epoxy group includes glycidoxymethyl group, 3 -Glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2- (3,4-epoxy-4-methylcyclohexyl) A propyl group is exemplified, and examples of the organic group having a (meth) acryloyloxy group include an acryloyloxymethyl group, a 3-acryloyloxypropyl group, 6 Examples include acryloyloxyhexyl group, 10-acryloyloxydecyl group, methacryloyloxymethyl group, 3-methacryloyloxypropyl group, 6-methacryloyloxyhexyl group, 10-methacryloyloxydecyl group, etc. Examples of the organic group having a vinyl group, an allyl group, a 5-hexenyl group, a 9-decenyl group, a 3-vinyloxypropyl group, a p-styryl group, a cyclohexenylethyl group, and the like, and an organic group having a haloalkyl group Chloromethyl group, 3-chloropropyl group, 6-chlorohexyl group, 10-chlorodecyl group, bromomethyl group, 3-bromopropyl group and the like, and as an organic group having an amino group, an aminomethyl group, 3-amino Propyl group, 6-aminopropyl group, N-methyl-3-aminopropyl group, , N-dimethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (6-aminohexyl) -3-aminopropyl group And N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl group and the like.
前記平均組成式(I)で表される第一のオルガノポリシロキサン及び平均組成式(II)で表される第二のオルガノポリシロキサンとして、異なるYを有するものを使用することも可能であるが、同一系統の官能基を有するものとすることが好ましい。この場合であっても、末端官能基とケイ素原子を接続するアルキレン基等や一つの有機基中の官能基置換数が異なるものとすることは差し支えない。 As the first organopolysiloxane represented by the average composition formula (I) and the second organopolysiloxane represented by the average composition formula (II), those having different Y can be used. It is preferable to have the same functional group. Even in this case, the number of functional group substitutions in the alkylene group or the like that connects the terminal functional group and the silicon atom or one organic group may be different.
平均組成式(I)及び(II)のオルガノポリシロキサンにおいて、上記した有機官能基のうちで、メルカプト基、エポキシ基又は(メタ)アクリロイロキシ基を有する有機基とした場合、その高い反応性から好ましいものであり、とりわけメルカプト基又はエポキシ基を有する有機基は、ガラスと光学フィルムの接着力を高める効果が高いので、より好ましい。 In the organopolysiloxanes of the average composition formulas (I) and (II), among the above-mentioned organic functional groups, when the organic group has a mercapto group, an epoxy group or a (meth) acryloyloxy group, it is preferable because of its high reactivity. In particular, an organic group having a mercapto group or an epoxy group is more preferable because it has a high effect of increasing the adhesion between glass and an optical film.
また、前記式(I)及び(II)において、R1は、少なくとも1種の脂肪族不飽和結合を有さない炭素原子数1〜8の非置換の一価炭化水素基であって、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、1−メチルプロピル基、ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、オクチル基、フェニル基、トリル基、ベンジル基、フェニルエチル基等のアルキル基、アリール基、アラルキル基が例示され、所望なら、R1として複数の基を導入することもできる。なかでも、上記した有機官能基の反応性に対する立体障害の影響やコスト面からは、特にR1をメチル基とすることが好ましい。In the formulas (I) and (II), R 1 is an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms that does not have at least one aliphatic unsaturated bond, Specifically, methyl group, ethyl group, propyl group, isopropyl group, 1-methylpropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, phenyl group, tolyl group, benzyl group, phenylethyl Examples thereof include alkyl groups such as groups, aryl groups, and aralkyl groups. If desired, a plurality of groups can be introduced as R 1 . Among these, from the viewpoint of the influence of steric hindrance on the reactivity of the organic functional group described above and the cost, it is particularly preferable that R 1 is a methyl group.
前記式(II)において、R2は炭素原子数3及び/又は4のアルキル基であり、具体的には、プロピル基、イソプロピル基、1−メチルプロピル基、ブチル基、イソブチル基又はtert−ブチル基であることができる。また、メトキシプロピル基も同等の効果を得ることができるものとしてR2に含まれる。所望なら、R2として複数の基を導入することもできる。なかでも、加水分解反応性を適度に低下させる点や、アルキル基の嵩高さが上記した有機官能基の含有量(当量)に及ぼす影響といった観点から、R2は特にプロピル基又はイソプロピル基とすることが好ましい。In the formula (II), R 2 is an alkyl group having 3 and / or 4 carbon atoms, specifically, a propyl group, an isopropyl group, a 1-methylpropyl group, a butyl group, an isobutyl group, or tert-butyl. Can be a group. A methoxypropyl group is also included in R 2 as an equivalent effect. If desired, a plurality of groups can be introduced as R 2 . Among these, R 2 is particularly a propyl group or an isopropyl group from the viewpoint of moderately reducing the hydrolysis reactivity and the influence of the bulkiness of the alkyl group on the content (equivalent) of the organic functional group described above. It is preferable.
更に、前記式(I)において、a、b、c、d及びeは、0.01≦a≦1、0≦b<2、0≦c≦2、0≦d≦2、0≦e≦1であって、かつ0.1≦c+d≦2.5及び2≦a+b+c+d+e≦3を満たす数である。また前記式(II)において、f、g、h、i、j及びkは、0.01≦f≦1、0≦g<2、0≦h≦2、0≦i≦2、0<j≦2、0≦k≦1であって、hとiが同時に0となることはなく、かつ0.1≦h+i+j≦2.5及び2≦f+g+h+i+j+k≦3を満たす数である。 Further, in the formula (I), a, b, c, d and e are 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 ≦ c ≦ 2, 0 ≦ d ≦ 2, 0 ≦ e ≦. 1 and a number satisfying 0.1 ≦ c + d ≦ 2.5 and 2 ≦ a + b + c + d + e ≦ 3. In the above formula (II), f, g, h, i, j and k are 0.01 ≦ f ≦ 1, 0 ≦ g <2, 0 ≦ h ≦ 2, 0 ≦ i ≦ 2, 0 <j. ≦ 2, 0 ≦ k ≦ 1, h and i are not 0 at the same time, and satisfy 0.1 ≦ h + i + j ≦ 2.5 and 2 ≦ f + g + h + i + j + k ≦ 3.
ここで係数a及びfは、ケイ素原子に対する有機官能基の置換度を表す数値であり、これが小さすぎると、オルガノポリシロキサンの使用時に、本来あるべき有機官能基の反応性による特性が発揮されず、少なくとも一分子中に一個の有機官能基を有するものとする必要があり、一方、有機官能基の置換度を1より大きくすることは合成法上やコスト面から困難であることから、0.01≦a≦1及び0.01≦f≦1の範囲とする。好ましくは0.1≦a≦1及び0.1≦f≦1の範囲、より好ましくは0.1≦a≦0.8及び0.1≦f≦0.8の範囲である。 Here, the coefficients a and f are numerical values representing the degree of substitution of the organic functional group with respect to the silicon atom, and if this is too small, the characteristic due to the reactivity of the organic functional group that should be originally not exhibited when the organopolysiloxane is used. It is necessary to have at least one organic functional group in one molecule. On the other hand, it is difficult to make the degree of substitution of the organic functional group greater than 1 from the viewpoint of synthesis and cost. The ranges are 01 ≦ a ≦ 1 and 0.01 ≦ f ≦ 1. The range is preferably 0.1 ≦ a ≦ 1 and 0.1 ≦ f ≦ 1, and more preferably the range is 0.1 ≦ a ≦ 0.8 and 0.1 ≦ f ≦ 0.8.
係数b及びgは、ケイ素原子に対する脂肪族不飽和結合を有さない炭素原子数1〜8の非置換の一価炭化水素基の置換度を表す数値であり、これが0であるか又は0に近い場合には、相対的にアルコキシ基の含有量が増加して加水分解反応やシリル化反応への寄与率が高まるし、場合によってはオルガノポリシロキサンの水に対する親和性が向上する。一方、この数値が大きい場合、一価炭化水素基の種類によっては、オルガノポリシロキサンに疎水性が付与される(アルキル基等)、アクリル樹脂との相溶性を向上させる(フェニル基等)、粘着剤の硬化物に柔軟性や離型性を付与する(メチル基)等の効果があるが、b又はgが大きくなると相対的にアルコキシ基の含有量が減少するため、アルコキシシリル基の反応性を活用する粘着剤用途には不向きとなってしまう。そこで、使用目的に応じて0≦b<2及び0≦g<2の範囲とする。好ましくは0≦b≦1及び0≦g≦1の範囲、より好ましくは0≦b≦0.8及び0≦g≦0.8の範囲である。 The coefficients b and g are numerical values representing the degree of substitution of an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms that does not have an aliphatic unsaturated bond to a silicon atom, and this is 0 or 0. When they are close, the content of alkoxy groups is relatively increased, and the contribution rate to the hydrolysis reaction or silylation reaction is increased. In some cases, the affinity of organopolysiloxane to water is improved. On the other hand, if this value is large, depending on the type of monovalent hydrocarbon group, hydrophobicity is imparted to the organopolysiloxane (alkyl group, etc.), compatibility with acrylic resin (phenyl group, etc.) is improved, There are effects such as imparting flexibility and releasability to the cured product of the agent (methyl group), but the content of alkoxy groups decreases relatively as b or g increases, so the reactivity of alkoxysilyl groups It becomes unsuitable for the adhesive use which utilizes the. Therefore, 0 ≦ b <2 and 0 ≦ g <2 are set in accordance with the purpose of use. The range is preferably 0 ≦ b ≦ 1 and 0 ≦ g ≦ 1, and more preferably the range is 0 ≦ b ≦ 0.8 and 0 ≦ g ≦ 0.8.
式(I)における係数c及びd、並びに式(II)における係数h、i及びjは、ケイ素原子に対する複数種のアルコキシ基の置換度を表す数値であり、c及びhはメトキシ基の置換度、d及びiはエトキシ基の置換度、jは上記平均組成式(II)で表されるオルガノポリシロキサンにおける炭素原子数3及び/又は4のアルコキシ基の置換度を示すものである。 The coefficients c and d in the formula (I) and the coefficients h, i and j in the formula (II) are numerical values representing the degree of substitution of a plurality of types of alkoxy groups with respect to silicon atoms, and c and h are the degrees of substitution of methoxy groups. , D and i represent the degree of substitution of the ethoxy group, and j represents the degree of substitution of the alkoxy group having 3 and / or 4 carbon atoms in the organopolysiloxane represented by the above average composition formula (II).
前記平均組成式(I)で表される第一のオルガノポリシロキサンは、加水分解反応性が高いメトキシ基及びエトキシ基の少なくとも一方を含むものであり、使用目的に応じて置換度を任意に設定することができるが、それぞれの含有率を表すc及びdは0≦c≦2、0≦d≦2の範囲であって、かつメトキシ基とエトキシ基の合計置換度を表すc+dは、0.1≦c+d≦2.5の範囲とする。好ましくは、0≦c≦1.8、0≦d≦1.8、かつ0.2≦c+d≦2.35の範囲である。式(I)中のc及びdがともに0を超える数であって、メトキシ基とエトキシ基の双方を含有するオルガノポリシロキサンは、加水分解反応性においてその幅が広がるとともに、前記平均組成式(II)で表される第二のオルガノポリシロキサンと併用した場合に、段階的に加水分解反応に寄与する、いわゆるグラデーション効果が期待できる。そこでc及びdは、より好ましくは0.1≦c≦1.8、0.1≦d≦1.8、かつ0.5≦c+d≦2.35の範囲である。 The first organopolysiloxane represented by the average composition formula (I) includes at least one of a methoxy group and an ethoxy group having high hydrolysis reactivity, and the degree of substitution is arbitrarily set according to the purpose of use. Although c and d representing the respective contents are in the range of 0 ≦ c ≦ 2 and 0 ≦ d ≦ 2, and c + d representing the total substitution degree of the methoxy group and the ethoxy group is 0. The range is 1 ≦ c + d ≦ 2.5. Preferably, the ranges are 0 ≦ c ≦ 1.8, 0 ≦ d ≦ 1.8, and 0.2 ≦ c + d ≦ 2.35. In the formula (I), both c and d are more than 0, and the organopolysiloxane containing both methoxy group and ethoxy group is broadened in hydrolysis reactivity, and the average composition formula ( When used in combination with the second organopolysiloxane represented by II), a so-called gradation effect that contributes to the hydrolysis reaction in stages can be expected. Therefore, c and d are more preferably in the range of 0.1 ≦ c ≦ 1.8, 0.1 ≦ d ≦ 1.8, and 0.5 ≦ c + d ≦ 2.35.
一方、前記平均組成式(II)で表される第二のオルガノポリシロキサンにおいて、加水分解反応性が高いメトキシ基及びエトキシ基の含有率を表すh及びiと、加水分解反応性が低いプロポキシ基やブトキシ基等の炭素原子数3及び/又は4のアルコキシ基の含有率を表すjは、それぞれ使用目的や所望する加水分解反応性の度合いに応じて適宜設定することが可能であるが、加水分解反応性を低下させて平均組成式(I)で表される第一のオルガノポリシロキサンと併用したときの加水分解反応性をコントロールし、かつ上記したように、併用時の加水分解反応において、第二のオルガノポリシロキサンだけが取り残されることなく段階的に加水分解反応に寄与させる、いわゆるグラデーション効果を発現させるという本発明の目的からは、0≦h≦2、0≦i≦2の範囲であって、hとiが同時に0となることはなく、0<j≦2の範囲とし、かつアルコキシ基の合計置換度を表すh+i+jは0.1≦h+i+j≦2.5の範囲とする。好ましくは、0≦h≦1.8、0≦i≦1.8で、hとiの少なくとも一方は0.1以上、0.1≦j≦1.8、0.2≦h+i+j≦2.35の範囲であり、より好ましくは、0.1≦h≦1.8、0.1≦i≦1.8、0.1≦j≦1.8、0.5≦h+i+j≦2.35の範囲である。式(II)においても、h及びiがともに0を超える数であって、メトキシ基とエトキシ基の双方を含有することが好ましい。 On the other hand, in the second organopolysiloxane represented by the average composition formula (II), h and i representing the content of methoxy group and ethoxy group having high hydrolysis reactivity, and propoxy group having low hydrolysis reactivity J representing the content of an alkoxy group having 3 and / or 4 carbon atoms such as butoxy group can be appropriately set depending on the purpose of use and the desired degree of hydrolysis reactivity. Controlling the hydrolysis reactivity when used in combination with the first organopolysiloxane represented by the average composition formula (I) by reducing the decomposition reactivity, and as described above, in the hydrolysis reaction during the combination, For the purpose of the present invention to develop a so-called gradation effect that contributes to the hydrolysis reaction step by step without leaving only the second organopolysiloxane. , 0 ≦ h ≦ 2, 0 ≦ i ≦ 2, h and i are not simultaneously 0, and 0 + j ≦ 2, and h + i + j representing the total substitution degree of the alkoxy group is The range is 0.1 ≦ h + i + j ≦ 2.5. Preferably, 0 ≦ h ≦ 1.8 and 0 ≦ i ≦ 1.8, and at least one of h and i is 0.1 or more, 0.1 ≦ j ≦ 1.8, 0.2 ≦ h + i + j ≦ 2. 35, more preferably 0.1 ≦ h ≦ 1.8, 0.1 ≦ i ≦ 1.8, 0.1 ≦ j ≦ 1.8, 0.5 ≦ h + i + j ≦ 2.35. It is a range. Also in the formula (II), it is preferable that h and i are both greater than 0 and contain both a methoxy group and an ethoxy group.
また、式(I)における係数e及び式(II)における係数kは、ケイ素原子に対する水酸基の置換度、即ちシラノール基の含有率を表す数値であり、このシラノール基はシリル化反応や縮合反応に預かることができ、オルガノポリシロキサンに親水性を付与する効果があるが、オルガノポリシロキサンの保存安定性確保という観点からは、できるだけ少なくすることが好ましい。そこで、0≦e≦1及び0≦k≦1の範囲とする。好ましくは0≦e≦0.5及び0≦k≦0.5の範囲、より好ましくは0≦e≦0.2及び0≦k≦0.2の範囲である。 The coefficient e in the formula (I) and the coefficient k in the formula (II) are numerical values representing the degree of substitution of the hydroxyl group with respect to the silicon atom, that is, the content of the silanol group. It can be stored and has the effect of imparting hydrophilicity to the organopolysiloxane, but it is preferably as small as possible from the viewpoint of ensuring the storage stability of the organopolysiloxane. Therefore, the ranges are 0 ≦ e ≦ 1 and 0 ≦ k ≦ 1. The range is preferably 0 ≦ e ≦ 0.5 and 0 ≦ k ≦ 0.5, more preferably the range of 0 ≦ e ≦ 0.2 and 0 ≦ k ≦ 0.2.
式(I)における各係数の合計(a+b+c+d+e)、及び式(II)における各係数の合計(f+g+h+i+j+k)は、上記平均組成式(I)及び(II)で表されるオルガノポリシロキサンの縮合度を表す〔4−(a+b+c+d+e)〕/2及び〔4−(f+g+h+i+j+k)〕/2を決定する数値であり、2≦a+b+c+d+e≦3及び2≦f+g+h+i+j+k≦3の範囲とする。各オルガノポリシロキサンの重合度は、ケイ素原子2個のダイマーからケイ素原子数百個程度のポリマーまでの範囲とすることができるが、平均重合度が2の場合は製造したオルガノポリシロキサン中のモノマー含有量が多くなって、シリコーンアルコキシオリゴマー本来の使用目的が損なわれるし、平均重合度が大きすぎると高粘度品やペースト状又は固体状となって、取り扱いが困難になるため、平均重合度を3〜100の範囲とすることが好ましく、更には3〜50の範囲とすることがより好ましい。このような観点から、上記した(a+b+c+d+e)及び(f+g+h+i+j+k)に関しても、好ましくは2≦a+b+c+d+e≦2.67及び2≦f+g+h+i+j+k≦2.67の範囲、より好ましくは2<a+b+c+d+e≦2.67及び2<f+g+h+i+j+k≦2.67の範囲である。 The sum of the coefficients in formula (I) (a + b + c + d + e) and the sum of the coefficients in formula (II) (f + g + h + i + j + k) indicate the degree of condensation of the organopolysiloxanes represented by the above average composition formulas (I) and (II). [4- (a + b + c + d + e)] / 2 and [4- (f + g + h + i + j + k)] / 2 are expressed, and the ranges are 2 ≦ a + b + c + d + e ≦ 3 and 2 ≦ f + g + h + i + j + k ≦ 3. The degree of polymerization of each organopolysiloxane can range from a dimer of 2 silicon atoms to a polymer of about several hundred silicon atoms, but if the average degree of polymerization is 2, the monomer in the produced organopolysiloxane If the content increases, the intended purpose of the silicone alkoxy oligomer is impaired, and if the average degree of polymerization is too large, it becomes a high-viscosity product, paste or solid, making it difficult to handle. The range is preferably 3 to 100, and more preferably 3 to 50. From this point of view, the above (a + b + c + d + e) and (f + g + h + i + j + k) are also preferably in the range of 2 ≦ a + b + c + d + e ≦ 2.67 and 2 ≦ f + g + h + i + j + k ≦ 2.67, more preferably 2 <a + b + c + d + e ≦ 2.67 and 2 <F + g + h + i + j + k ≦ 2.67.
有機官能基とメトキシ基及び/又はエトキシ基とを一分子内に含有する第一のオルガノポリシロキサン、及び、有機官能基とメトキシ基及び/又はエトキシ基と炭素数3及び/又は4のアルコキシ基とを一分子内に含有する第二のオルガノポリシロキサンは、それぞれ前記平均組成式(I)及び(II)で表され、係数a〜e及び係数f〜kがそれぞれ上記範囲を満たす数であればよく、直鎖状、分岐状、環状のもの、及びこれらが組み合わさった構造を持っていてもよい。 First organopolysiloxane containing organic functional group and methoxy group and / or ethoxy group in one molecule, and organic functional group and methoxy group and / or ethoxy group and alkoxy group having 3 and / or 4 carbon atoms The second organopolysiloxane containing 1 in a molecule is represented by the average composition formulas (I) and (II), and the coefficients a to e and the coefficients f to k are numbers satisfying the above ranges, respectively. It may be linear, branched, cyclic, or a combination of these.
[オルガノポリシロキサンの製造方法]
次に、オルガノポリシロキサンの製造方法について説明する。前記平均組成式(I)で表され、有機官能基とメトキシ基及び/又はエトキシ基とを一分子内に含有する第一のオルガノポリシロキサンは、従来公知の各種処方によって得ることができる。例えば、上記した有機官能基とメトキシ基及び/又はエトキシ基を含有するシランカップリング剤を原料として、単独で部分加水分解・重縮合する方法や、その他のアルコキシシラン類及び/又はその部分加水分解物及び/又はその縮合物と部分共加水分解・重縮合する方法等を挙げることができる。かくして得られる第一のオルガノポリシロキサンは、多くの場合、液体である。[Method for producing organopolysiloxane]
Next, the manufacturing method of organopolysiloxane is demonstrated. The first organopolysiloxane represented by the average composition formula (I) and containing an organic functional group and a methoxy group and / or an ethoxy group in one molecule can be obtained by various conventionally known formulations. For example, the above-mentioned organic functional group and silane coupling agent containing a methoxy group and / or ethoxy group as a raw material, a method of partial hydrolysis / polycondensation alone, other alkoxysilanes and / or partial hydrolysis thereof And a method of partial cohydrolysis and polycondensation with the product and / or its condensate. The first organopolysiloxane thus obtained is often a liquid.
また、前記平均組成式(II)で表され、有機官能基とメトキシ基及び/又はエトキシ基と炭素原子数3及び/又は4のアルコキシ基とを一分子内に含有する第二のオルガノポリシロキサンも、従来公知の各種処方によって得ることができる。一般的な手段として、例えば次のような方法を挙げることができる。 The second organopolysiloxane represented by the above average composition formula (II) and containing an organic functional group, a methoxy group and / or an ethoxy group, and an alkoxy group having 3 and / or 4 carbon atoms in one molecule. Can also be obtained by various conventionally known formulations. Examples of general means include the following method.
(1)上記した有機官能基と炭素原子数が異なる複数種のアルコキシ基を含有するアルコキシシランを単独で部分加水分解・重縮合する方法、
(2)有機官能基を含有するアルコキシシラン及びそれとは炭素原子数が異なるアルコキシ基を含有し、有機官能基を含有しないアルコキシシランを、部分共加水分解・重縮合する方法、
(3)同様の部分加水分解・重縮合操作によって得られた有機官能基とメトキシ基及び/又はエトキシ基とを含有するオルガノポリシロキサンに、炭素原子数3及び/又は4のアルコールとのエステル交換反応により、炭素原子数3及び/又は4のアルコキシ基を導入する方法等。(1) A method of partially hydrolyzing and polycondensing an alkoxysilane containing a plurality of types of alkoxy groups having different carbon atoms from the organic functional group described above,
(2) A method of partially cohydrolyzing and polycondensing an alkoxysilane containing an organic functional group and an alkoxysilane containing an alkoxy group having a different number of carbon atoms from that, and not containing an organic functional group,
(3) Transesterification of an organopolysiloxane containing an organic functional group and a methoxy group and / or ethoxy group obtained by the same partial hydrolysis / polycondensation operation with an alcohol having 3 and / or 4 carbon atoms A method of introducing an alkoxy group having 3 and / or 4 carbon atoms by reaction.
本発明においては、前記平均組成式(II)で表されるオルガノポリシロキサンの構造設計の自由度、原料入手の容易性といった観点から、上記(2)の処方に基づき、少なくとも一種の下記一般式(III)で表される有機官能基含有アルコキシシラン及び/又はその部分加水分解物と、少なくとも一種の下記一般式(IV)で表されるアルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物との混合物を、部分共加水分解及び重縮合させて、オルガノポリシロキサンとすることが好ましい。 In the present invention, from the viewpoints of the degree of freedom in the structural design of the organopolysiloxane represented by the average composition formula (II) and the availability of raw materials, at least one of the following general formulas An organofunctional group-containing alkoxysilane represented by (III) and / or a partial hydrolyzate thereof, and at least one alkoxy group-containing silane compound represented by the following general formula (IV) and / or a partial hydrolyzate thereof: Preferably, the mixture with the condensate thereof is partially cohydrolyzed and polycondensed to form an organopolysiloxane.
YR1 mSi(OCH3)n(OC2H5)3-m-n …(III)
R1 pSi(OCH3)q(OC2H5)r(OR2)4-p-q-r …(IV)YR 1 m Si (OCH 3 ) n (OC 2 H 5 ) 3-mn (III)
R 1 p Si (OCH 3 ) q (OC 2 H 5 ) r (OR 2 ) 4-pqr (IV)
ここで、Y、R1及びR2は、それぞれ前記式(II)におけるのと同じ意味を表し、mは0〜2の整数、nは0〜3の整数であるが、m+nは3以下であり、pは0〜2の整数、qは0〜4の整数、rは0〜4の整数であるが、p+q+rは4以下であり、但し、一般式(IV)のアルコキシ基含有シラン化合物として、OR2基を有する成分を少なくとも一種用いるものとする。Here, Y, R 1 and R 2 each represent the same meaning as in formula (II), m is an integer from 0 to 2, n is an integer from 0 to 3, but m + n is 3 or less. Yes, p is an integer of 0-2, q is an integer of 0-4, r is an integer of 0-4, but p + q + r is 4 or less, provided that the alkoxy group-containing silane compound of the general formula (IV) , At least one component having an OR 2 group is used.
また変形法として、以下のような方法でオルガノポリシロキサンとすることもできる。即ち、まず、上記一般式(III)で表される有機官能基含有アルコキシシランと、上記一般式(IV)で表される少なくとも一種のアルコキシ基含有シラン化合物とを予め部分共加水分解させる。次にこの部分共加水分解生成物を、上記一般式(IV)で表され、先の部分共加水分解に用いたのとは異なるアルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物を混合し、部分加水分解及び重縮合させて、オルガノポリシロキサンを得る。この方法でも、上記一般式(IV)で表されるアルコキシ基含有シラン化合物として、OR2基を有する成分を少なくとも一種用いるものとする。As a modification method, an organopolysiloxane can be obtained by the following method. That is, first, the organic functional group-containing alkoxysilane represented by the general formula (III) and at least one alkoxy group-containing silane compound represented by the general formula (IV) are partially cohydrolyzed in advance. Next, this partial cohydrolysis product is represented by the above general formula (IV), and is different from the alkoxy group-containing silane compound and / or partial hydrolyzate thereof and / or different from that used in the partial cohydrolysis. The condensate is mixed, partially hydrolyzed and polycondensed to obtain organopolysiloxane. Also in this method, at least one component having an OR 2 group is used as the alkoxy group-containing silane compound represented by the general formula (IV).
上記一般式(III)で表される有機官能基含有アルコキシシランの具体例を挙げると、有機官能基として、メルカプトメチル基、3−メルカプトプロピル基、6−メルカプトヘキシル基、10−メルカプトデシル基、2−(4−メルカプトメチルフェニル)エチル基、グリシドキシメチル基、3−グリシドキシプロピル基、5,6−エポキシヘキシル基、9,10−エポキシデシル基、2−(3,4−エポキシシクロヘキシル)エチル基、2−(3,4−エポキシ−4−メチルシクロヘキシル)プロピル基、アクリロイロキシメチル基、3−アクリロイロキシプロピル基、6−アクリロイロキシヘキシル基、10−アクリロイロキシデシル基、メタクリロイロキシメチル基、3−メタクリロイロキシプロピル基、6−メタクリロイロキシヘキシル基、10−メタクリロイロキシデシル基、ビニル基、アリル基、5−ヘキセニル基、9−デセニル基、3−ビニルオキシプロピル基、p−スチリル基、シクロヘキセニルエチル基、クロロメチル基、3−クロロプロピル基、6−クロロヘキシル基、10−クロロデシル基、ブロモメチル基、3−ブロモプロピル基、アミノメチル基、3−アミノプロピル基、6−アミノプロピル基、N−メチル−3−アミノプロピル基、N,N−ジメチル−3−アミノプロピル基、N−フェニル−3−アミノプロピル基、N−(2−アミノエチル)−3−アミノプロピル基、N−(6−アミノヘキシル)−3−アミノプロピル基、N−(ビニルベンジル)−2−アミノエチル−3−アミノプロピル基等を有するトリメトキシシラン化合物、トリエトキシシラン化合物、メチルジメトキシシラン化合物、メチルジエトキシシラン化合物、エチルジメトキシシラン化合物、エチルジエトキシシラン化合物、プロピルジメトキシシラン化合物、プロピルジエトキシシラン化合物、ジメチルメトキシシラン化合物、ジメチルジエトキシシラン化合物、エトキシジメトキシシラン化合物、メトキシジエトキシシラン化合物等が例示される。 Specific examples of the organic functional group-containing alkoxysilane represented by the general formula (III) include, as the organic functional group, mercaptomethyl group, 3-mercaptopropyl group, 6-mercaptohexyl group, 10-mercaptodecyl group, 2- (4-mercaptomethylphenyl) ethyl group, glycidoxymethyl group, 3-glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxy (Cyclohexyl) ethyl group, 2- (3,4-epoxy-4-methylcyclohexyl) propyl group, acryloyloxymethyl group, 3-acryloyloxypropyl group, 6-acryloyloxyhexyl group, 10-acryloyloxydecyl Group, methacryloyloxymethyl group, 3-methacryloyloxypropyl group, 6-methacryloyloxyhe Sil group, 10-methacryloyloxydecyl group, vinyl group, allyl group, 5-hexenyl group, 9-decenyl group, 3-vinyloxypropyl group, p-styryl group, cyclohexenylethyl group, chloromethyl group, 3- Chloropropyl group, 6-chlorohexyl group, 10-chlorodecyl group, bromomethyl group, 3-bromopropyl group, aminomethyl group, 3-aminopropyl group, 6-aminopropyl group, N-methyl-3-aminopropyl group, N, N-dimethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (6-aminohexyl) -3-aminopropyl Group, trimethoxysilane compound having N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl group, etc., triethoxy Run compound, methyldimethoxysilane compound, methyldiethoxysilane compound, ethyldimethoxysilane compound, ethyldiethoxysilane compound, propyldimethoxysilane compound, propyldiethoxysilane compound, dimethylmethoxysilane compound, dimethyldiethoxysilane compound, ethoxydimethoxysilane Examples thereof include a compound and a methoxydiethoxysilane compound.
次に、上記一般式(IV)で表されるアルコキシ基含有シラン化合物の具体例を挙げると、p=0のアルコキシシランとして、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、テトライソブトキシシラン等が、p=1のアルコキシシランとして、メチル基、エチル基、プロピル基、イソプロピル基、1−メチルプロピル基、ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、オクチル基、フェニル基、トリル基、ベンジル基、フェニルエチル基等を有するトリメトキシシラン、トリエトキシシラン、トリプロポキシシラン、トリイソプロポキシシラン、トリブトキシシラン、トリイソブトキシシラン等が、p=2のアルコキシシランとして、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジプロポキシシラン、ジメチルジブトキシシラン、メチルエチルジメトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等が、それぞれ例示される。 Next, specific examples of the alkoxy group-containing silane compound represented by the general formula (IV) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, p = 0 alkoxysilane, Tetrabutoxysilane, tetraisobutoxysilane, etc. are p = 1 alkoxysilanes such as methyl, ethyl, propyl, isopropyl, 1-methylpropyl, butyl, isobutyl, tert-butyl, hexyl , Octyl group, phenyl group, tolyl group, benzyl group, phenylethyl group, etc., trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisobutoxysilane, etc., p = 2 Dimethyl as an alkoxysilane Dimethoxysilane, dimethyl diethoxy silane, dimethyl dipropoxy silane, dimethyl dibutoxy silane, methyl ethyl dimethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, etc., are respectively illustrated.
なお、原料の入手し易さやコスト面からは、上記一般式(III)におけるmが0で、nが3又は0のもの、即ち、有機官能基を含有するトリメトキシシラン、トリエトキシシラン及び/又はその部分加水分解物と、上記一般式(IV)におけるR1がメチル基で、pが1及び/又は0のもの、即ち、メチルトリアルコキシシラン、テトラアルコキシシラン及び/又はその部分加水分解物及び/又はその縮合物とを使用することが好ましく、更には、上記一般式(IV)におけるq及びrがともに0であるアルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物を必須成分とすることがより好ましい。From the viewpoint of easy availability of raw materials and cost, m in the general formula (III) is 0 and n is 3 or 0, that is, trimethoxysilane, triethoxysilane and / or organic functional group-containing ones. Or a partial hydrolyzate thereof, and R 1 in the above general formula (IV) is a methyl group and p is 1 and / or 0, that is, methyltrialkoxysilane, tetraalkoxysilane and / or a partial hydrolyzate thereof. And / or a condensate thereof, and further, an alkoxy group-containing silane compound in which q and r in the general formula (IV) are both 0 and / or a partial hydrolyzate thereof and / or a condensation thereof. More preferably, the product is an essential component.
とりわけ、上記一般式(III)で表される有機官能基含有アルコキシシランとして3−メルカプトプロピルトリメトシシシラン、3−メルカプトプロピルトリエトキシシラン、3−グリシドキシプロピルトリメトシシシラン、3−グリシドキシプロピルトリエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリエトキシシランから選択される少なくとも一種を使用し、上記一般式(IV)で表されるアルコキシ基含有シラン化合物としてメチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリイソプロポキシシラン、メチルトリブトキシシラン、メチルトリイソブトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、テトライソブトキシシランから選択される少なくとも一種(但し、プロポキシ基、イソプロポキシ基、ブトキシ基又はイソブトキシ基を有する少なくとも一種のシラン化合物を必須成分とする)を使用することが、特に好ましい。 In particular, as the organofunctional group-containing alkoxysilane represented by the general formula (III), 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy At least one selected from propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the above general formula (IV) As the alkoxy group-containing silane compound represented by the formula, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisobutoxysilane, tetramethoxysilane, At least one selected from laethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane (provided that at least one silane compound having a propoxy group, isopropoxy group, butoxy group or isobutoxy group is used) It is particularly preferable to use an essential component).
これらの有機官能基含有アルコキシシラン及び/又はその部分加水分解物と、アルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物は、それぞれ複数種を併用することができるが、上記一般式(III)で表される有機官能基含有アルコキシシラン及び/又はその部分加水分解物を二種以上使用する場合、同一の有機官能基を有するものとすることが好ましい。また、オルガノポリシロキサン中のメトキシ基、エトキシ基、炭素原子数3及び/又は4のアルコキシ基の比率を任意に設計するためには、上記一般式(IV)で表されるアルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物として、アルコキシ基の種類が異なる二種以上を併用することが好ましい。 These organic functional group-containing alkoxysilanes and / or partial hydrolysates thereof, and alkoxy group-containing silane compounds and / or partial hydrolysates thereof and / or condensates thereof can each be used in combination of a plurality of types. When using 2 or more types of the organic functional group containing alkoxysilane represented by the said general formula (III) and / or its partial hydrolyzate, it is preferable to have the same organic functional group. Further, in order to arbitrarily design the ratio of methoxy group, ethoxy group, alkoxy group having 3 and / or 4 carbon atoms in organopolysiloxane, an alkoxy group-containing silane compound represented by the above general formula (IV) And as the partial hydrolyzate and / or condensate thereof, it is preferable to use two or more different types of alkoxy groups in combination.
上記した一般式(III)で表される有機官能基含有アルコキシシラン及び/又はその部分加水分解物と、一般式(IV)で表されるアルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物との配合比率は特に限定されないが、前者の配合比率が少なすぎると、得られるオルガノポリシロキサンの使用時に本来あるべき有機官能基の反応性に基づく特性が十分に発揮されず、少なくとも一分子中に一個の有機官能基を有するものとする必要があることから、両成分のSi原子換算モル比で1:99〜99:1の範囲とすることが好ましく、更には10:90〜80:20の範囲とすることがより好ましい。 The organic functional group-containing alkoxysilane represented by the general formula (III) and / or a partial hydrolyzate thereof, the alkoxy group-containing silane compound represented by the general formula (IV) and / or a partial hydrolyzate thereof, and Although the blending ratio with the condensate thereof is not particularly limited, if the former blending ratio is too small, the characteristics based on the reactivity of the organic functional group that should be originally used when the obtained organopolysiloxane is not sufficiently exhibited. Since it is necessary to have at least one organic functional group in one molecule, the molar ratio of both components is preferably in the range of 1:99 to 99: 1, and more preferably 10: More preferably, it is in the range of 90-80: 20.
また、これら各種原料の配合順序や混合方法、及び部分共加水分解、重縮合を行う方法も特に限定されず、従来公知の方法に基づき、例えば、上記した有機官能基含有アルコキシシラン及び/又はその部分加水分解物と、アルコキシ基含有シラン化合物及び/又はその部分加水分解物及び/又はその縮合物との混合物中に、加水分解・縮合反応触媒の存在下、水を加えて部分共加水分解及び重縮合反応を行うことによって得ることができるし、この際、必要に応じて適当な有機溶媒を使用することも可能である。 Further, the blending order and mixing method of these various raw materials, and the method of performing partial cohydrolysis and polycondensation are not particularly limited, and are based on conventionally known methods, for example, the above-described organic functional group-containing alkoxysilane and / or its In a mixture of the partial hydrolyzate and the alkoxy group-containing silane compound and / or the partial hydrolyzate and / or the condensate thereof, water is added in the presence of a hydrolysis / condensation reaction catalyst to perform partial cohydrolysis and It can be obtained by conducting a polycondensation reaction, and at this time, an appropriate organic solvent can be used as necessary.
この反応における加水分解・縮合反応触媒としては、従来から公知の種々のものを使用することができる。具体例としては、酢酸、トリフロロ酢酸、酪酸、シュウ酸、マレイン酸、クエン酸、メタンスルホン酸、p−トルエンスルホン酸、トリフロロメタンスルホン酸等の有機酸類、塩酸、硝酸、リン酸、硫酸等の無機酸類、水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、酢酸ナトリウム、酢酸カリウム、アンモニア、水酸化アンモニウム、トリエチルアミン等の塩基性化合物類、フッ化カリウム、フッ化アンモニウム等の含フッ素化合物類、テトライソプロピルチタネート、テトラブチルチタネート、ジオクチル錫ジラウレート、アルミニウムキレート類等の有機金属化合物類等を挙げることができる。上記触媒は単独で使用してもよく、又は複数種を併用してもよいが、触媒の使用量は、原料全体の中に存在するSi原子モル数に対して、0.0001〜10モル%の範囲とすることが好ましく、更には0.001〜3モル%の範囲とすることがより好ましい。 As the hydrolysis / condensation reaction catalyst in this reaction, various conventionally known catalysts can be used. Specific examples include organic acids such as acetic acid, trifluoroacetic acid, butyric acid, oxalic acid, maleic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, etc. Inorganic acids, basic compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, potassium acetate, ammonia, ammonium hydroxide, triethylamine, and fluorine-containing compounds such as potassium fluoride and ammonium fluoride Examples thereof include organometallic compounds such as compounds, tetraisopropyl titanate, tetrabutyl titanate, dioctyl tin dilaurate, and aluminum chelates. The above catalyst may be used alone or in combination of two or more kinds, but the amount of the catalyst used is 0.0001 to 10 mol% with respect to the number of moles of Si atoms present in the whole raw material. Preferably, it is more preferable to set it as the range of 0.001-3 mol%.
前述のとおり、本発明に用いる各オルガノポリシロキサンの重合度は、ケイ素原子2個のダイマーからケイ素原子数百個程度のポリマーまでであればよいが、部分加水分解、重縮合に使用する水の量によって平均重合度が決まる。水を過剰に添加するとその分のアルコキシ基が加水分解され、分岐構造の多いレジン体となって、目的とするシリコーンアルコキシオリゴマーが得られなくなるため、加水分解に用いる水の量は厳密に決定する必要がある。例えば、使用するアルコキシシラン原料が全てケイ素原子1個のモノマーである場合、平均重合度Zのオルガノポリシロキサンを調製するためには、Zモルのアルコキシシラン原料に対して(Z−1)モルの水を使用して部分加水分解、重縮合を行えばよい。 As described above, the degree of polymerization of each organopolysiloxane used in the present invention may be from a dimer having 2 silicon atoms to a polymer having about several hundred silicon atoms, but water used for partial hydrolysis and polycondensation. The average degree of polymerization is determined by the amount. If water is added excessively, the alkoxy group is hydrolyzed to form a resin having a lot of branched structures, and the desired silicone alkoxy oligomer cannot be obtained. Therefore, the amount of water used for hydrolysis is strictly determined. There is a need. For example, when the alkoxysilane raw material used is a monomer having one silicon atom, in order to prepare an organopolysiloxane having an average polymerization degree of Z, (Z-1) What is necessary is just to perform partial hydrolysis and polycondensation using water.
この際、必要に応じてアルコール類、エーテル類、エステル類、ケトン類等の有機溶媒を使用してもよい。これらの有機溶媒の具体例としては、メタノール、エタノール、n−プロピルアルコール、イソプロピルアルコール、プロピレングリコールモノメチルエーテル等のアルコール類、ジエチルエーテル、ジプロピルエーテル等のエーテル類、酢酸メチル、酢酸エチル、アセト酢酸エチル等のエステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類等を挙げることができる。また、上記の如き極性溶媒とともに、ヘキサン、トルエン、キシレン等の非極性溶媒を併用してもよい。特に、メタノール、エタノール、イソプロピルアルコール等のアルコール類を使用することが好ましい。 At this time, an organic solvent such as alcohols, ethers, esters, and ketones may be used as necessary. Specific examples of these organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and propylene glycol monomethyl ether, ethers such as diethyl ether and dipropyl ether, methyl acetate, ethyl acetate and acetoacetic acid. Examples include esters such as ethyl, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Moreover, you may use together nonpolar solvents, such as hexane, toluene, and xylene, with the above polar solvents. In particular, it is preferable to use alcohols such as methanol, ethanol and isopropyl alcohol.
有機溶媒の使用量は、原料となるアルコキシシラン及び/又はその部分加水分解物及び/又はその縮合物の合計100質量部に対して、0〜1000質量部の範囲とすればよいが、使用量が少ないと加水分解開始時の反応系が均一とならない場合があり、多すぎてもそれ以上の添加効果がみられないばかりか、ポットイールドが低下して経済的に不利となるため、10〜500質量部の範囲とすることが好ましく、更には20〜200質量部の範囲とすることがより好ましい。 The amount of the organic solvent used may be in the range of 0 to 1000 parts by mass with respect to 100 parts by mass in total of the alkoxysilane and / or its partial hydrolyzate and / or its condensate as raw materials. If the amount is too small, the reaction system at the start of hydrolysis may not be uniform, and if it is too much, not only the addition effect is seen, but also the pot yield is lowered and economically disadvantageous. The range is preferably 500 parts by mass, and more preferably 20 to 200 parts by mass.
部分(共)加水分解及び重縮合反応における実際の操作としては、アルコキシシラン原料、触媒及び有機溶媒からなる混合系に、所定量の水又は水/有機溶媒の混合液を滴下するか、アルコキシシラン原料及び有機溶媒からなる混合系に、所定量の水/触媒の混合溶液又は水/触媒/有機溶媒の混合溶液を滴下することが好ましい。この際、加水分解反応性の高いメトキシ基やエトキシ基を有するアルコキシシラン原料と、加水分解反応性の低いプロポキシ基やブトキシ基等の炭素原子数3及び/又は4のアルコキシ基を有するアルコキシシラン原料とを予め別々に部分加水分解した後、両成分を混合して、場合によって更に部分共加水分解を行ってから、重縮合反応を行うことも可能である。各反応は0〜150℃の温度範囲で実施すればよいが、一般的には、室温より低い温度では反応の進行が遅くなるため実用的でなく、また高温すぎる場合も、メルカプト基、エポキシ基等の熱分解やアクリロイロキシ基の熱重合等、有機官能基への悪影響が発生するため、20〜130℃の温度範囲とすることが好ましい。反応後、使用した触媒の中和、吸着、濾過等による除去操作や、使用した有機溶媒と副生したアルコール、低沸点物の留去等による精製工程を行い、目的とするオルガノポリシロキサンを得ることができる。かくして得られる第二のオルガノポリシロキサンは、多くの場合、液体である。 As an actual operation in the partial (co) hydrolysis and polycondensation reaction, a predetermined amount of water or a mixture of water / organic solvent is dropped into a mixed system composed of an alkoxysilane raw material, a catalyst and an organic solvent, or alkoxysilane. It is preferable to drop a predetermined amount of a mixed solution of water / catalyst or a mixed solution of water / catalyst / organic solvent into a mixed system composed of a raw material and an organic solvent. In this case, an alkoxysilane raw material having a methoxy group or an ethoxy group having a high hydrolysis reactivity and an alkoxysilane raw material having an alkoxy group having 3 and / or 4 carbon atoms such as a propoxy group or a butoxy group having a low hydrolysis reactivity It is also possible to carry out the polycondensation reaction after separately hydrolyzing and separately mixing the two components and optionally further carrying out partial cohydrolysis. Each reaction may be carried out in a temperature range of 0 to 150 ° C., but in general, the reaction proceeds slowly at a temperature lower than room temperature, which is not practical, and even when the temperature is too high, a mercapto group, an epoxy group It is preferable that the temperature be in the range of 20 to 130 ° C., since adverse effects on the organic functional group such as thermal decomposition such as thermal polymerization and thermal polymerization of acryloyloxy groups occur. After the reaction, the removal of the used catalyst by neutralization, adsorption, filtration, etc., and the purification process by distilling off the used organic solvent and by-produced alcohol and low-boiling substances, etc. are performed to obtain the desired organopolysiloxane. be able to. The second organopolysiloxane thus obtained is often a liquid.
[粘着剤組成物]
本発明においては、上記で説明したようなアクリル樹脂に、同じく上記で説明したような架橋剤、第一のオルガノポリシロキサン及び第二のオルガノポリシロキサンを配合して、粘着剤組成物とする。架橋剤は、粘着剤組成物を構成するアクリル樹脂100質量部(2種類以上用いる場合はその合計量)に対して、通常0.1〜10質量部程度、好ましくは0.1〜7質量部程度、更に好ましくは0.2〜3質量部程度の割合で配合される。アクリル樹脂100質量部に対する架橋剤の量が0.1質量部以上であると、粘着剤層の耐久性が向上する傾向にあることから好ましい。また、その量が10質量部以下であると、粘着剤付き光学フィルムを液晶表示装置に適用したときのいわゆる白抜けが目立たなくなることから好ましい。[Adhesive composition]
In the present invention, the acrylic resin as described above is blended with the crosslinking agent as described above, the first organopolysiloxane, and the second organopolysiloxane to form an adhesive composition. The crosslinking agent is usually about 0.1 to 10 parts by mass, preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the acrylic resin constituting the pressure-sensitive adhesive composition (when two or more types are used, the total amount) More preferably, it is blended at a ratio of about 0.2 to 3 parts by mass. The amount of the crosslinking agent with respect to 100 parts by mass of the acrylic resin is preferably 0.1 parts by mass or more because the durability of the pressure-sensitive adhesive layer tends to be improved. Moreover, when the amount is 10 parts by mass or less, so-called white spots are not noticeable when the optical film with an adhesive is applied to a liquid crystal display device.
第一のオルガノポリシロキサン及び第二のオルガノポリシロキサンは、粘着剤組成物を構成するアクリル樹脂100質量部(2種類以上用いる場合は、その合計量)に対し、オルガノポリシロキサンの合計量として、通常0.0001〜10質量部程度、好ましくは0.01〜5質量部、更に好ましくは0.1〜1質量部の割合で使用される。アクリル樹脂100質量部に対するオルガノポリシロキサンの配合量が合計で0.0001質量部以上であると、粘着剤層とガラス基板との密着性が向上することから好ましい。また、その量が10質量部以下であると、粘着剤層からオルガノポリシロキサン混合物がブリードアウトすることが抑制される傾向にあることから好ましい。 The first organopolysiloxane and the second organopolysiloxane are as a total amount of the organopolysiloxane with respect to 100 parts by mass of the acrylic resin constituting the pressure-sensitive adhesive composition (when two or more types are used, the total amount). Usually, about 0.0001-10 mass parts, Preferably it is 0.01-5 mass parts, More preferably, it is used in the ratio of 0.1-1 mass part. It is preferable that the total amount of the organopolysiloxane blended with respect to 100 parts by mass of the acrylic resin is 0.0001 parts by mass or more because adhesion between the pressure-sensitive adhesive layer and the glass substrate is improved. Moreover, when the amount is 10 parts by mass or less, it is preferable that the organopolysiloxane mixture tends to be suppressed from bleeding out from the pressure-sensitive adhesive layer.
第一のオルガノポリシロキサン及び第二のオルガノポリシロキサンの混合比率については特に限定されず、使用目的に応じて適宜選択することができるが、両者が混合された状態で加水分解反応性を制御するという観点からは、前者/後者の混合比率を質量比で10/90〜90/10の範囲とすることが好ましく、更には質量比で20/80〜80/20の範囲とすることがより好ましい。第一のオルガノポリシロキサン及び第二のオルガノポリシロキサンは、予め混合してから、アクリル樹脂及び架橋剤に配合してもよいし、別々に用意されたものをアクリル樹脂及び架橋剤に配合してもよい。予め混合する場合であっても、また粘着剤組成物調製時に配合する場合であっても、必要成分を単純混合すればよく、その混合方法や混合時の温度条件等は特に限定されない。 The mixing ratio of the first organopolysiloxane and the second organopolysiloxane is not particularly limited and can be appropriately selected depending on the purpose of use, but the hydrolysis reactivity is controlled in a state where both are mixed. From the viewpoint, the former / latter mixing ratio is preferably in the range of 10/90 to 90/10 by mass ratio, and more preferably in the range of 20/80 to 80/20 by mass ratio. . The first organopolysiloxane and the second organopolysiloxane may be mixed in advance and then blended into the acrylic resin and the crosslinking agent, or those prepared separately may be blended into the acrylic resin and the crosslinking agent. Also good. Even when mixing in advance or when blending at the time of preparing the pressure-sensitive adhesive composition, the necessary components may be simply mixed, and the mixing method and temperature conditions during mixing are not particularly limited.
以上説明した粘着剤組成物には、更に、架橋触媒、耐候安定剤、タッキファイヤー、可塑剤、軟化剤、染料、顔料、無機フィラー等を配合してもよい。なかでも、粘着剤に架橋剤とともに架橋触媒を配合すると、粘着剤層を短時間の熟成で調製することができ、得られる粘着剤付き光学フィルムを液晶セルガラスに貼り合わせたときに、粘着剤層と光学フィルムとの間に浮きや剥れが発生したり、粘着剤層内で発泡が起こったりすることを抑制することができ、しかもリワーク性も一層良好になることがある。架橋触媒としては例えば、ヘキサメチレンジアミン、エチレンジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、トリメチレンジアミン、ポリアミノ樹脂、メラミン樹脂の如きアミン系化合物等を挙げることができる。粘着剤に架橋触媒としてアミン系化合物を配合する場合、架橋剤としてはイソシアネート系化合物が好適である。 The pressure-sensitive adhesive composition described above may further contain a crosslinking catalyst, a weather stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and the like. Among them, when a crosslinking catalyst is blended with a crosslinking agent in the pressure-sensitive adhesive, the pressure-sensitive adhesive layer can be prepared by aging in a short time, and when the obtained optical film with pressure-sensitive adhesive is bonded to a liquid crystal cell glass, the pressure-sensitive adhesive Occurrence of floating or peeling between the layer and the optical film or foaming in the pressure-sensitive adhesive layer can be suppressed, and reworkability can be further improved. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin. When an amine compound is added to the adhesive as a crosslinking catalyst, an isocyanate compound is suitable as the crosslinking agent.
粘着剤組成物は通常、上記のような各成分を有機溶媒に溶解した状態で調製される。このために用いる有機溶媒は、上記の各成分を溶解するものであればよく、例えば、トルエンやキシレンの如き芳香族炭化水素類、酢酸エチルや酢酸ブチルの如きエステル類、アセトンやメチルエチルケトン、メチルイソブチルケトンの如きケトン類等が用いられる。 The pressure-sensitive adhesive composition is usually prepared in a state where the above components are dissolved in an organic solvent. The organic solvent used for this purpose is not limited as long as it dissolves each of the above-mentioned components. For example, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones are used.
[粘着剤付き光学フィルム]
本発明の粘着剤付き光学フィルムは、光学フィルムの少なくとも一方の面に、以上のような粘着剤組成物から形成される粘着剤層を設けたものである。ここで用いる光学フィルムとは、光学特性を有するフィルムであり、例えば、偏光フィルム、位相差フィルム等が挙げられる。[Optical film with adhesive]
The optical film with a pressure-sensitive adhesive of the present invention is obtained by providing a pressure-sensitive adhesive layer formed of the above pressure-sensitive adhesive composition on at least one surface of an optical film. The optical film used here is a film having optical characteristics, and examples thereof include a polarizing film and a retardation film.
偏光フィルムとは、自然光等の入射光に対して、偏光を出射する機能を持つ光学フィルムである。偏光フィルムには、ある方向の振動面を有する直線偏光を吸収し、それと直交する振動面を有する直線偏光を透過する性質を有する直線偏光フィルム、ある方向の振動面を有する直線偏光を反射し、それと直交する振動面を有する直線偏光を透過する性質を有する偏光分離フィルム、偏光フィルムと後述する位相差フィルムを積層した楕円偏光フィルム等がある。偏光フィルム、特に直線偏光フィルム(偏光子とか、偏光子フィルムとか呼ばれることもある)の好適な具体例として、一軸延伸されたポリビニルアルコール系樹脂フィルムにヨウ素や二色性染料等の二色性色素が吸着配向されているものが挙げられる。 A polarizing film is an optical film having a function of emitting polarized light with respect to incident light such as natural light. The polarizing film absorbs linearly polarized light having a vibration surface in a certain direction and reflects linearly polarized film having a property of transmitting linearly polarized light having a vibration surface orthogonal to the vibration surface, and reflects linearly polarized light having a vibration surface in a certain direction, There are a polarizing separation film having a property of transmitting linearly polarized light having a vibration plane orthogonal to the polarizing film, an elliptically polarizing film in which a polarizing film and a retardation film described later are laminated. As a suitable specific example of a polarizing film, particularly a linear polarizing film (sometimes called a polarizer or a polarizer film), a dichroic dye such as iodine or a dichroic dye is added to a uniaxially stretched polyvinyl alcohol resin film. Are adsorbed and oriented.
位相差フィルムとは、光学異方性を示す光学フィルムであって、例えば、ポリビニルアルコール、ポリカーボネート、ポリエステル、ポリアリレート、ポリイミド、ポリオレフィン、環状ポリオレフィン、ポリスチレン、ポリサルホン、ポリエーテルサルホン、ポリビニリデンフルオライド/ポリメチルメタクリレート、液晶ポリエステル、アセチルセルロース、エチレン−酢酸ビニル共重合体ケン化物、ポリ塩化ビニル等からなる高分子フィルムを1.01〜6倍程度に延伸することにより得られる延伸フィルム等が挙げられる。なかでも、ポリカーボネートフィルムや環状ポリオレフィン系フィルムを一軸延伸又は二軸延伸した高分子フィルムが好ましい。一軸性位相差フィルム、広視野角位相差フィルム、低光弾性率位相差フィルム等と称されるものがあるが、いずれに対しても適用可能である。 The retardation film is an optical film exhibiting optical anisotropy, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin, polystyrene, polysulfone, polyethersulfone, polyvinylidene fluoride. / Stretched film obtained by stretching a polymer film composed of polymethyl methacrylate, liquid crystal polyester, acetyl cellulose, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, etc. to about 1.01 to 6 times It is done. Among these, a polymer film obtained by uniaxially stretching or biaxially stretching a polycarbonate film or a cyclic polyolefin film is preferable. Although there exist what is called a uniaxial phase difference film, a wide viewing angle phase difference film, a low photoelasticity phase difference film, etc., it is applicable to any of them.
また、液晶性化合物の塗布・配向によって光学異方性を発現させたフィルムや、無機層状化合物の塗布によって光学異方性を発現させたフィルムも、位相差フィルムとして用いることができる。このような位相差フィルムには、温度補償型位相差フィルムと称されるもの、また、新日本石油(株)から“LCフィルム”の商品名で販売されている、棒状液晶がねじれ配向したフィルム、同じく新日本石油(株)から“NHフィルム”の商品名で販売されている棒状液晶が傾斜配向したフィルム、富士フイルム(株)から“WVフィルム”の商品名で販売されている円盤状液晶が傾斜配向したフィルム、住友化学(株)から“VACフィルム”の商品名で販売されている完全二軸配向型のフィルム、同じく住友化学(株)から“new VAC フィルム”の商品名で販売されている二軸配向型のフィルム等がある。 Moreover, the film which expressed optical anisotropy by application | coating and orientation of a liquid crystalline compound, and the film which expressed optical anisotropy by application | coating of an inorganic layered compound can also be used as retardation film. Such retardation films include what are called temperature-compensated retardation films, and films with a twisted orientation of rod-like liquid crystals sold under the trade name “LC film” by Nippon Oil Corporation. Also, a film with a tilted orientation of a rod-shaped liquid crystal sold under the trade name “NH film” by Shin Nippon Oil Co., Ltd., and a disk-shaped liquid crystal sold under the trade name “WV film” by FUJIFILM Corporation. Is a film with a tilt orientation, a fully biaxially oriented film sold under the trade name “VAC film” by Sumitomo Chemical Co., Ltd., and also sold under the product name “new VAC film” by Sumitomo Chemical Co., Ltd. A biaxially oriented film.
更に、これら光学フィルムに保護フィルムが貼着されているものも、光学フィルムとして用いることができる。保護フィルムとしては、透明な樹脂フィルムが用いられ、その透明樹脂としては、例えば、トリアセチルセルロースやジアセチルセルロースに代表されるアセチルセルロース系樹脂、ノルボルネン系樹脂に代表される非晶性環状ポリオレフィン系樹脂、ポリメチルメタクリレートに代表されるメタクリル樹脂、ポリエステル樹脂、ポリオレフィン系樹脂、ポリカーボネート樹脂、ポリエーテルエーテルケトン樹脂、ポリスルホン樹脂等が挙げられる。保護フィルムを構成する樹脂には、サリチル酸エステル系化合物、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、トリアジン系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物等の紫外線吸収剤が配合されていてもよい。保護フィルムとしては、トリアセチルセルロースフィルム等のアセチルセルロース系樹脂フィルムや、ノルボルネン系樹脂フィルム等の非晶性環状ポリオレフィン系樹脂フィルムが好適に用いられる。非晶性環状ポリオレフィン系樹脂フィルムの市販品としては、例えば、JSR(株)から販売されている“アートンフィルム”、(株)オプテスから販売されている“ゼオノアフィルム”等(いずれも商品名)がある。また、前述の位相差フィルムを直接保護フィルムとして用いることもできる。 Furthermore, those in which a protective film is attached to these optical films can also be used as the optical film. As the protective film, a transparent resin film is used. As the transparent resin, for example, an acetylcellulose-based resin typified by triacetylcellulose or diacetylcellulose, or an amorphous cyclic polyolefin-based resin typified by norbornene-based resin is used. And methacrylic resin represented by polymethyl methacrylate, polyester resin, polyolefin resin, polycarbonate resin, polyether ether ketone resin, polysulfone resin and the like. The resin constituting the protective film may contain an ultraviolet absorber such as a salicylic acid ester compound, a benzophenone compound, a benzotriazole compound, a triazine compound, a cyanoacrylate compound, or a nickel complex salt compound. As the protective film, an acetylcellulose-based resin film such as a triacetylcellulose film or an amorphous cyclic polyolefin-based resin film such as a norbornene-based resin film is preferably used. Commercially available amorphous cyclic polyolefin resin films include, for example, “Arton Film” sold by JSR Corporation, “Zeonor Film” sold by Optes Corporation, etc. (all trade names) There is. Moreover, the above-mentioned retardation film can also be directly used as a protective film.
上記で説明した光学フィルムのなかでも、直線偏光フィルムは、それを構成する偏光子、例えば、ポリビニルアルコール系樹脂からなる偏光子フィルムの片面又は両面に、保護フィルムが貼着された状態で用いられることが多い。また、前述した楕円偏光フィルムは、直線偏光フィルムと位相差フィルムを積層したものであるが、その直線偏光フィルムも、偏光子フィルムの片面又は両面に、保護フィルムが貼着された状態であることが多い。このような楕円偏光フィルムに、本発明による粘着剤層を形成する場合は、通常、その位相差フィルム側に粘着剤層が形成される。本発明により粘着剤層が設けられる光学フィルムの好適な例として、偏光子の少なくとも一方の面にアセチルセルロース系樹脂又は非晶性環状ポリオレフィン系樹脂からなる保護フィルムが貼着された偏光フィルムを含むものを挙げることができる。 Among the optical films described above, the linearly polarizing film is used in a state where a protective film is attached to one or both sides of a polarizer constituting the polarizer, for example, a polarizer film made of a polyvinyl alcohol-based resin. There are many cases. Moreover, although the above-mentioned elliptically polarizing film is a laminate of a linearly polarizing film and a retardation film, the linearly polarizing film is also in a state where a protective film is attached to one side or both sides of the polarizer film. There are many. When the pressure-sensitive adhesive layer according to the present invention is formed on such an elliptically polarizing film, the pressure-sensitive adhesive layer is usually formed on the retardation film side. Preferred examples of the optical film provided with the pressure-sensitive adhesive layer according to the present invention include a polarizing film in which a protective film made of an acetylcellulose-based resin or an amorphous cyclic polyolefin-based resin is attached to at least one surface of a polarizer. Things can be mentioned.
粘着剤付き光学フィルムは、例えば、剥離フィルムの上に上記で説明した粘着剤組成物を塗布して粘着剤層を形成し、得られた粘着剤層に更に光学フィルムを積層する方法、光学フィルムの上に粘着剤組成物を塗布して粘着剤層を形成し、その粘着剤面に剥離フィルムを貼り合わせて保護し、粘着剤付き光学フィルムとする方法等により、製造できる。ここで、剥離フィルムとしては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリアリレート等の各種樹脂からなるフィルムを基材とし、この基材の粘着剤層との接合面に、シリコーン処理の如き離型処理が施されたもの等が挙げられる。粘着剤層は、前述の如く有機溶剤溶液となっている粘着剤組成物を、上記の剥離フィルム又は光学フィルムの上に塗布し、乾燥する方法により、形成することができる。塗工には、公知の各種コーターを用いることができる。塗工後は通常、0〜50℃程度の温度及び20〜80%程度の相対湿度で、3〜14日間程度熟成される。熟成の好ましい条件は、温度が20〜30℃程度、相対湿度が55〜75%程度、期間が5〜7日程度である。この熟成によって、粘着剤の架橋反応が進行する。粘着剤層を剥離フィルムの上に設けた場合、熟成は、その剥離フィルム上に粘着剤層を形成した状態で行っておいてもよいし、剥離フィルム上の粘着剤層を光学フィルムに積層した後に行ってもよい。 An optical film with an adhesive is, for example, a method of applying an adhesive composition described above on a release film to form an adhesive layer, and further laminating the optical film on the obtained adhesive layer, an optical film A pressure-sensitive adhesive composition is applied on the surface to form a pressure-sensitive adhesive layer, and a release film is bonded to the surface of the pressure-sensitive adhesive to protect it, thereby producing an optical film with a pressure-sensitive adhesive. Here, as the release film, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate and the like is used as a base material, and the bonding surface with the adhesive layer of the base material is treated with silicone. The thing etc. which the mold release process was given are mentioned. The pressure-sensitive adhesive layer can be formed by a method in which the pressure-sensitive adhesive composition that is an organic solvent solution as described above is applied onto the release film or the optical film and dried. Various known coaters can be used for coating. After coating, it is usually aged for about 3 to 14 days at a temperature of about 0 to 50 ° C. and a relative humidity of about 20 to 80%. Preferred conditions for aging are a temperature of about 20-30 ° C., a relative humidity of about 55-75%, and a period of about 5-7 days. By this aging, the crosslinking reaction of the adhesive proceeds. When the pressure-sensitive adhesive layer is provided on the release film, the aging may be performed in a state where the pressure-sensitive adhesive layer is formed on the release film, or the pressure-sensitive adhesive layer on the release film is laminated on the optical film. It may be done later.
粘着剤層の厚みは特に限定されないが、通常は30μm以下であるのが好ましく、また10μm以上であるのが好ましい。粘着剤層の厚みが30μm以下であると、高温高湿下での接着性が向上し、ガラス基板と粘着剤層との間に浮きや剥れの発生する可能性が低くなる傾向にあり、しかもリワーク性が向上する傾向にあることから好ましく、またその厚みが10μm以上であると、そこに貼合されている光学フィルムの寸法が変化しても、その寸法変化に粘着剤層が追随して変動するので、液晶セルの周縁部の明るさと中心部の明るさとの間に差がなくなり、白抜けや色ムラが抑制される傾向にあることから好ましい。 Although the thickness of an adhesive layer is not specifically limited, Usually, it is preferable that it is 30 micrometers or less, and it is preferable that it is 10 micrometers or more. When the thickness of the pressure-sensitive adhesive layer is 30 μm or less, the adhesiveness under high temperature and high humidity is improved, and there is a tendency that the possibility of floating or peeling between the glass substrate and the pressure-sensitive adhesive layer is reduced. Moreover, it is preferable because reworkability tends to be improved, and if the thickness is 10 μm or more, the adhesive layer follows the change in dimensions even if the dimensions of the optical film bonded thereto change. Therefore, there is no difference between the brightness at the peripheral edge of the liquid crystal cell and the brightness at the center, which is preferable because white spots and color unevenness tend to be suppressed.
本発明の粘着剤付き光学フィルムは、その粘着剤層でガラス基板に積層して、光学積層体とすることができる。ここで、ガラス基板としては、例えば、液晶セルのガラス基板、防眩用ガラス、サングラス用ガラス等を挙げることができる。なかでも、液晶セルの前面側(視認側)のガラス基板に粘着剤付き光学フィルム(上偏光フィルム)を積層し、液晶セルの背面側のガラス基板に別の粘着剤付き光学フィルム(下偏光フィルム)を積層してなる光学積層体は、液晶表示装置として使用することができる。ガラス基板の材料としては、例えば、ソーダライムガラス、低アルカリガラス、無アルカリガラス等が挙げられる。粘着剤付き光学フィルムをガラス基板に積層して光学積層体とするには、例えば、上記のようにして得られる粘着剤付き光学フィルムから剥離フィルムを剥がし、露出した粘着剤層をガラス基板の表面に貼り合わせればよい。 The optical film with pressure-sensitive adhesive of the present invention can be laminated on a glass substrate with the pressure-sensitive adhesive layer to form an optical laminate. Here, as a glass substrate, the glass substrate of a liquid crystal cell, the glass for glare-proof, the glass for sunglasses etc. can be mentioned, for example. Among them, an optical film with an adhesive (upper polarizing film) is laminated on the glass substrate on the front side (viewing side) of the liquid crystal cell, and another optical film with an adhesive (lower polarizing film) on the glass substrate on the rear side of the liquid crystal cell. ) Can be used as a liquid crystal display device. Examples of the material for the glass substrate include soda lime glass, low alkali glass, non-alkali glass, and the like. In order to laminate an optical film with an adhesive on a glass substrate to form an optical laminate, for example, the release film is peeled off from the optical film with an adhesive obtained as described above, and the exposed adhesive layer is removed from the surface of the glass substrate. You just have to stick together.
本発明の粘着剤付き光学フィルムは、ガラス基板に貼着して光学積層体とした後、なんらかの不都合があってその光学フィルムをガラス基板から剥離する場合に、粘着剤層は光学フィルムに伴って剥離され、粘着剤層と接していたガラス基板の表面に、曇りや糊残り等がほとんど発生しないことから、剥離後のガラス基板に再び、粘着剤付き光学フィルムを貼り直すことが容易である。即ち、いわゆるリワーク性に優れている。 The optical film with the pressure-sensitive adhesive of the present invention is attached to a glass substrate to form an optical laminate, and when there is some inconvenience and the optical film is peeled from the glass substrate, the pressure-sensitive adhesive layer is accompanied by the optical film. Since the surface of the glass substrate that has been peeled off and is in contact with the pressure-sensitive adhesive layer hardly causes fogging or adhesive residue, it is easy to re-attach the optical film with the pressure-sensitive adhesive again to the glass substrate after peeling. That is, it is excellent in so-called reworkability.
本発明の粘着剤付き光学フィルムを液晶セルガラスの少なくとも一方の面に貼り合わせて形成される液晶表示装置は、例えば、ノート型、ディスクトップ型、PDA(Personal Digital Assistance)等を包含するパーソナルコンピュータ用液晶ディスプレイ、テレビ、車載用ディスプレイ、電子辞書、デジタルカメラ、デジタルビデオカメラ、電子卓上計算機、時計等に用いることができる。 The liquid crystal display device formed by bonding the optical film with an adhesive of the present invention to at least one surface of the liquid crystal cell glass is, for example, a personal computer including a notebook type, a desktop type, a PDA (Personal Digital Assistance), etc. It can be used for liquid crystal displays, televisions, in-vehicle displays, electronic dictionaries, digital cameras, digital video cameras, electronic desk calculators, watches, etc.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はこれらの例によって限定されるものではない。例中、使用量乃至含有量を表す部及び%は、特に断りのない限り質量基準である。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the examples, the parts and% representing the amount used or the content are based on mass unless otherwise specified.
以下の例において、アクリル樹脂の不揮発分は、JIS K 5407に準じた方法にて測定した値である。具体的には、粘着剤溶液を任意の質量でシャーレにとり、防爆オーブンにて115℃で2時間乾燥させた後の残留不揮発分質量を、最初に測りとった溶液の質量に対する割合で表したものである。アクリル樹脂の重量平均分子量は、GPC装置に、カラムとして東ソー(株)製の“TSK gel GMHHR−H(S)”2本を直列につないで配置し、溶出液としてテトラヒドロフランを用いて、試料濃度5mg/ml、試料導入量100μl、温度40℃、流速1ml/分の条件で、標準ポリスチレン換算により測定した値である。In the following examples, the nonvolatile content of the acrylic resin is a value measured by a method according to JIS K 5407. Specifically, the adhesive solution was taken in a petri dish at an arbitrary mass, and the residual nonvolatile mass after drying at 115 ° C. for 2 hours in an explosion-proof oven was expressed as a percentage of the mass of the solution first measured. It is. The weight average molecular weight of the acrylic resin was determined by placing two “TSK gel GMH HR- H (S)” manufactured by Tosoh Corporation as a column in series in a GPC apparatus, and using tetrahydrofuran as an eluent. This is a value measured in terms of standard polystyrene under conditions of a concentration of 5 mg / ml, a sample introduction amount of 100 μl, a temperature of 40 ° C., and a flow rate of 1 ml / min.
また、各例で得られたオルガノポリシロキサンの分析は、以下に示す方法で行った。 Moreover, the analysis of the organopolysiloxane obtained in each example was performed by the method shown below.
(1)オルガノポリシロキサンの平均分子量及び平均重合度
ゲルパーミエーションクロマトグラフィー(GPC)分析により、ポリスチレン標準サンプルから作成した検量線を基準として重量平均分子量を求め、更にそれから平均重合度を算出した。(1) Average molecular weight and average degree of polymerization of organopolysiloxane By gel permeation chromatography (GPC) analysis, the weight average molecular weight was determined based on a calibration curve prepared from a polystyrene standard sample, and the average degree of polymerization was further calculated therefrom.
(2)オルガノポリシロキサン中のアルコキシ基含有量
アルカリクラッキング−ガスクロマトグラフィー(GC)分析法〔シリコーンハンドブック、792〜793頁(1990年,日刊工業新聞社発行)参照〕により、アルコキシ基含有量を測定し、前記平均組成式(I)における係数c及びd、並びに前記平均組成式(II)における係数h、i及びjを決定した。(2) Alkoxy group content in organopolysiloxane Alkali group content was determined by alkali cracking-GC (GC) analysis method (see Silicone Handbook, pages 792-793 (1990, published by Nikkan Kogyo Shimbun)). Measured to determine the coefficients c and d in the average composition formula (I) and the coefficients h, i and j in the average composition formula (II).
(3)オルガノポリシロキサンの構造解析
ケイ素核磁気共鳴スペクトル(29Si−NMR)分析及びプロトン核磁気共鳴スペクトル(1H−NMR)分析により行い、測定結果より前記平均組成式(I)における係数a、b及びe、並びに前記平均組成式(II)における係数f、g及びkを決定した。(3) Structural analysis of organopolysiloxane Conducted by silicon nuclear magnetic resonance spectrum ( 29 Si-NMR) analysis and proton nuclear magnetic resonance spectrum ( 1 H-NMR) analysis. From the measurement results, the coefficient a in the average composition formula (I) , B and e, and the coefficients f, g and k in the average composition formula (II) were determined.
(4)オルガノポリシロキサンのメルカプト基当量
酢酸/ヨウ化カリウム/ヨウ素酸カリウム添加−チオ硫酸ナトリウム溶液滴定法〔分析化学便覧、改訂二版、432〜433頁(1976年,丸善株式会社発行)参照〕に準拠して測定した。(4) Mercapto group equivalent of organopolysiloxane Acetic acid / potassium iodide / potassium iodate added-sodium thiosulfate solution titration method [Analytical Chemistry Handbook, 2nd revised edition, pages 432-433 (1976, issued by Maruzen Co., Ltd.)] ] And was measured according to.
(5)オルガノポリシロキサンの粘度
JIS K 8803に準じた方法により25℃における粘度を測定した。(5) Viscosity of organopolysiloxane The viscosity at 25 ° C. was measured by a method according to JIS K 8803.
まず、本発明で規定するアクリル樹脂を製造した例を示す。
[重合例1]
冷却管、窒素導入管、温度計及び撹拌機を備えた反応器に、酢酸エチル81.8部、アクリル酸ブチル98.9部及びアクリル酸1.1部の混合溶液を仕込み、窒素ガスで装置内の空気を置換して酸素不含としながら、内温を55℃に上げた。その後、アゾビスイソブチロニトリル(重合開始剤)0.14部を酢酸エチル10部に溶かした溶液を全量添加した。開始剤添加1時間後に、モノマーを除くアクリル樹脂の濃度が35%になるよう、添加速度17.3部/hrで酢酸エチルを連続的に反応器に添加しながら、内温54〜56℃で12時間保温し、最後に酢酸エチルを添加して、アクリル樹脂の濃度が20%となるように調節した。得られたアクリル樹脂Aは、GPCによるポリスチレン換算の重量平均分子量Mwが1,670,000、Mw/Mnが4.4であった。First, the example which manufactured the acrylic resin prescribed | regulated by this invention is shown.
[Polymerization Example 1]
A reactor equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer was charged with a mixed solution of 81.8 parts of ethyl acetate, 98.9 parts of butyl acrylate and 1.1 parts of acrylic acid, and the apparatus was equipped with nitrogen gas The internal temperature was raised to 55 ° C. while substituting the inside air to make it oxygen-free. Thereafter, a total amount of a solution prepared by dissolving 0.14 part of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. One hour after the addition of the initiator, while adding ethyl acetate continuously to the reactor at an addition rate of 17.3 parts / hr so that the concentration of the acrylic resin excluding the monomer was 35%, the internal temperature was 54 to 56 ° C. The temperature was kept for 12 hours, and finally ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The obtained acrylic resin A had a polystyrene equivalent weight average molecular weight Mw by GPC of 1,670,000 and Mw / Mn of 4.4.
次に、本発明で用いるオルガノポリシロキサンを合成した例を示す。
[オルガノポリシロキサン合成例1](第一のオルガノポリシロキサン)
撹拌装置、冷却コンデンサー、温度計及び滴下ロートを取り付けた容量1Lのフラスコに、3−メルカプトプロピルトリメトキシシラン39.3g(0.2モル)、メチルトリメトキシシラン40.9g(0.3モル)、テトラエトキシシラン104.2g(0.5モル)、メタノール80.2g及びエタノール104.2gを仕込み、内温20〜30℃でフラスコ内を撹拌しながら、0.1N塩酸水溶液16.2g(水:0.9モル、塩化水素:1.62×10-3モル)とメタノール16.2gとの混合溶液を30分間かけて滴下し、更に昇温して還流下で2時間熟成を行った。Next, an example in which an organopolysiloxane used in the present invention is synthesized will be shown.
[Synthesis example 1 of organopolysiloxane] (first organopolysiloxane)
In a 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 39.3 g (0.2 mol) of 3-mercaptopropyltrimethoxysilane and 40.9 g (0.3 mol) of methyltrimethoxysilane , 104.2 g (0.5 mol) of tetraethoxysilane, 80.2 g of methanol and 104.2 g of ethanol were added, and the inside of the flask was stirred at an internal temperature of 20-30 ° C. : 0.9 mol, hydrogen chloride: 1.62 × 10 −3 mol) and 16.2 g of methanol were added dropwise over 30 minutes, and the mixture was further heated and aged for 2 hours under reflux.
次いで、フッ化カリウムの1%エタノール溶液9.4g(KF:1.62×10-3モル)を添加し、更に還流下で2時間熟成して、部分共加水分解及び重縮合反応を行った。引き続き、常圧下で内温を80℃まで昇温しながらアルコール成分を留去し、更に30Torr(約4kPa)の減圧条件下に、内温を100℃まで昇温して残存アルコール成分と低沸点成分を留去した後、濾過を行って無色透明液状のオルガノポリシロキサンCを得た(収量:117.0g、収率:90%)。Next, 9.4 g of a 1% ethanol solution of potassium fluoride (KF: 1.62 × 10 −3 mol) was added, and further aged for 2 hours under reflux to carry out partial cohydrolysis and polycondensation reaction. . Subsequently, the alcohol component was distilled off while raising the internal temperature to 80 ° C. under normal pressure, and the internal temperature was raised to 100 ° C. under a reduced pressure of 30 Torr (about 4 kPa) to reduce the residual alcohol component and the low boiling point. After the components were distilled off, filtration was performed to obtain colorless and transparent liquid organopolysiloxane C (yield: 117.0 g, yield: 90%).
このオルガノポリシロキサンCは、前記平均組成式(I)において、Yが3−メルカプトプロピル基、R1がメチル基であり、使用した各原料(有機溶媒以外)のモル比、上記した分析結果から求めた重量平均分子量、平均重合度、前記式(I)に相当する平均組成式、メルカプト基当量、及び粘度は、以下の通りであった。This organopolysiloxane C has an average composition formula (I) in which Y is a 3-mercaptopropyl group, R 1 is a methyl group, the molar ratio of each raw material (other than the organic solvent) used, and the above analysis results. The obtained weight average molecular weight, average degree of polymerization, average composition formula corresponding to the formula (I), mercapto group equivalent, and viscosity were as follows.
“オルガノポリシロキサンC”の原料モル比、平均組成式及び物性値
原料モル比:
HS(CH2)3Si(OCH3)3/CH3Si(OCH3)3/Si(OC2H5)4
=0.2/0.3/0.5
触媒:HCl/KF/水=0.00162/0.00162/0.9
重量平均分子量:1,380
平均重合度:10.6
平均組成式:
[HS(CH2)3]0.2(CH3)0.3Si(OCH3)0.61(OC2H5)1.08O0.905
メルカプト基当量:測定値638g/モル、理論値651g/モル
粘度:20.5mm2/sRaw material molar ratio, average composition formula and physical property value raw material molar ratio of “organopolysiloxane C”:
HS (CH 2 ) 3 Si (OCH 3 ) 3 / CH 3 Si (OCH 3 ) 3 / Si (OC 2 H 5 ) 4
= 0.2 / 0.3 / 0.5
Catalyst: HCl / KF / water = 0.00162 / 0.00162 / 0.9
Weight average molecular weight: 1,380
Average degree of polymerization: 10.6
Average composition formula:
[HS (CH 2 ) 3 ] 0.2 (CH 3 ) 0.3 Si (OCH 3 ) 0.61 (OC 2 H 5 ) 1.08 O 0.905
Mercapto group equivalent: measured value 638 g / mol, theoretical value 651 g / mol viscosity: 20.5 mm 2 / s
[オルガノポリシロキサン合成例2](第二のオルガノポリシロキサン)
撹拌装置、冷却コンデンサー、温度計及び滴下ロートを取り付けた容量1Lのフラスコに、テトラプロポキシシラン132.2g(0.5モル)及びイソプロピルアルコール132.2gを仕込み、撹拌混合しながらオイルバス中で加熱して内温を50℃まで昇温した。フラスコ内を撹拌しながら、1N塩酸水溶液7.2g(水:0.4モル、塩化水素:7.2×10-3モル)とイソプロピルアルコール7.2gとの混合溶液を10分間かけて滴下し、更に昇温して還流下で2時間熟成して予備加水分解反応液D1を得た。[Synthesis example 2 of organopolysiloxane] (second organopolysiloxane)
A 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel was charged with 132.2 g (0.5 mol) of tetrapropoxysilane and 132.2 g of isopropyl alcohol and heated in an oil bath while stirring and mixing. The internal temperature was raised to 50 ° C. While stirring the flask, a mixed solution of 7.2 g of 1N aqueous hydrochloric acid (water: 0.4 mol, hydrogen chloride: 7.2 × 10 −3 mol) and 7.2 g of isopropyl alcohol was added dropwise over 10 minutes. The mixture was further heated and aged for 2 hours under reflux to obtain a prehydrolysis reaction solution D1.
これとは別に、3−メルカプトプロピルトリエトキシシラン47.7g(0.2モル)、メチルトリエトキシシラン17.8g(0.1モル)、メチルトリイソプロポキシシラン44.1g(0.2モル)、エタノール65.5g及びイソプロピルアルコール44.1gの混合溶液中に、内温20〜30℃で1N塩酸水溶液7.2g(水:0.4モル、塩化水素:7.2×10-3モル)とイソプロピルアルコール7.2gとの混合溶液を10分間かけて滴下し、更に内温20〜30℃で30分間熟成して予備加水分解反応液D2を得た。Apart from this, 4-mercaptopropyltriethoxysilane 47.7 g (0.2 mol), methyltriethoxysilane 17.8 g (0.1 mol), methyltriisopropoxysilane 44.1 g (0.2 mol) In a mixed solution of 65.5 g of ethanol and 44.1 g of isopropyl alcohol, 7.2 g of 1N hydrochloric acid aqueous solution at an internal temperature of 20 to 30 ° C. (water: 0.4 mol, hydrogen chloride: 7.2 × 10 −3 mol) A mixed solution of isopropyl alcohol and 7.2 g was added dropwise over 10 minutes, and further aged at an internal temperature of 20 to 30 ° C. for 30 minutes to obtain a prehydrolysis reaction liquid D2.
上記の予備加水分解反応液D1中に予備加水分解反応液D2を添加して、撹拌混合した後、内温20〜30℃で1N塩酸水溶液1.8g(水:0.1モル、塩化水素:1.8×10-3モル)とイソプロピルアルコール1.8gとの混合溶液を添加してから、オイルバス中で加熱して還流下で2時間熟成を行った。次いで、フッ化カリウム0.94g(KF:1.62×10-2モル)を添加し、更に還流下で2時間熟成して、部分共加水分解及び重縮合反応を行った。
引き続き、常圧下で内温を80℃まで昇温しながらアルコール成分を留去し、更に30Torr(約4kPa)の減圧条件下に、内温を100℃まで昇温して残存アルコール成分と低沸点成分を留去した後、濾過を行って無色透明液状のオルガノポリシロキサンDを得た(収量:140.8g、収率:90%)。The prehydrolysis reaction solution D2 is added to the prehydrolysis reaction solution D1 and mixed with stirring. Then, 1.8 g of 1N hydrochloric acid aqueous solution (water: 0.1 mol, hydrogen chloride: 1.8 × 10 −3 mol) and 1.8 g of isopropyl alcohol were added, and then the mixture was heated in an oil bath and aged for 2 hours under reflux. Next, 0.94 g of potassium fluoride (KF: 1.62 × 10 −2 mol) was added, and the mixture was further aged for 2 hours under reflux to perform partial cohydrolysis and polycondensation reaction.
Subsequently, the alcohol component was distilled off while raising the internal temperature to 80 ° C. under normal pressure, and the internal temperature was raised to 100 ° C. under a reduced pressure of 30 Torr (about 4 kPa) to reduce the residual alcohol component and the low boiling point. After the components were distilled off, filtration was performed to obtain colorless and transparent liquid organopolysiloxane D (yield: 140.8 g, yield: 90%).
このオルガノポリシロキサンDは、前記平均組成式(II)において、Yが3−メルカプトプロピル基、R1がメチル基、R2がプロピル基及びイソプロピル基であり、使用した各原料(有機溶媒以外)のモル比、上記した分析結果から求めた重量平均分子量、平均重合度、前記式(II)に相当する平均組成式、メルカプト基当量、及び粘度は、以下の通りであった。This organopolysiloxane D has the above average composition formula (II), wherein Y is a 3-mercaptopropyl group, R 1 is a methyl group, R 2 is a propyl group and an isopropyl group, and each raw material used (other than an organic solvent) , The weight average molecular weight, the average degree of polymerization, the average composition formula corresponding to the formula (II), the mercapto group equivalent, and the viscosity were as follows.
“オルガノポリシロキサンD”の原料モル比、平均組成式及び物性値
原料モル比:
HS(CH2)3Si(OC2H5)3/CH3Si(OC2H5)3/
CH3Si(OC3H7)3/Si(OC3H7)4=0.2/0.1/0.2/0.5
触媒:HCl/KF/水=0.0162/0.0162/0.9
重量平均分子量:1,620
平均重合度:10.3
平均組成式:
[HS(CH2)3]0.2(CH3)0.3Si(OC2H5)0.39(OC3H7)1.31O0.9
メルカプト基当量:測定値803g/モル、理論値785g/モル
粘度:33.6mm2/sRaw material molar ratio, average composition formula and physical property value raw material molar ratio of “organopolysiloxane D”:
HS (CH 2 ) 3 Si (OC 2 H 5 ) 3 / CH 3 Si (OC 2 H 5 ) 3 /
CH 3 Si (OC 3 H 7 ) 3 / Si (OC 3 H 7 ) 4 = 0.2 / 0.1 / 0.2 / 0.5
Catalyst: HCl / KF / water = 0.0162 / 0.0162 / 0.9
Weight average molecular weight: 1,620
Average degree of polymerization: 10.3
Average composition formula:
[HS (CH 2 ) 3 ] 0.2 (CH 3 ) 0.3 Si (OC 2 H 5 ) 0.39 (OC 3 H 7 ) 1.31 O 0.9
Mercapto group equivalent: measured value 803 g / mol, theoretical value 785 g / mol viscosity: 33.6 mm 2 / s
次に、上記で製造したアクリル樹脂及びオルガノポリシロキサンを用いて、粘着剤を調製し、光学フィルムに適用した実施例及び比較例を示す。ここでは、架橋剤として次のものを用いた。
“コロネートL”:トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、日本ポリウレタン工業(株)製商品名
“TAZM”:トリメチロールプロパン トリ−β−アジリジニルプロピオネート(液体)、相互薬工(株)製商品名Next, Examples and Comparative Examples in which pressure-sensitive adhesives were prepared using the acrylic resin and organopolysiloxane produced above and applied to an optical film are shown. Here, the following were used as a crosslinking agent.
“Coronate L”: Ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate (solid content concentration 75%), trade name “TAZM”: Trimethylolpropane tri-β-aziridinylpro manufactured by Nippon Polyurethane Industry Co., Ltd. Pionate (liquid), trade name manufactured by Mutual Yako Co., Ltd.
また、比較例のシラン化合物として、それぞれ次のものを用いた。
“KBM−803”:3−メルカプトプロピルトリメトキシシラン(液体)、信越化学工業(株)製商品名
“KBM−303”:2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン(液体)、信越化学工業(株)製商品名Moreover, the following were each used as the silane compound of a comparative example.
“KBM-803”: 3-mercaptopropyltrimethoxysilane (liquid), trade name “KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd .: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (liquid), Product name manufactured by Shin-Etsu Chemical Co., Ltd.
[実施例1、2及び比較例1〜4]
(a)粘着剤の製造
重合例1で得たアクリル樹脂Aの酢酸エチル溶液を不揮発分で100部用い、そこに架橋剤として“コロネートL”と“TAZM”を表1に示す量、及び表1に示すオルガノポリシロキサン(又はシラン化合物)をそれぞれ表1に示す量配合し、粘着剤組成物を調製した。但し、表1中、架橋剤“コロネートL”の配合量(部)は、固形分の量である。[Examples 1 and 2 and Comparative Examples 1 to 4]
(A) Production of pressure-sensitive adhesive 100 parts by volume of the ethyl acetate solution of acrylic resin A obtained in Polymerization Example 1 was used in a nonvolatile content, and the amounts shown in Table 1 were “Coronate L” and “TAZM” as crosslinking agents. The organopolysiloxane (or silane compound) shown in No. 1 was blended in the amounts shown in Table 1 to prepare an adhesive composition. However, in Table 1, the blending amount (part) of the crosslinking agent “Coronate L” is the amount of solids.
(b)粘着剤付き光学フィルムの作製
上記の各粘着剤組成物を、離型処理されたポリエチレンテレフタレートフィルム(“PET 3811”、リンテック(株)製商品名;セパレーターと呼ぶ)の離型処理面に、アプリケーターを用いて乾燥後の厚さが15μmとなるように塗布し、90℃で1分間乾燥させ、シート状の粘着剤を得た。次いで、ヨウ素が吸着配向したポリビニルアルコール偏光子の両面をトリアセチルセルロースからなる保護フィルムで挟んだ3層構造の偏光フィルムの片面に、上記で得たシート状粘着剤のセパレーターと反対側の面(粘着剤面)をラミネーターにより貼り合わせたのち、温度23℃、相対湿度65%の条件で7日間熟成させ、粘着剤付き偏光フィルムを得た。また、それらの粘着剤付き偏光フィルムをアルミニウム箔付きパックで密閉し、温度60℃で更に6日間熟成させ、熱による経時変化を促進させた。(B) Production of optical film with pressure-sensitive adhesive The release-treated surface of each of the above-mentioned pressure-sensitive adhesive compositions was subjected to a release-treated polyethylene terephthalate film ("PET 3811", product name manufactured by Lintec Corporation; called a separator). Then, it was applied using an applicator so that the thickness after drying was 15 μm, and dried at 90 ° C. for 1 minute to obtain a sheet-like pressure-sensitive adhesive. Next, on one side of a polarizing film having a three-layer structure in which both sides of a polyvinyl alcohol polarizer to which iodine is adsorbed and oriented are sandwiched between protective films made of triacetyl cellulose, the surface opposite to the separator of the sheet-like adhesive obtained above ( The pressure-sensitive adhesive surface) was pasted with a laminator and then aged for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain a polarizing film with a pressure-sensitive adhesive. Moreover, these polarizing films with an adhesive were sealed with a pack with an aluminum foil, and further aged for 6 days at a temperature of 60 ° C., thereby accelerating changes with time.
(c)光学積層体(偏光フィルムのガラス貼着品)の作製
上記(b)で作製した粘着剤付き偏光フィルム(23℃×65%RH×7日間熟成したもの、及びその後更に60℃×6日間熟成したもの)を、液晶セル用ガラス基板(“1737”、コーニング社製商品名)の両面にクロスニコルとなるよう、それぞれ粘着剤層側で貼着し、光学積層体を作製した。(C) Production of optical layered product (polarized film glass-attached product) Polarized film with pressure-sensitive adhesive produced in (b) above (23 ° C. × 65% RH × 7 days aged, and then further 60 ° C. × 6 The product was aged for 2 days, and was adhered on both sides of the glass substrate for liquid crystal cell (“1737”, product name manufactured by Corning) so as to be crossed Nicol, respectively, thereby producing an optical laminate.
(d)光学積層体の耐熱性及び耐湿熱性の評価
上記(c)で得られた光学積層体について、温度80℃の乾燥条件下で300時間保管する耐熱試験を行い、また温度60℃、相対湿度90%で300時間保管する耐湿熱試験を行い、それぞれ試験後の光学積層体を目視で観察し、以下の4段階で評価した。結果を表2にまとめた。
〈耐熱性及び耐湿熱性の評価基準〉
◎:浮き、剥れ、発泡等の外観変化が全くみられない。
○:浮き、剥れ、発泡等の外観変化がほとんどみられない。
△:浮き、剥れ、発泡等の外観変化がやや目立つ。
×:浮き、剥れ、発泡等の外観変化が顕著に認められる。(D) Evaluation of heat resistance and heat-and-moisture resistance of the optical layered body The optical layered body obtained in (c) above was subjected to a heat resistance test that was stored for 300 hours under dry conditions at a temperature of 80 ° C. A moisture and heat resistance test was performed for storage for 300 hours at a humidity of 90%. Each optical laminate after the test was visually observed and evaluated in the following four stages. The results are summarized in Table 2.
<Evaluation criteria for heat resistance and moist heat resistance>
A: No change in appearance such as floating, peeling or foaming is observed.
○: Almost no change in appearance such as floating, peeling or foaming.
Δ: Appearance changes such as floating, peeling and foaming are slightly noticeable.
X: Remarkable changes in appearance such as floating, peeling, foaming, etc.
(e)粘着剤付き光学フィルムのリワーク性評価
リワーク性の評価は次のように行った。まず、(b)で作製した粘着剤付き偏光フィルム(23℃×65%RH×7日間熟成したもの、及びその後更に60℃×6日間熟成したもの)をそれぞれ25mm×150mmの大きさの試験片に裁断した。次に、この試験片をその粘着剤層側で、貼付装置(“ラミパッカー”、フジプラ(株)製商品名)を用いて液晶セル用ガラス基板に貼り付け、50℃、5kgf/cm2(490.3kPa)で20分間オートクレーブ処理を行った。次に、温度23℃、相対湿度50%の雰囲気中にて24時間保管したサンプルと、50℃のオーブン中にて48時間保管したサンプルとの2種類を作製し、温度23℃、相対湿度50%の雰囲気中にて、この貼着試験片から偏光フィルムを300mm/分の速度で180°方向に剥離し、それぞれのガラス基板表面の状態を観察して、以下の基準で分類した。結果を、併せて表2に示した。
〈リワーク性評価基準〉
◎:ガラス板表面に曇り等が全く認められない。
○:ガラス板表面に曇り等がほとんど認められない。
△:ガラス板表面に曇り等が認められる。
×:ガラス板表面に粘着剤の残りが認められる。(E) Reworkability evaluation of optical film with adhesive The reworkability was evaluated as follows. First, a polarizing plate with an adhesive produced in (b) (23 ° C. × 65% RH × 7 days aged and then 60 ° C. × 6 days aged), each having a size of 25 mm × 150 mm test piece Cut to. Next, this test piece was attached to the glass substrate for a liquid crystal cell on the pressure-sensitive adhesive layer side using a sticking device (“Lami Packer”, a product name manufactured by Fuji Plastic Co., Ltd.), and 50 ° C., 5 kgf / cm 2 (490). .3 kPa) for 20 minutes. Next, two types of samples, a sample stored for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and a sample stored for 48 hours in an oven at 50 ° C. were prepared. In a% atmosphere, the polarizing film was peeled off from this sticking test piece at a rate of 300 mm / min in the 180 ° direction, and the state of each glass substrate surface was observed, and classified according to the following criteria. The results are also shown in Table 2.
<Reworkability evaluation criteria>
A: No fogging or the like is observed on the glass plate surface.
A: Almost no fogging or the like is observed on the glass plate surface.
(Triangle | delta): Cloudiness etc. are recognized by the glass plate surface.
X: The remainder of an adhesive is recognized by the glass plate surface.
表1及び表2からわかるように、アクリル樹脂及び架橋剤に、本発明で規定する2種類のオルガノポリシロキサンを配合した実施例1及び2は、耐熱性、耐湿熱性及びリワーク性のいずれにおいても良好な性能を示し、また、それらの粘着剤付き光学フィルムを60℃で6日間熟成した後も、耐熱性、耐湿熱性及びリワーク性において、ほぼ満足できる結果が得られた。 As can be seen from Tables 1 and 2, Examples 1 and 2 in which two types of organopolysiloxanes defined in the present invention were blended with an acrylic resin and a cross-linking agent were both in heat resistance, moist heat resistance and reworkability. Even after aging the optical films with pressure-sensitive adhesives at 60 ° C. for 6 days, almost satisfactory results were obtained in heat resistance, moist heat resistance and reworkability.
これに対して、第一のオルガノポリシロキサンのみを配合した比較例1、第二のオルガノポリシロキサンのみを配合した比較例2、並びにモノマータイプのシラン化合物を配合した比較例3及び4は、耐熱性、耐湿熱性及びリワーク性のいずれかにおいて、不十分な結果であった。 In contrast, Comparative Example 1 in which only the first organopolysiloxane was blended, Comparative Example 2 in which only the second organopolysiloxane was blended, and Comparative Examples 3 and 4 in which a monomer type silane compound was blended were heat resistant. In any of the properties, heat and humidity resistance and reworkability, the results were insufficient.
Claims (11)
(B)架橋剤、
(C)下記平均組成式(I)
YaR1 bSi(OCH3)c(OC2H5)d(OH)eO(4-a-b-c-d-e)/2 …(I)
(式中、Yはメルカプト基、エポキシ基、(メタ)アクリロイロキシ基、アルケニル基、
ハロアルキル基及びアミノ基から選ばれる少なくとも1種を有する有機基を表し;
R1は、少なくとも1種の脂肪族不飽和結合を有さない炭素原子数1〜8の非置換の一価炭化水素基を表し;
a、b、c、d及びeは、0.01≦a≦1、0≦b<2、0≦c≦2、0≦d≦2、0≦e≦1であって、かつ0.1≦c+d≦2.5及び2≦a+b+c+d+e≦3を満たす数である。)
で表される第一のオルガノポリシロキサン、及び
(D)下記平均組成式(II)
YfR1 gSi(OCH3)h(OC2H5)i(OR2)j(OH)kO(4-f-g-h-i-j-k)/2
…(II)
(式中、Y及びR1は、上記と同じ意味を表し;
R2は、炭素原子数3及び/又は4のアルキル基あるいはメトキシプロピル基を表し;
f、g、h、i、j及びkは、0.01≦f≦1、0≦g<2、0≦h≦2、0≦i≦2、0<j≦2、0≦k≦1であって、hとiが同時に0となることはなく、かつ0.1≦h+i+j≦2.5及び2≦f+g+h+i+j+k≦3を満たす数である。)
で表される第二のオルガノポリシロキサン
を含有することを特徴とする粘着剤組成物。(A) acrylic resin,
(B) a crosslinking agent,
(C) The following average composition formula (I)
Y a R 1 b Si (OCH 3 ) c (OC 2 H 5 ) d (OH) e O (4-abcde) / 2 (I)
Wherein Y is a mercapto group, an epoxy group, a (meth) acryloyloxy group, an alkenyl group,
Represents an organic group having at least one selected from a haloalkyl group and an amino group;
R 1 represents an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond;
a, b, c, d and e are 0.01 ≦ a ≦ 1, 0 ≦ b <2, 0 ≦ c ≦ 2, 0 ≦ d ≦ 2, 0 ≦ e ≦ 1, and 0.1 ≦ c + d ≦ 2.5 and 2 ≦ a + b + c + d + e ≦ 3. )
And (D) the following average composition formula (II)
Y f R 1 g Si (OCH 3 ) h (OC 2 H 5 ) i (OR 2 ) j (OH) k O (4-fghijk) / 2
... (II)
Wherein Y and R 1 represent the same meaning as above;
R 2 represents an alkyl group having 3 and / or 4 carbon atoms or a methoxypropyl group;
f, g, h, i, j and k are 0.01 ≦ f ≦ 1, 0 ≦ g <2, 0 ≦ h ≦ 2, 0 ≦ i ≦ 2, 0 <j ≦ 2, 0 ≦ k ≦ 1. In this case, h and i are not 0 at the same time, and are numbers satisfying 0.1 ≦ h + i + j ≦ 2.5 and 2 ≦ f + g + h + i + j + k ≦ 3. )
A pressure-sensitive adhesive composition comprising a second organopolysiloxane represented by the formula:
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KR102024253B1 (en) * | 2016-09-09 | 2019-09-23 | 주식회사 엘지화학 | Pressure Sensitive Adhesive composition using foldable display |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07331206A (en) * | 1994-06-01 | 1995-12-19 | Soken Kagaku Kk | Pressure-sensitive adhesive composition for liquid crystal element and liquid crystal element |
JPH0820646A (en) * | 1994-07-06 | 1996-01-23 | Shin Etsu Chem Co Ltd | Production of hydrolyzable functional group-containing organic polysiloxane and curable resin composition |
JPH08199130A (en) * | 1995-01-24 | 1996-08-06 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive composition |
JP2006290994A (en) * | 2005-04-08 | 2006-10-26 | Daio Paper Corp | Adhesive sheet |
JP2008174672A (en) * | 2007-01-22 | 2008-07-31 | Shin Etsu Chem Co Ltd | Organopolysiloxane containing plural kinds of alkoxy groups in which organic functional group and number of carbon atoms differ |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7585570B2 (en) * | 2005-04-14 | 2009-09-08 | Sumitomo Chemical Company, Limited | Adhesives and optical laminates including the same |
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- 2008-01-18 JP JP2008555035A patent/JP5251519B2/en active Active
- 2008-01-18 WO PCT/JP2008/050597 patent/WO2008090815A1/en active Application Filing
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07331206A (en) * | 1994-06-01 | 1995-12-19 | Soken Kagaku Kk | Pressure-sensitive adhesive composition for liquid crystal element and liquid crystal element |
JPH0820646A (en) * | 1994-07-06 | 1996-01-23 | Shin Etsu Chem Co Ltd | Production of hydrolyzable functional group-containing organic polysiloxane and curable resin composition |
JPH08199130A (en) * | 1995-01-24 | 1996-08-06 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive composition |
JP2006290994A (en) * | 2005-04-08 | 2006-10-26 | Daio Paper Corp | Adhesive sheet |
JP2008174672A (en) * | 2007-01-22 | 2008-07-31 | Shin Etsu Chem Co Ltd | Organopolysiloxane containing plural kinds of alkoxy groups in which organic functional group and number of carbon atoms differ |
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KR101455605B1 (en) | 2014-10-28 |
TW200904930A (en) | 2009-02-01 |
TWI437066B (en) | 2014-05-11 |
CN101595193A (en) | 2009-12-02 |
WO2008090815A1 (en) | 2008-07-31 |
KR20090122199A (en) | 2009-11-26 |
CN101595193B (en) | 2012-03-28 |
JP5251519B2 (en) | 2013-07-31 |
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