JP2011116830A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and pressure-sensitive adhesive laminated product - Google Patents
Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and pressure-sensitive adhesive laminated product Download PDFInfo
- Publication number
- JP2011116830A JP2011116830A JP2009273989A JP2009273989A JP2011116830A JP 2011116830 A JP2011116830 A JP 2011116830A JP 2009273989 A JP2009273989 A JP 2009273989A JP 2009273989 A JP2009273989 A JP 2009273989A JP 2011116830 A JP2011116830 A JP 2011116830A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- acid ester
- acrylic acid
- 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
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000010410 layer Substances 0.000 title claims abstract description 44
- -1 amine compound Chemical class 0.000 claims abstract description 76
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000011243 crosslinked material Substances 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 17
- 239000000178 monomer Substances 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000004642 Polyimide Substances 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- 229920002799 BoPET Polymers 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 8
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 150000003053 piperidines Chemical class 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Chemical class 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002357 guanidines Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
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- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
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- VPCUASPSUAEJFE-UHFFFAOYSA-N 2-diphenoxyphosphoryloxyethyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1OP(=O)(OCCOC(=O)C(=C)C)OC1=CC=CC=C1 VPCUASPSUAEJFE-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、感圧接着剤組成物、感圧接着剤層及び感圧接着性積層体に関する。 The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive laminate.
例えば電子部品、またはそれらを構成する材料に対して、その安全上の基準として、UL規格合格を求められることが多くなっており、その中でも難燃性の規格合格を要求される場合が多い。例えば、電子部品などに使用される電気絶縁テープは、UL規格としてUL94本規格に合格する高い難燃特性が求められている。このテープに難燃性を付与するために、従来から塩素や臭素等のハロゲン系化合物を難燃剤とするものや、ハロゲン系化合物と酸化アンチモンを併用した系が知られている。しかしながら、難燃剤としてハロゲン系化合物を用いた場合は、燃焼時に人体へ悪影響を及ぼすハロゲン系ガスが発生することが問題となっており、ハロゲン系化合物を用いずに難燃化する方法が求められている。 For example, electronic parts or materials constituting them are often required to pass the UL standard as safety standards, and among them, the flame retardant standard is often required. For example, electrical insulating tapes used for electronic parts and the like are required to have high flame resistance characteristics that pass UL94 standard as UL standard. In order to impart flame retardancy to this tape, conventionally known are those using halogen compounds such as chlorine and bromine as flame retardants, and systems using both halogen compounds and antimony oxide. However, when a halogen-based compound is used as a flame retardant, there is a problem that a halogen-based gas that adversely affects the human body during combustion is a problem, and a method for making flame retardant without using a halogen-based compound is required. ing.
感圧接着剤の難燃化においても同様のことが問題となっており、ハロゲン系化合物を用いずに難燃化する方法が検討されている。そこで、ポリリン酸アンモニウム、ポリリン酸メラミン、赤リン、リン酸エステル等のリン系化合物を難燃剤として用いた粘着剤や粘着シートが提案されている(例えば、特許文献1〜4参照)。しかしながら、上述するようなリン系化合物を添加した場合、粘着物性の低下や、被接着体の劣化が問題となっていた。また、リン系化合物の種類によっては、粘着剤に凝集物が生じてしまうことがあった。なお、粘着剤に凝集物が生じた場合、粘着剤を塗工して形成される粘着剤層が不透明となり、用途が限定されるという問題も生じていた。 The same is a problem in the flame-retardant of pressure-sensitive adhesives, and a method of flame-retarding without using a halogen-based compound has been studied. Thus, pressure-sensitive adhesives and pressure-sensitive adhesive sheets using phosphorus compounds such as ammonium polyphosphate, melamine polyphosphate, red phosphorus, and phosphate esters as flame retardants have been proposed (for example, see Patent Documents 1 to 4). However, when a phosphorus compound as described above is added, there is a problem in that the physical properties of the adhesive are deteriorated and the adherend is deteriorated. Further, depending on the type of phosphorus compound, an aggregate may be generated in the pressure-sensitive adhesive. In the case where aggregates are generated in the pressure-sensitive adhesive, the pressure-sensitive adhesive layer formed by applying the pressure-sensitive adhesive becomes opaque, and there is a problem that the use is limited.
本発明は、難燃性に優れると共に、粘着性及び透明性に優れた感圧接着剤層を形成できる感圧接着剤組成物、感圧接着剤層及び感圧接着剤層を具備する感圧接着性積層体を提供することを目的とする。 The present invention provides a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive layer capable of forming a pressure-sensitive adhesive layer having excellent flame retardancy and excellent tackiness and transparency. An object is to provide an adhesive laminate.
本発明者らは、上記の目的を達成するために鋭意検討した結果、リン酸エステル基を有する(メタ)アクリル酸エステル系重合体と、アミン系化合物とを含有させることにより、難燃性、粘着性及び透明性に優れた感圧接着剤層を形成できる感圧接着剤組成物、感圧接着剤層及び感圧接着剤層を具備する感圧接着性積層体が得られることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have included a (meth) acrylic acid ester-based polymer having a phosphoric acid ester group and an amine compound, thereby providing flame retardancy, It has been found that a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive layer excellent in tackiness and transparency, a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive layer and a pressure-sensitive adhesive layer can be obtained, The present invention has been completed.
前記課題を解決する本発明の第1の態様は、リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、炭素数1〜18のアルキル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、を含む(メタ)アクリル酸エステル系重合体と、アミン系化合物と、を含むことを特徴とする感圧接着剤組成物にある。 1st aspect of this invention which solves the said subject consists of a repeating unit which consists of (meth) acrylic acid ester which has a phosphate ester group, and (meth) acrylic acid ester which has a C1-C18 alkyl group. A pressure-sensitive adhesive composition comprising: a (meth) acrylic acid ester-based polymer containing a repeating unit; and an amine-based compound.
本発明の第2の態様は、前記(メタ)アクリル酸エステル系重合体100質量部に対して、前記アミン系化合物の総量が0.1〜50質量部となるように配合したものであることを特徴とする第1の態様に記載の感圧接着剤組成物にある。 2nd aspect of this invention mix | blends so that the total amount of the said amine-type compound may be 0.1-50 mass parts with respect to 100 mass parts of said (meth) acrylic acid ester-type polymers. In the pressure-sensitive adhesive composition according to the first aspect,
本発明の第3の態様は、前記リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットは、下記一般式(1)で表されることを特徴とする第1又は2の態様に記載の感圧接着剤組成物にある。 According to a third aspect of the present invention, in the first or second aspect, the repeating unit comprising the (meth) acrylic acid ester having a phosphate ester group is represented by the following general formula (1). In the pressure-sensitive adhesive composition described.
本発明の第4の態様は、前記アミン系化合物は、2級アミン化合物、3級アミン化合物、アミジン類化合物及びグアニジン類化合物の少なくとも一種であることを特徴とする第1〜3のいずれか1つの態様に記載の感圧接着剤組成物にある。 According to a fourth aspect of the present invention, in any one of the first to third aspects, the amine compound is at least one of a secondary amine compound, a tertiary amine compound, an amidine compound, and a guanidine compound. In a pressure sensitive adhesive composition as described in one embodiment.
本発明の第5の態様は、前記(メタ)アクリル酸エステル系重合体は、前記リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットの割合が10〜50モル%であることを特徴とする第1〜4の何れか1つの態様に記載の感圧接着剤組成物にある。 According to a fifth aspect of the present invention, in the (meth) acrylic acid ester-based polymer, the proportion of repeating units composed of the (meth) acrylic acid ester having a phosphate group is 10 to 50 mol%. The pressure-sensitive adhesive composition according to any one of the first to fourth aspects is characterized.
本発明の第6の態様は、第1〜5の何れか1つの態様に記載の感圧接着剤組成物の架橋物からなる感圧接着剤層にある。 6th aspect of this invention exists in the pressure sensitive adhesive layer which consists of a crosslinked material of the pressure sensitive adhesive composition as described in any one 1st-5th aspect.
本発明の第7の態様は、基材の少なくとも片面に第6の態様に記載の感圧接着剤層を有することを特徴とする感圧接着性積層体にある。 According to a seventh aspect of the present invention, there is provided a pressure-sensitive adhesive laminate comprising the pressure-sensitive adhesive layer according to the sixth aspect on at least one surface of a substrate.
本発明の感圧接着剤組成物は、リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、炭素数1〜18のアルキル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、を含む(メタ)アクリル酸エステル系重合体と、アミン系化合物とを含有させるものであり、難燃性に優れると共に、粘着性及び透明性に優れた感圧接着剤層を形成できるものである。また、かかる感圧接着剤組成物は、粘着物性の低下や被接着体の劣化を防止することができるものである。また、難燃性、粘着性及び透明性を併有した感圧接着剤層及び感圧接着性積層体を提供することができる。 The pressure-sensitive adhesive composition of the present invention includes a repeating unit composed of a (meth) acrylic acid ester having a phosphate ester group and a repeating unit composed of a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms. , A (meth) acrylic acid ester-based polymer, and an amine-based compound, which can form a pressure-sensitive adhesive layer having excellent flame retardancy and excellent tackiness and transparency. is there. Moreover, such a pressure-sensitive adhesive composition can prevent a decrease in pressure-sensitive physical properties and deterioration of an adherend. In addition, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive laminate having both flame retardancy, tackiness, and transparency can be provided.
以下、本発明を(1)感圧接着剤組成物、(2)感圧接着剤層、及び(3)感圧接着性積層体に項分けして詳細に説明する。 Hereinafter, the present invention will be described in detail by classifying into (1) a pressure-sensitive adhesive composition, (2) a pressure-sensitive adhesive layer, and (3) a pressure-sensitive adhesive laminate.
(1)感圧接着剤組成物
本発明の感圧接着剤組成物は、リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、炭素数1〜18のアルキル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、を含む(メタ)アクリル酸エステル系重合体と、アミン系化合物とを含有させてなるものである。
(1) Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of the present invention has a repeating unit composed of (meth) acrylic acid ester having a phosphate ester group and an alkyl group having 1 to 18 carbon atoms (meta ) A (meth) acrylate polymer containing a repeating unit made of an acrylate ester and an amine compound.
なお、(メタ)アクリル酸とは、アクリル酸又はメタクリル酸の総称であり、他の「(メタ)」もこれに準拠する。また、重合体とは、単独重合体及び共重合体の総称であるものとする。 In addition, (meth) acrylic acid is a general term for acrylic acid or methacrylic acid, and other “(meth)” conforms to this. Moreover, a polymer shall be a general term for a homopolymer and a copolymer.
本発明にかかる(メタ)アクリル酸エステル系重合体は、リン酸エステル基を有する(メタ)アクリル酸エステル(以下、「単量体(A)」という)からなる繰返しユニットと、炭素数1〜18のアルキル基を有する(メタ)アクリル酸エステル(以下、「単量体(B)」という)からなる繰返しユニットと、を含むものである。この(メタ)アクリル酸エステル系重合体は、リン酸エステル基を有する(メタ)アクリル酸エステルと、炭素数1〜18のアルキル基を有する(メタ)アクリル酸エステルとを共重合させたものであればよいが、他の単量体を共重合させてもよく、分子内に架橋性官能基を有する単量体と共重合させたものであるのが好ましい。なお、(メタ)アクリル酸エステル系重合体は、適切な官能基を有する(メタ)アクリル酸エステル単量体を重合させて(メタ)アクリル酸エステル系重合体の主鎖部分を形成した後で、前記適切な官能基とリン酸エステル基を有する化合物を反応させて、重合体の主鎖にリン酸エステル基を導入したものであってもよい。 The (meth) acrylic acid ester polymer according to the present invention comprises a repeating unit composed of a (meth) acrylic acid ester having a phosphate group (hereinafter referred to as “monomer (A)”), and a carbon number of 1 to 1. And a repeating unit composed of a (meth) acrylic acid ester having 18 alkyl groups (hereinafter referred to as “monomer (B)”). This (meth) acrylic acid ester polymer is a copolymer of a (meth) acrylic acid ester having a phosphoric acid ester group and a (meth) acrylic acid ester having a C 1-18 alkyl group. However, it may be copolymerized with other monomers, and is preferably copolymerized with a monomer having a crosslinkable functional group in the molecule. The (meth) acrylic acid ester polymer is obtained by polymerizing a (meth) acrylic acid ester monomer having an appropriate functional group to form the main chain portion of the (meth) acrylic acid ester polymer. The compound having a suitable functional group and a phosphate ester group may be reacted to introduce a phosphate ester group into the main chain of the polymer.
単量体(A)からなる繰返しユニットとしては、例えば、下記一般式(1)で表される繰返しユニットが挙げられる。単量体(A)からなる繰返しユニットを含むことにより、難燃性に優れるものとすることができると共に、粘着性及び透明性に優れたものとすることができる。また、下記一般式(1)で表される繰返しユニットを含むことにより、感圧接着剤組成物は、より難燃性に優れたものとなる。 Examples of the repeating unit composed of the monomer (A) include a repeating unit represented by the following general formula (1). By including the repeating unit composed of the monomer (A), the flame retardancy can be improved, and the adhesiveness and transparency can be improved. Moreover, by including the repeating unit represented by the following general formula (1), the pressure-sensitive adhesive composition is more excellent in flame retardancy.
一般式(1)で表される繰返しユニットを形成する単量体(A)の具体例としては、(メタ)アクリロイルオキシエチルジエチルホスフェート、(メタ)アクリロイルオキシエチルジプロピルホスフェート、(メタ)アクリロイルオキシエチルジフェニルホスフェート、(メタ)アクリロイルオキシメチルホスフェート、(メタ)アクリロイルオキシエチルホスフェート、(メタ)アクリロイルオキシプロピルホスフェート、(メタ)アクリロイルオキシペンチルホスフェート、(メタ)アクリロイルオキシヘキシルホスフェートなどを挙げることができる。これらは単独で用いてもよいし、2種以上を組み合わせてもよい。 Specific examples of the monomer (A) that forms the repeating unit represented by the general formula (1) include (meth) acryloyloxyethyl diethyl phosphate, (meth) acryloyloxyethyldipropyl phosphate, (meth) acryloyloxy. Examples thereof include ethyl diphenyl phosphate, (meth) acryloyloxymethyl phosphate, (meth) acryloyloxyethyl phosphate, (meth) acryloyloxypropyl phosphate, (meth) acryloyloxypentyl phosphate, (meth) acryloyloxyhexyl phosphate and the like. These may be used alone or in combination of two or more.
また、単量体(B)としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n−オクチル、(メタ)アクリル酸n−ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシル、(メタ)アクリル酸n−ドデシル、(メタ)アクリル酸n−トリデシル、(メタ)アクリル酸n−テトラデシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸パルミチル、(メタ)アクリル酸ステアリルなどの(メタ)アクリル酸エステル等を挙げることができる。これらは単独で用いてもよいし、2種以上を組み合わせて用いてもよい。単量体(B)からなる繰返しユニットを含むことにより、粘着性に優れた感圧接着剤組成物とすることができる。 The monomer (B) includes methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Pentyl acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate n Nonyl, isononyl (meth) acrylate, decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, myristyl (meth) acrylate (Meth) acrylic acid such as palmitic acid (meth) acrylate and stearyl (meth) acrylate Mention may be made of the ether and the like. These may be used alone or in combination of two or more. By including a repeating unit composed of the monomer (B), a pressure-sensitive adhesive composition having excellent tackiness can be obtained.
他の単量体としては、単量体(A)や単量体(B)と共重合可能な化合物であれば特に制限はないが、分子内に架橋性官能基を有する単量体を共重合させるのが好ましい。 The other monomer is not particularly limited as long as it is a compound copolymerizable with the monomer (A) or the monomer (B), but a monomer having a crosslinkable functional group in the molecule is not limited. Polymerization is preferred.
本発明にかかる(メタ)アクリル酸エステル系重合体は、単量体(A)、(B)及び必要に応じて共重合される他の単量体の少なくとも1つが架橋性官能基を有するようにすることが好ましい。架橋性官能基を有することにより、架橋剤と反応して感圧接着剤層を形成できる。 In the (meth) acrylic acid ester polymer according to the present invention, at least one of the monomers (A) and (B) and other monomers copolymerized as necessary has a crosslinkable functional group. It is preferable to make it. By having a crosslinkable functional group, it can react with a crosslinking agent to form a pressure sensitive adhesive layer.
分子内に架橋性官能基を有する単量体としては、官能基として水酸基、カルボキシル基、イソシアナート基、エポキシ基の少なくとも1種を含むものが好ましい。分子内に架橋性官能基を有する単量体の具体例としては、(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3−ヒドロキシプロピル、(メタ)アクリル酸2−ヒドロキシブチル、(メタ)アクリル酸3−ヒドロキシブチル、(メタ)アクリル酸4−ヒドロキシブチルなどの(メタ)アクリル酸ヒドロキシアルキルエステル;(メタ)アクリル酸モノメチルアミノエチル、(メタ)アクリル酸モノエチルアミノエチル、(メタ)アクリル酸モノメチルアミノプロピル、(メタ)アクリル酸モノエチルアミノプロピルなどの(メタ)アクリル酸モノアルキルアミノアルキル;アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸、シトラコン酸などのエチレン性不飽和カルボン酸などが挙げられる。これらの単量体は単独で用いてもよく、2種以上を組み合わせて用いてもよい。 As the monomer having a crosslinkable functional group in the molecule, those containing at least one of a hydroxyl group, a carboxyl group, an isocyanate group, and an epoxy group as the functional group are preferable. Specific examples of the monomer having a crosslinkable functional group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; monomethylaminoethyl (meth) acrylate, (meth) Monoethylaminoalkyl (meth) acrylates such as monoethylaminoethyl acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itacon Examples thereof include ethylenically unsaturated carboxylic acids such as acid and citraconic acid. These monomers may be used independently and may be used in combination of 2 or more type.
本発明においては、他の単量体としてはさらに、架橋性官能基を有しない単量体を共重合してもよい。このような単量体としては、ビニル安息香酸、スチレン、α−メチルスチレンなどの芳香族ビニル化合物;ビニルグリシジルエーテルなどのビニルエーテル化合物;(メタ)アクリルアミド、N−メチル(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミドなどの(メタ)アクリルアミド化合物;(メタ)アクリロニトリルなどのニトリル化合物;ブタジエン、イソプレンなどが挙げられる。 In the present invention, as the other monomer, a monomer having no crosslinkable functional group may be copolymerized. Examples of such monomers include aromatic vinyl compounds such as vinyl benzoic acid, styrene, and α-methyl styrene; vinyl ether compounds such as vinyl glycidyl ether; (meth) acrylamide, N-methyl (meth) acrylamide, and N-methylol. (Meth) acrylamide compounds such as (meth) acrylamide; Nitrile compounds such as (meth) acrylonitrile; butadiene, isoprene and the like.
本発明に係る(メタ)アクリル酸エステル系重合体は、重量平均分子量(Mw)は、10,000〜1,000,000が好ましく、さらに好ましくは60,000〜900,000である。これにより、ブリードアウトを防止して、粘着物性に優れた感圧接着剤層を形成できる感圧接着剤組成物とすることができる。なお、重量平均分子量はGPC(ゲル・パーミエーション・クロマトグラフィー)により測定して得られたものをいう。 The (meth) acrylic acid ester polymer according to the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 1,000,000, more preferably 60,000 to 900,000. Thereby, it can be set as the pressure sensitive adhesive composition which can prevent a bleed out and can form the pressure sensitive adhesive layer excellent in adhesive physical property. In addition, a weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).
本発明に係る(メタ)アクリル酸エステル系重合体は、単量体(A)の共重合の割合が10〜50モル%であることが好ましく、さらに好ましくは15〜40モル%、特に好ましくは20〜30モル%である。単量体(A)の共重合の割合を10モル%以上とすることにより、難燃性に優れたものとなる。 In the (meth) acrylic acid ester polymer according to the present invention, the copolymerization ratio of the monomer (A) is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, particularly preferably. It is 20-30 mol%. By setting the copolymerization ratio of the monomer (A) to 10 mol% or more, the flame retardancy is excellent.
なお、本発明にかかる(メタ)アクリル酸エステル系重合体は、溶液重合や塊状重合等の任意の公知の重合方法によって製造することができる。重合の際に用いる開始剤の例としては、アゾビスイソブチルニトリル、ベンゾイルパーオキサイド、ジ−t−ブチルパーオキサイド、クメンハイドロパーオキサイドなどが挙げられる。 In addition, the (meth) acrylic acid ester-type polymer concerning this invention can be manufactured by arbitrary well-known polymerization methods, such as solution polymerization and block polymerization. Examples of the initiator used in the polymerization include azobisisobutylnitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like.
共重合体形態については特に限定はなく、ランダム、ブロック、グラフト共重合体のいずれであってもよい。 The form of the copolymer is not particularly limited, and any of random, block, and graft copolymers may be used.
本発明では、アミン系化合物を配合することにより、時間の経過に伴いリン酸エステル基を有する(メタ)アクリル酸エステル系重合体からリン酸系化合物が脱離したとしてもリン酸系化合物をトラップすることができる。 In the present invention, by adding an amine compound, the phosphate compound is trapped even if the phosphate compound is desorbed from the (meth) acrylate polymer having a phosphate group over time. can do.
本発明にかかるアミン系化合物としては、第1級アミン化合物、第2級アミン化合物、第3級アミン化合物、イミダゾール化合物、アミジン化合物、グアニジン化合物等が挙げられる。 Examples of the amine compound according to the present invention include primary amine compounds, secondary amine compounds, tertiary amine compounds, imidazole compounds, amidine compounds, and guanidine compounds.
第1級アミン化合物としては、メチルアミン、エチルアミン、ブチルアミン、S−ブチルアミン、t−ブチルアミン、アミルアミン、オクチルアミン、アリルアミン、エトキシメチルアミン、ベンジルアミン、シクロヘキシルアミン等が挙げられる。第2級アミン化合物としては、ピペリジン、ピペリジン誘導体(例えば、LA−57、LA−67、LA−68LD、LA−77Y;ADEKA社製)、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジアリルアミン、ジヘキシルアミン、ジドデシルアミン、ヘキサメチレンテトラミン等が挙げられる。第3級アミン化合物としては、N,N,N’,N’−テトラメチルエチレンジアミン、1,4−ジアザビシクロ[2.2.2]オクタン、1,8−ジアザビシクロ[5.4.0]ウンデカ−7−エン(DBU)、N−エチルモルホリン、ピペリジン誘導体(例えば、LA−52、LA−62、LA−63P、LA−81;ADEKA社製)、トリメチルアミン、トリエチルアミン、トリプロピルアミン、4−ジメチルアミノピリジン等が挙げられる。イミダゾール化合物としては、N−メチルイミダゾール、2−メチルイミダゾール、N−ビニルイミダゾール、1,2−ジメチルイミダゾール、2−フェニルイミダゾール等が挙げられる。アミジン化合物としては、アセトアミジン、ベンズアミジン、N,N’−ジフェニルホルムアミジン等が挙げられる。グアニジン化合物としては、グアニジン、トリフェニルグアニジン、トリシクロヘキシルグアニジン、1,3−ジシクロヘキシル−2−フェニルグアニジン、1,1,3,3−テトラメチルグアニジン、1,2,3−トリフェニルグアニジン、1,3−ジフェニルグアニジン等が挙げられる。 Examples of the primary amine compound include methylamine, ethylamine, butylamine, S-butylamine, t-butylamine, amylamine, octylamine, allylamine, ethoxymethylamine, benzylamine, cyclohexylamine and the like. As the secondary amine compound, piperidine, piperidine derivatives (for example, LA-57, LA-67, LA-68LD, LA-77Y; manufactured by ADEKA), dimethylamine, diethylamine, dipropylamine, diallylamine, dihexylamine, Examples include didodecylamine and hexamethylenetetramine. Tertiary amine compounds include N, N, N ′, N′-tetramethylethylenediamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undeca- 7-ene (DBU), N-ethylmorpholine, piperidine derivatives (for example, LA-52, LA-62, LA-63P, LA-81; manufactured by ADEKA), trimethylamine, triethylamine, tripropylamine, 4-dimethylamino Examples include pyridine. Examples of the imidazole compound include N-methylimidazole, 2-methylimidazole, N-vinylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole and the like. Examples of amidine compounds include acetamidine, benzamidine, N, N′-diphenylformamidine, and the like. Guanidine compounds include guanidine, triphenylguanidine, tricyclohexylguanidine, 1,3-dicyclohexyl-2-phenylguanidine, 1,1,3,3-tetramethylguanidine, 1,2,3-triphenylguanidine, 1, Examples include 3-diphenylguanidine.
これらの中でも、第2級アミン化合物、第3級アミン化合物、アミジン化合物及びグアニジン化合物が好ましく、特に、第2級アミン化合物、第3級アミン化合物が好ましい。塩基性が強く、脱離等で生成するリン酸系化合物をトラップする能力が高く、粘着物性の経時変化をより抑制することができるためである。 Among these, secondary amine compounds, tertiary amine compounds, amidine compounds and guanidine compounds are preferable, and secondary amine compounds and tertiary amine compounds are particularly preferable. This is because it has a strong basicity and has a high ability to trap phosphoric acid compounds produced by elimination and the like, and it is possible to further suppress changes in adhesive properties over time.
本発明の感圧接着剤組成物は、上述した単量体(A)と単量体(B)とからなる(メタ)アクリル酸エステル系重合体100質量部に対して、アミン系化合物の総量が0.1〜50質量部となるように配合したものであるのが好ましく、1〜30質量部配合したものであるのが特に好ましい。これにより、粘着物性の経時変化がより小さい感圧接着剤層を形成する感圧接着剤組成物とすることができる。なお、(メタ)アクリル酸エステル系重合体に対するアミン系化合物の配合比が低くなりすぎると所望の効果が十分に得られなくなる虞があり、アミン系化合物の配合比が高くなりすぎるとブリードにより、粘着力の低下を招く虞がある。 The pressure-sensitive adhesive composition of the present invention is a total amount of the amine compound with respect to 100 parts by mass of the (meth) acrylic acid ester polymer composed of the monomer (A) and the monomer (B). Is preferably blended so as to be 0.1 to 50 parts by mass, particularly preferably 1 to 30 parts by mass. Thereby, it can be set as the pressure-sensitive-adhesive composition which forms the pressure-sensitive-adhesive layer with a small time-dependent change of adhesive physical property. If the compounding ratio of the amine compound to the (meth) acrylic acid ester polymer is too low, the desired effect may not be sufficiently obtained. If the compounding ratio of the amine compound is too high, bleeding may occur. There is a risk of reducing the adhesive strength.
さらに、感圧接着剤組成物には、必要に応じて、紫外線吸収剤、軟化剤(可塑剤)、硬化促進剤、充填剤、老化防止剤、粘着付与剤、顔料、染料、カップリング剤等の各種添加剤等を添加することができる。粘着付与剤としては、例えば、ロジン及びその誘導体、ポリテルペン、テルペンフェノール樹脂、クマロン−インデン樹脂、石油系樹脂、スチレン樹脂、キシレン樹脂等が挙げられる。軟化剤としては、例えば、液状ポリエーテル、グリコールエステル、液状ポリテルペン、液状ポリアクリレート、フタル酸エステル、トリメリット酸エステル等が挙げられる。 Furthermore, the pressure-sensitive adhesive composition includes an ultraviolet absorber, a softening agent (plasticizer), a curing accelerator, a filler, an anti-aging agent, a tackifier, a pigment, a dye, a coupling agent, and the like as necessary. Various additives can be added. Examples of the tackifier include rosin and derivatives thereof, polyterpene, terpene phenol resin, coumarone-indene resin, petroleum resin, styrene resin, xylene resin and the like. Examples of the softening agent include liquid polyether, glycol ester, liquid polyterpene, liquid polyacrylate, phthalic acid ester, trimellitic acid ester, and the like.
さらに、感圧接着剤組成物は、必要に応じて有機溶剤系等の溶媒を含んでいてもよい。なお、感圧接着剤組成物が溶媒を含む場合、固形成分(リン酸基を有する(メタ)アクリル酸エステル系重合体、架橋剤)の濃度は特に限定されず、所定の基材にそのまま塗工できる濃度であっても、塗工の際に希釈して用いる濃度であってもよい。 Furthermore, the pressure-sensitive adhesive composition may contain a solvent such as an organic solvent as required. When the pressure-sensitive adhesive composition contains a solvent, the concentration of the solid component ((meth) acrylic acid ester-based polymer having a phosphate group, cross-linking agent) is not particularly limited, and is applied directly to a predetermined substrate. Even if it is the density | concentration which can be processed, the density | concentration used by diluting in the case of coating may be sufficient.
かかる溶媒としては、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶媒;酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系溶媒;1,2−ジメトキシエタン、テトラヒドロフラン、1,4−ジオキサンなどのエーテル系溶媒;クロロホルム、四塩化炭素、クロロベンゼンなどのハロゲン系溶媒;ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒;N,N−ジメチルホルムアミド、N,N−ジメチルアセタミド、N−メチルピロリドンなどのアミド系溶媒;ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素系溶媒;シクロペンタン、シクロヘキサンなどの脂環式炭化水素系溶媒;およびこれらの溶媒の2種以上からなる混合溶媒;などが挙げられる。 Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; 1,2-dimethoxyethane, tetrahydrofuran, 1,4- Ether solvents such as dioxane; halogen solvents such as chloroform, carbon tetrachloride and chlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene and xylene; N, N-dimethylformamide, N, N-dimethylacetamide, Amide solvents such as N-methylpyrrolidone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and a mixed solvent composed of two or more of these solvents And so on.
本発明の感圧接着剤組成物は、必要に応じて希釈した後、所定の基材に塗工して、架橋させることにより感圧接着剤層となる。なお、感圧接着剤組成物を塗工する際は、粘度調整のため、これらの有機溶剤等を使用して濃度調整をするのが好ましい。濃度は10〜60質量%の範囲になるように調製するのが好ましい。 After the pressure-sensitive adhesive composition of the present invention is diluted as necessary, it is applied to a predetermined substrate and crosslinked to form a pressure-sensitive adhesive layer. In addition, when applying a pressure sensitive adhesive composition, it is preferable to adjust a density | concentration using these organic solvents etc. for viscosity adjustment. The concentration is preferably adjusted to be in the range of 10 to 60% by mass.
(2)感圧接着剤層
本発明の感圧接着剤層は、上述した感圧接着剤組成物の架橋物からなるものである。
(2) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer of the present invention comprises a crosslinked product of the pressure-sensitive adhesive composition described above.
架橋剤は、種類に特に制限はなく、具体例としては、イソシアネート化合物、エポキシ化合物、金属キレート化合物、メラミン系樹脂、アジリジン化合物、金属アルコキシド、金属塩などが挙げられる。適度な凝集力を得る観点から、イソシアネート化合物やエポキシ化合物が特に好ましく用いられる。これらの化合物は、1種単独で用いても、2種以上を混合して用いてもよい。 The type of the crosslinking agent is not particularly limited, and specific examples include isocyanate compounds, epoxy compounds, metal chelate compounds, melamine resins, aziridine compounds, metal alkoxides, metal salts and the like. From the viewpoint of obtaining an appropriate cohesive force, an isocyanate compound or an epoxy compound is particularly preferably used. These compounds may be used alone or in combination of two or more.
イソシアネート化合物としては、ブチ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などの低級脂肪族ポリイソシアネート類;シクロペンチレンジイソシアネート、シクロヘキシレンジイソシアネート、イソホロンジイソシアネートなどの脂環族イソシアネート類;2,4−トリレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ジイソシアネート類;トリメチロールプロパン/トリレンジイソシアネート3付加物(例えば、日本ポリウレタン工業社製、商品名:コロネートL,東洋インキ社製、商品名:BHS−8515、綜研化学社製、商品名:L−45)、トリメチロールプロパン/ヘキサメチレンジイソシアネート3付加物(例えば、日本ポリウレタン工業社製、商品名:コロネートHL)、ヘキサメチレンジイソシアネートのイソシアヌレート体(例えば、日本ポリウレタン工業社製、商品名:コロネートHX)などのイソシアネート付加物;などが挙げられる。これらのイソシアネート化合物は単独で用いても、2種以上を混合して用いてもよい。 As the isocyanate compound, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, aromatic diisocyanates such as xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate 3 adduct (for example, Nippon Polyurethane Industry, trade name: Coronate L, Toyo Ink, trade name: BHS- 8515, manufactured by Soken Chemical Co., Ltd., trade name: L-45), trimethylolpropane / hexamethylene diisocyanate 3 adduct (for example, Nippon Polyurethane Industry) Ltd., trade name: Coronate HL), an isocyanurate of hexamethylene diisocyanate (for example, Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX) isocyanate adducts and the like; and the like. These isocyanate compounds may be used alone or in combination of two or more.
エポキシ化合物としては、N,N,N’,N’−テトラグリシジル−m−キシレンジアミン(例えば、三菱瓦斯化学社製、商品名:TETRAD−X)や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(例えば、三菱瓦斯化学社製、商品名:TETRAD−C)などとして市販されているものが挙げられる。これらの化合物は1種単独で用いても、2種以上を混合して用いてもよい。 Examples of the epoxy compound include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (for example, Mitsubishi Gas Chemical Company, trade name: TETRAD-X), and 1,3-bis (N, N-dioxy). Examples include glycidylaminomethyl) cyclohexane (for example, trade name: TETRAD-C manufactured by Mitsubishi Gas Chemical Company, Inc.). These compounds may be used alone or in combination of two or more.
これらの架橋剤は、本発明の感圧接着剤組成物に予め含有させておいてもよい。これらの架橋剤の使用量は、本発明にかかるリン酸エステル基を有する(メタ)アクリル酸エステル系重合体100質量部に対して、0.01〜15質量部含有されていることが好ましく、0.5〜5質量部含有されていることがより好ましい。架橋剤を上記範囲とすることにより、良好な密着性と耐久性が得られる。架橋剤の含有量が0.01質量部よりも少ない場合、架橋形成が不十分となり、感圧接着剤組成物の凝集力が小さくなって、糊残りの原因となることがある。一方、含有量が15質量部より多い場合、凝集力が大きくなり、流動性が低下し被着体への濡れが不十分となって、はがれの原因となることがある。 These crosslinking agents may be previously contained in the pressure-sensitive adhesive composition of the present invention. The amount of these crosslinking agents used is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer having a phosphate group according to the present invention, More preferably, 0.5 to 5 parts by mass is contained. By setting the crosslinking agent in the above range, good adhesion and durability can be obtained. When the content of the cross-linking agent is less than 0.01 parts by mass, the cross-linking is insufficient and the cohesive force of the pressure-sensitive adhesive composition is reduced, which may cause adhesive residue. On the other hand, when the content is more than 15 parts by mass, the cohesive force is increased, the fluidity is lowered, the wetness to the adherend is insufficient, and peeling may be caused.
(3)感圧接着性積層体
本発明の感圧接着性積層体は、基材の少なくとも片面に、本発明の感圧接着剤層を有するものである。ここでいう基材は、ベース基材の他、剥離シートを含むものである。
(3) Pressure-sensitive adhesive laminate The pressure-sensitive adhesive laminate of the present invention has the pressure-sensitive adhesive layer of the present invention on at least one side of a substrate. The base material here includes a release sheet in addition to the base base material.
なお、支持体としてのベース基材を有していてもよいし、有していなくてもよい。具体例としては、ベース基材の少なくとも片面に感圧接着剤層を有するものや、ベース基材に替えて、剥離シートの剥離処理面に感圧接着剤層を有するものが挙げられる。また、必要に応じて感圧接着剤層の上に剥離シートを貼着してもよい。剥離シートにより、感圧接着剤層を保護することができる In addition, you may have a base base material as a support body, and it does not need to have it. Specific examples include those having a pressure-sensitive adhesive layer on at least one side of the base substrate, and those having a pressure-sensitive adhesive layer on the release treatment surface of the release sheet instead of the base substrate. Moreover, you may stick a peeling sheet on a pressure sensitive adhesive layer as needed. The release sheet can protect the pressure-sensitive adhesive layer
ベース基材は、特に限定されるものではなく、例えば、ポリビニルアルコール、トリアセチルセルロース、ポリメチルメタクリレート、ポリカーボネート、ポリスルホン系樹脂、ポリノルボルネン系樹脂等のシート状プラスチック材料の他、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリ塩化ビニル、エチレン・酢酸ビニル共重合体、ポリウレタン、ポリスチレン、ポリイミド等の樹脂フィルム、プラスチックフィルムの表面にポリイミド等の樹脂をコーティングしたもの、含浸紙等の紙、金属箔、織布、不織布、又はこれらの積層体が挙げられる。ベース基材は、感圧接着性積層体の用途により、適宜、選択する。このようなベース基材の厚さは、通常6〜300μm、好ましくは12〜200μmである。 The base substrate is not particularly limited. For example, in addition to sheet-like plastic materials such as polyvinyl alcohol, triacetyl cellulose, polymethyl methacrylate, polycarbonate, polysulfone resin, polynorbornene resin, polyethylene, polypropylene, polyethylene Resin film such as terephthalate, polyvinyl chloride, ethylene / vinyl acetate copolymer, polyurethane, polystyrene, polyimide, etc., the surface of plastic film coated with resin such as polyimide, paper such as impregnated paper, metal foil, woven fabric, Nonwoven fabrics or laminates thereof can be mentioned. The base substrate is appropriately selected depending on the use of the pressure-sensitive adhesive laminate. The thickness of such a base substrate is usually 6 to 300 μm, preferably 12 to 200 μm.
剥離シートは、特に限定されるものではなく、紙やフィルム等のシートに、剥離剤で剥離処理したものを使用することができる。紙としては、例えば、グラシン紙のような高密度原紙、クレーコート紙、クラフト紙、または上質紙にポリエチレン等のフィルムをラミネートした紙等が挙げられる。フィルムとしては、例えば、ポリエチレンテレフタレート、ポリプロプレン、ポリエチレン等の樹脂からなるフィルムまたはそれらの発泡フィルムが挙げられる。剥離剤としては、フッ素樹脂、シリコーン樹脂、または長鎖アルキル基含有カルバメート樹脂等が挙げられる。剥離剤を乾燥質量で0.1〜3g/m2程度になるようにシートに塗工し、熱硬化やUV硬化等によって剥離層を設けたものが剥離シートとして適宜使用される。 The release sheet is not particularly limited, and it is possible to use a sheet such as paper or film that has been subjected to a release treatment with a release agent. Examples of the paper include high-density base paper such as glassine paper, clay-coated paper, kraft paper, or paper obtained by laminating a film such as polyethylene on high-quality paper. Examples of the film include a film made of a resin such as polyethylene terephthalate, polypropylene, polyethylene, or a foamed film thereof. Examples of the release agent include a fluororesin, a silicone resin, and a long chain alkyl group-containing carbamate resin. A release agent is suitably used as a release sheet by applying a release agent to a sheet so that the dry mass is about 0.1 to 3 g / m 2 and providing a release layer by heat curing or UV curing.
本発明の感圧接着性積層体の製造方法について説明する。
まず、感圧接着剤組成物を、有機溶剤系により希釈して感圧接着剤組成物塗工液を調製する。
A method for producing the pressure-sensitive adhesive laminate of the present invention will be described.
First, the pressure sensitive adhesive composition is diluted with an organic solvent system to prepare a pressure sensitive adhesive composition coating solution.
そして、得られた感圧接着剤組成物塗工液をベース基材の表面に直接塗工して、ベース基材上に感圧接着剤層を形成してもよいし、剥離シート上に感圧接着剤組成物塗工液を塗布して、感圧接着剤層を形成したのち、これをベース基材に貼着し、該感圧接着剤層をベース基材または別の剥離シートに転写してもよい。感圧接着剤組成物を基材上へ塗布する方法としては特に限定されず、例えばロールナイフコーター、ダイコーター、ロールコーター、バーコーター、グラビアロールコーター、リバースロールコーター、ディッピング等の方法が挙げられる。これらの方法によって感圧接着剤組成物塗工液を塗布した後、溶媒を除去すると共に、架橋を促進させるために感圧接着剤層を加熱処理してもよく、加熱処理温度は、例えば、50〜150℃である。感圧接着剤組成物を架橋してなる感圧接着剤層の厚さは、乾燥状態で1〜200μm程度が好ましく、10〜100μm程度がより好ましい。 Then, the obtained pressure-sensitive adhesive composition coating liquid may be directly applied to the surface of the base substrate to form a pressure-sensitive adhesive layer on the base substrate, or the pressure-sensitive adhesive layer may be formed on the release sheet. A pressure-sensitive adhesive composition coating solution is applied to form a pressure-sensitive adhesive layer, which is then attached to a base substrate, and the pressure-sensitive adhesive layer is transferred to the base substrate or another release sheet. May be. The method for applying the pressure-sensitive adhesive composition onto the substrate is not particularly limited, and examples thereof include a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, and a dipping method. . After applying the pressure-sensitive adhesive composition coating liquid by these methods, the pressure-sensitive adhesive layer may be heat-treated to remove the solvent and promote crosslinking, and the heat treatment temperature is, for example, 50-150 ° C. The thickness of the pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition is preferably about 1 to 200 μm and more preferably about 10 to 100 μm in a dry state.
本発明の感圧接着性積層体は、上述した感圧接着剤組成物の架橋物からなる感圧接着剤層を具備するものであり、難燃性、粘着性及び透明性に優れるものである。感圧接着剤組成物における感圧接着剤層は、好ましくは、JIS K 7136規格に準拠して測定されるヘイズ値が5%以下である。 The pressure-sensitive adhesive laminate of the present invention comprises a pressure-sensitive adhesive layer composed of a crosslinked product of the pressure-sensitive adhesive composition described above, and is excellent in flame retardancy, tackiness and transparency. . The pressure-sensitive adhesive layer in the pressure-sensitive adhesive composition preferably has a haze value of 5% or less measured according to JIS K 7136 standard.
本発明の感圧接着性積層体は電子部材、またはそれらを構成する材料として好適に使用できるものである。また、電気製品の外装、建築材料、自動車部品、火気取り扱い現場のラベル等に用いて好適なものである。 The pressure-sensitive adhesive laminate of the present invention can be suitably used as an electronic member or a material constituting them. Moreover, it is suitable for use in exteriors of electrical products, building materials, automobile parts, labels for handling fire, and the like.
以下、実施例及び比較例により本発明をさらに具体的に説明するが、これらは本発明の範囲を何ら制限するものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, these do not restrict | limit the scope of the present invention at all.
(実施例1)
攪拌機、還流冷却器、窒素導入口、及び温度計を取り付けた反応容器に、単量体(B)としてアクリル酸n−ブチル47質量部(0.36モル)、アクリル酸2−ヒドロキシエチル3質量部(0.025モル)、単量体(A)としてメタクリロイルオキシエチルジフェニルホスフェート(大八化学工業製:MR−260)50質量部(0.13モル)、アゾビスイソブチロニトリル0.3質量部、酢酸エチル150質量部を投入し、常温で1時間かけて窒素置換をした。その後、70℃に昇温し、8時間重合を行った。得られた重合体をGPC(ポリスチレン換算)にて分子量測定を行ったところ、重量平均分子量(Mw)が650,000であった。
Example 1
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet, and thermometer, 47 parts by mass (0.36 mol) of n-butyl acrylate as monomer (B), 3 mass of 2-hydroxyethyl acrylate Parts (0.025 mol), methacryloyloxyethyl diphenyl phosphate (manufactured by Daihachi Chemical Industry: MR-260) as a monomer (A) 50 parts by mass (0.13 mol), azobisisobutyronitrile 0.3 Part by mass and 150 parts by mass of ethyl acetate were added, and nitrogen substitution was performed at room temperature for 1 hour. Then, it heated up at 70 degreeC and superposition | polymerization was performed for 8 hours. When the obtained polymer was subjected to molecular weight measurement by GPC (polystyrene conversion), the weight average molecular weight (Mw) was 650,000.
得られた重合溶液100質量部に対して、イソシアナート系架橋剤(東洋インキ製造社製:BHS8515、固形分37.5質量%)1.0質量部、アミン系化合物として、1,4−ジアザビシクロ[2.2.2]オクタン(和光純薬製:固形分100質量%)0.4質量部を加え、感圧接着剤組成物を得た。 With respect to 100 parts by mass of the resulting polymerization solution, 1.0 part by mass of an isocyanate-based crosslinking agent (manufactured by Toyo Ink Manufacturing Co., Ltd .: BHS8515, solid content 37.5% by mass), 1,4-diazabicyclo as an amine compound [2.2.2] Octane (manufactured by Wako Pure Chemical Industries, Ltd .: 100% by mass) 0.4 parts by mass was added to obtain a pressure-sensitive adhesive composition.
この組成物を厚さ50μmのポリエチレンテレフタレート(PET)フィルム(東レ社製:ルミラー50T60)にアプリケーターを用いて塗布し、90℃で1分間加熱・乾燥することにより、厚さ約20μmの感圧接着剤層とし、この層の面に剥離フィルム(リンテック社製:PET381031)をラミネートし、感圧接着性積層体を作製した。 This composition is applied to a polyethylene terephthalate (PET) film (Toray Co., Ltd .: Lumirror 50T60) with a thickness of 50 μm using an applicator, heated and dried at 90 ° C. for 1 minute, and pressure-sensitive adhesive with a thickness of about 20 μm. A pressure sensitive adhesive laminate was prepared by laminating a release film (PIN 381031 manufactured by Lintec Corporation) on the surface of this layer.
(実施例2)
1,4−ジアザビシクロ[2.2.2]オクタンの代わりに、ピペリジン誘導体(ADEKA社製:LA−63P、固形分100質量%)0.4質量部用いた以外は実施例1と同様にして、感圧接着性積層体を作製した。
(Example 2)
Instead of 1,4-diazabicyclo [2.2.2] octane, a piperidine derivative (manufactured by ADEKA: LA-63P, solid content: 100% by mass) was used in the same manner as in Example 1 except that 0.4 parts by mass was used. A pressure sensitive adhesive laminate was prepared.
(実施例3)
1,4−ジアザビシクロ[2.2.2]オクタンの代わりに、2−メチルイミダゾール(和光純薬社製:固形分100質量%)0.4質量部用いた以外は実施例1と同様にして、感圧接着性積層体を作製した。
(Example 3)
Instead of 1,4-diazabicyclo [2.2.2] octane, the same procedure as in Example 1 was carried out except that 0.4 parts by mass of 2-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd .: solid content: 100% by mass) was used. A pressure sensitive adhesive laminate was prepared.
(実施例4)
1,4−ジアザビシクロ[2.2.2]オクタンの代わりに、ピペリジン誘導体(ADEKA社製:LA−63P、固形分100質量%)4質量部用いた以外は実施例1と同様にして、感圧接着性積層体を作製した。
Example 4
In the same manner as in Example 1 except that 4 parts by mass of a piperidine derivative (ADEKA: LA-63P, solid content: 100% by mass) was used instead of 1,4-diazabicyclo [2.2.2] octane. A pressure-bonding laminate was produced.
(実施例5)
アクリル酸n−ブチルの代わりにアクリル酸2−エチルヘキシル47質量部を使用した以外は実施例1と同様にして、感圧接着性積層体を作製した。
(Example 5)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that 47 parts by mass of 2-ethylhexyl acrylate was used instead of n-butyl acrylate.
(実施例6)
PETフィルムの代わりに厚み25μmのポリイミド(PI)フィルム(東レ・デュポン社製:カプトン100H)を用いた以外は実施例1と同様にして、感圧接着性積層体を作製した。
(Example 6)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that a polyimide (PI) film having a thickness of 25 μm (manufactured by Toray DuPont: Kapton 100H) was used instead of the PET film.
(実施例7)
PETフィルムの代わりに厚み25μmのPIフィルム(東レ・デュポン社製:カプトン100H)を用いた以外は実施例2と同様にして、感圧接着性積層体を作製した。
(Example 7)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 2 except that a 25 μm thick PI film (manufactured by Toray DuPont: Kapton 100H) was used instead of the PET film.
(実施例8)
PETフィルムの代わりに厚み25μmのPIフィルム(東レ・デュポン社製:カプトン100H)を用いた以外は実施例3と同様にして、感圧接着性積層体を作製した。
(Example 8)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 3 except that a 25 μm-thick PI film (manufactured by Toray DuPont: Kapton 100H) was used instead of the PET film.
(実施例9)
PETフィルムの代わりに厚み25μmのPIフィルム(東レ・デュポン社製:カプトン100H)を用いた以外は実施例4と同様にして、感圧接着性積層体を作製した。
Example 9
A pressure-sensitive adhesive laminate was prepared in the same manner as in Example 4 except that a 25 μm thick PI film (Toray DuPont: Kapton 100H) was used instead of the PET film.
(実施例10)
PETフィルムの代わりに厚み25μmのPIフィルム(東レ・デュポン社製:カプトン100H)を用いた以外は実施例5と同様にして、感圧接着性積層体を作製した。
(Example 10)
A pressure-sensitive adhesive laminate was prepared in the same manner as in Example 5 except that a 25 μm-thick PI film (manufactured by Toray DuPont: Kapton 100H) was used instead of the PET film.
(比較例1)
攪拌機、還流冷却器、窒素導入口、及び温度計を取り付けた反応容器にアクリル酸n−ブチル45質量部、アクリル酸2−エチルヘキシル50質量部、アクリル酸3質量部、アクリル酸2−ヒドロキシエチル2質量部、アゾビスイソブチロニトリル0.3質量部、酢酸エチル150質量部を投入し、1時間かけて窒素置換をした。その後、60℃に昇温し8時間重合を行った。得られた重合体のMwは600,000であった。得られた重合溶液100質量部に対して、トリレンジイソシアナート系架橋剤(東洋インキ製造社製:BHS8515、固形分濃度37.5質量%)1質量部と、リン酸エステル系難燃剤(ビスフェノールAビス(ジフェニルホスフェート)(大八化学社製:CR−741、固形分100質量%)10質量部とを加え、感圧接着剤組成物を得た。
(Comparative Example 1)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet, and thermometer, 45 parts by mass of n-butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 3 parts by mass of acrylic acid, 2-hydroxyethyl acrylate 2 Part by mass, 0.3 part by mass of azobisisobutyronitrile, and 150 parts by mass of ethyl acetate were added, and nitrogen substitution was performed over 1 hour. Then, it heated up at 60 degreeC and superposed | polymerized for 8 hours. Mw of the obtained polymer was 600,000. To 100 parts by mass of the obtained polymerization solution, 1 part by mass of tolylene diisocyanate crosslinking agent (Toyo Ink Manufacturing Co., Ltd .: BHS8515, solid content concentration 37.5% by mass) and phosphate ester flame retardant (bisphenol) 10 parts by mass of A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd .: CR-741, solid content 100% by mass) was added to obtain a pressure-sensitive adhesive composition.
この組成物を厚さ50μmのポリエチレンテレフタレート(PET)フィルム(東レ社製:ルミラー50T60)にアプリケーターを用いて塗布し、90℃で1分間加熱・乾燥することにより、厚さ約20μmの感圧接着剤層とし、この層の面に剥離フィルム(リンテック社製:PET381031)をラミネートし、感圧接着性積層体を作製した。 This composition is applied to a polyethylene terephthalate (PET) film (Toray Co., Ltd .: Lumirror 50T60) with a thickness of 50 μm using an applicator, heated and dried at 90 ° C. for 1 minute, and pressure-sensitive adhesive with a thickness of about 20 μm. A pressure sensitive adhesive laminate was prepared by laminating a release film (PIN 381031 manufactured by Lintec Corporation) on the surface of this layer.
(比較例2)
リン酸エステル系難燃剤を20質量部とした以外は比較例1と同様にして、感圧接着性積層体を作製した。
(Comparative Example 2)
A pressure-sensitive adhesive laminate was produced in the same manner as in Comparative Example 1 except that the phosphate ester flame retardant was changed to 20 parts by mass.
(比較例3)
1,4−ジアザビシクロ[2.2.2]オクタンを使用しない以外は、実施例1と同様にして、感圧接着性積層体を作成した。
(Comparative Example 3)
A pressure-sensitive adhesive laminate was prepared in the same manner as in Example 1 except that 1,4-diazabicyclo [2.2.2] octane was not used.
(比較例4)
PETフィルムの代わりに厚さ25μmのポリイミド(PI)フィルム(東レ・デュポン社製:カプトン100H)を用いた以外は、比較例1と同様に感圧接着性積層体を作製した。
(Comparative Example 4)
A pressure-sensitive adhesive laminate was prepared in the same manner as in Comparative Example 1 except that a polyimide (PI) film having a thickness of 25 μm (Toray DuPont: Kapton 100H) was used instead of the PET film.
(比較例5)
PETフィルムの代わりに厚さ25μmのポリイミド(PI)フィルム(東レ・デュポン社製:カプトン100H)を用いた以外は、比較例2と同様に感圧接着性積層体を作製した。
(Comparative Example 5)
A pressure-sensitive adhesive laminate was prepared in the same manner as in Comparative Example 2 except that a polyimide (PI) film (Toray DuPont: Kapton 100H) having a thickness of 25 μm was used instead of the PET film.
(比較例6)
PETフィルムの代わりに厚さ25μmのポリイミド(PI)フィルム(東レ・デュポン社製:カプトン100H)を用いた以外は、比較例3と同様に感圧接着性積層体を作製した。
(Comparative Example 6)
A pressure-sensitive adhesive laminate was prepared in the same manner as in Comparative Example 3 except that a polyimide (PI) film having a thickness of 25 μm (manufactured by Toray DuPont: Kapton 100H) was used instead of the PET film.
上記の各実施例及び各比較例の感圧接着性積層体の評価を、以下のようにして行った。その結果をベース基材にPETフィルムを用いたものを表1に、PIフィルムを用いたものを表2に示す。 Evaluation of the pressure-sensitive adhesive laminates of the above Examples and Comparative Examples was performed as follows. The results are shown in Table 1 for the base substrate using the PET film and Table 2 for the PI film.
<難燃性評価>
燃焼性試験は、感圧接着性積層体の剥離フィルムを剥離し、アンダーライターズラボラトリーズ社発行のプラスチック材料の燃焼性試験規格UL94の垂直燃焼試験方法に基づいてUL94VTMランクを判定した。
<Flame retardance evaluation>
In the flammability test, the release film of the pressure-sensitive adhesive laminate was peeled off, and the UL94VTM rank was determined based on the vertical flammability test method of the flammability test standard UL94 issued by Underwriters Laboratories.
<粘着力変化>
感圧接着性積層体を、23℃×50%RH、及び70℃×Dry7日間促進後のSUS板に対する粘着力をJIS Z 0237に準拠して測定した。そして、その粘着力の変化率を算出した。なお、試験用感圧接着性積層体の粘着力の変化率が、20%未満であった場合を○、20〜50%であった場合を△、50%以上を×として評価した。
<Adhesive strength change>
The pressure-sensitive adhesive laminate was measured for adhesion to an SUS plate after being accelerated at 23 ° C. × 50% RH and 70 ° C. × Dry for 7 days according to JIS Z 0237. And the change rate of the adhesive force was computed. In addition, the case where the change rate of the adhesive force of the pressure-sensitive adhesive laminate for test was less than 20% was evaluated as ◯, the case where it was 20 to 50% was evaluated as Δ, and 50% or more was evaluated as ×.
<透明性評価>
感圧接着性積層体の剥離フィルムを剥離し、PETフィルムを基材とした感圧接着性積層体の感圧接着剤層のヘイズ値を、可視光透過率測定装置(日本電色工業株式会社製、ヘイズメーターNDH2000)を使用し、JIS K 7136規格に準拠して測定した。なお、光線入射面は、感圧接着剤層面とした。
<Transparency evaluation>
The release film of the pressure-sensitive adhesive laminate is peeled off, and the haze value of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive laminate based on the PET film is measured using a visible light transmittance measuring device (Nippon Denshoku Industries Co., Ltd.). Manufactured by Haze Meter NDH2000) and measured according to JIS K 7136 standard. The light incident surface was the pressure sensitive adhesive layer surface.
(結果のまとめ)
ベース基材としてPETフィルムを用いた実施例1〜5の感圧接着性積層体は、難燃性評価判定がVTM−2であり、難燃性に優れるものであり、粘着力の変化率が20%未満であった。また、ヘイズ値は1.2%以下であり、透明性に優れたものであった。
(Summary of results)
The pressure-sensitive adhesive laminates of Examples 1 to 5 using a PET film as the base substrate have a flame retardancy evaluation determination of VTM-2, which is excellent in flame retardancy, and the rate of change in adhesive strength is It was less than 20%. Further, the haze value was 1.2% or less, and the transparency was excellent.
これに対し、アミン系化合物を含まない比較例3及び比較例6の感圧接着性積層体は、促進条件後の粘着力の低下が大きかった。これは、リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットからリン酸系化合物が脱離したためと考えられる。また、リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットやアミン系化合物いずれも含まず、リン酸エステル系難燃剤の配合量が少ない比較例1及び比較例4は、促進条件後の粘着力の低下が大きく、リン酸エステル系難燃剤のブリードアウトにより粘着力が低下したと考えられる。さらに、リン酸エステル系難燃剤を多く配合した比較例2及び比較例5では、難燃性に優れるものの、感圧接着剤とリン酸エステル系難燃剤が相溶しないため、難燃剤が感圧接着剤中に局在化してしまい粘着力が低く、使用できるものではなかった。 On the other hand, the pressure-sensitive adhesive laminates of Comparative Example 3 and Comparative Example 6 that did not contain an amine compound had a large decrease in adhesive strength after the accelerating conditions. This is presumably because the phosphate compound was eliminated from the repeating unit consisting of (meth) acrylic acid ester having a phosphate ester group. In addition, Comparative Example 1 and Comparative Example 4 that do not include any repeating unit or amine compound composed of (meth) acrylic acid ester having a phosphate ester group and have a small amount of the phosphate ester flame retardant are after the promotion conditions. It is considered that the adhesive strength was greatly reduced and the adhesive strength was reduced by bleeding out of the phosphate ester flame retardant. Furthermore, in Comparative Example 2 and Comparative Example 5 in which a large amount of phosphate ester flame retardant is blended, although the flame retardant is excellent, the pressure sensitive adhesive and the phosphate ester flame retardant are not compatible, so the flame retardant is pressure sensitive. Since it was localized in the adhesive, the adhesive strength was low and it could not be used.
また、ベース基材としてPIフィルムを用いた実施例6〜10の感圧接着性積層体は、非常に難燃性に優れ、粘着力の変化がないものであり、また、凝集物は確認されなかった。 In addition, the pressure-sensitive adhesive laminates of Examples 6 to 10 using a PI film as a base substrate are very excellent in flame retardancy and have no change in adhesive strength, and no agglomerates are confirmed. There wasn't.
以上より、リン酸エステル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、炭素数1〜18のアルキル基を有する(メタ)アクリル酸エステルからなる繰返しユニットと、を含む(メタ)アクリル酸エステル系重合体と、アミン系化合物と、を含む感圧接着剤組成物は、難燃性に優れると共に、粘着性及び透明性に優れ、経時的な粘着物性の低下がほとんどないものであることがわかった。
As mentioned above, (meth) acrylic acid containing the repeating unit which consists of a (meth) acrylic acid ester which has a phosphate ester group, and the repeating unit which consists of a C1-C18 alkyl group (meth) acrylic acid ester A pressure-sensitive adhesive composition containing an ester polymer and an amine compound is excellent in flame retardancy, excellent in tackiness and transparency, and hardly deteriorates in adhesive properties over time. I understood.
Claims (7)
アミン系化合物と、
を含むことを特徴とする感圧接着剤組成物。 A (meth) acrylic acid ester-based polymer comprising a repeating unit composed of a (meth) acrylic acid ester having a phosphoric acid ester group and a repeating unit composed of a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms. Coalescence,
An amine compound,
A pressure-sensitive adhesive composition comprising:
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JP2001261723A (en) * | 2000-03-23 | 2001-09-26 | Denki Kagaku Kogyo Kk | Flame-retarded resin composition, flame-retarded adhesive composition and metallic joined product |
JP2007046018A (en) * | 2005-08-12 | 2007-02-22 | Denki Kagaku Kogyo Kk | Pressure-sensitive adhesive, pressure-sensitive adhesive sheet obtained using the same, and manufacturing method of electronic component using pressure-sensitive adhesive sheet |
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JP2001261723A (en) * | 2000-03-23 | 2001-09-26 | Denki Kagaku Kogyo Kk | Flame-retarded resin composition, flame-retarded adhesive composition and metallic joined product |
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US20180022967A1 (en) * | 2014-12-30 | 2018-01-25 | 3M Innovative Properties Company | Halogen-free flame retardant pressure sensitive adhesive and tape |
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