JP2011116831A - 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
- JP2011116831A JP2011116831A JP2009273990A JP2009273990A JP2011116831A JP 2011116831 A JP2011116831 A JP 2011116831A JP 2009273990 A JP2009273990 A JP 2009273990A JP 2009273990 A JP2009273990 A JP 2009273990A JP 2011116831 A JP2011116831 A JP 2011116831A
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- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- mass
- 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 136
- 239000010410 layer Substances 0.000 title claims abstract description 41
- -1 amine compound Chemical class 0.000 claims abstract description 74
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 28
- 239000010452 phosphate Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000011243 crosslinked material Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 16
- 125000002270 phosphoric acid ester group Chemical group 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 64
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 34
- 239000004642 Polyimide Substances 0.000 description 24
- 229920001721 polyimide Polymers 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000003063 flame retardant Substances 0.000 description 16
- 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 14
- 150000001875 compounds Chemical class 0.000 description 14
- 229920002799 BoPET Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 125000000524 functional group Chemical group 0.000 description 10
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 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 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 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
- 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
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 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 compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- 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
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 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
- 239000012790 adhesive layer Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 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
- 230000006866 deterioration Effects 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003097 polyterpenes Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UPPUJFRSINZXTE-UHFFFAOYSA-N (2,2,3,3,4-pentamethylpiperidin-1-yl) 2-methylprop-2-enoate Chemical compound CC1CCN(OC(=O)C(C)=C)C(C)(C)C1(C)C UPPUJFRSINZXTE-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 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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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
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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、アミン系化合物及び特定のアミド系化合物から選択される少なくとも１つとを共重合させることにより、難燃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 found that a (meth) acrylic acid ester having a phosphate ester group and a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms Pressure-sensitive adhesive composition and pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer excellent in flame retardancy and transparency by copolymerizing with at least one selected from amine compounds and specific amide compounds The inventors have found that a pressure-sensitive adhesive laminate having an adhesive layer can be obtained, and completed the present invention.
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（Ａ）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（Ｂ）からなる繰返しユニットと、前記（Ａ）及び前記（Ｂ）と共重合可能であるアミン系化合物、ジメチル（メタ）アクリルアミド、アクリロイルモルフォリンからなる群から選択される少なくとも１つ（Ｃ）と、を含む（メタ）アクリル酸エステル系重合体を含むことを特徴とする感圧接着剤組成物にある。 The 1st aspect of this invention which solves the said subject is a (meth) acrylic acid which has a repeating unit which consists of (meth) acrylic acid ester (A) which has a phosphate ester group, and a C1-C18 alkyl group. A repeating unit comprising an ester (B) and at least one selected from the group consisting of an amine compound, dimethyl (meth) acrylamide, and acryloylmorpholine copolymerizable with the above (A) and (B) (C And a (meth) acrylic acid ester-based polymer.
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は、前記（Ａ）を１０〜９４．９質量％、前記（Ｂ）を５〜７０質量％、前記（Ｃ）を０．１〜２０質量％用いて共重合させ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。 According to a second aspect of the present invention, the (meth) acrylic acid ester-based polymer contains 10-94.9% by mass of the (A), 5-70% by mass of the (B), and (C). The pressure-sensitive adhesive composition according to the first aspect, which is copolymerized using 0.1 to 20% by mass.
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に記載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 group is represented by the following general formula (1). The pressure-sensitive adhesive composition according to the embodiment.
本発明の第４の態様は、第１〜３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。 The 4th 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-3rd aspect.
本発明の第５の態様は、基材の少なくとも片面に第４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 fifth aspect of the present invention, there is provided a pressure-sensitive adhesive laminate comprising the pressure-sensitive adhesive layer according to the fourth 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、アミン系化合物及び特定のアミド系化合物から選択される少なくとも１つとを共重合させることにより、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 (meth) acrylic acid ester having a phosphate ester group, a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms, an amine compound, and a specific amide. By copolymerizing at least one selected from a system compound, a pressure-sensitive adhesive layer having excellent flame retardancy and excellent tackiness and transparency can be formed. 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（Ａ）（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（Ｂ）（以下、「単量体（Ｂ）」という）からなる繰返しユニットと、（Ａ）及び（Ｂ）と共重合可能であるアミン系化合物、ジメチル（メタ）アクリルアミド、アクリロイルモルフォリンからなる群から選択される少なくとも１つ（Ｃ）（以下、「単量体（Ｃ）」という）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からなるものである。
(1) Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of the present invention comprises (meth) acrylic acid ester (A) having a phosphate ester group (hereinafter referred to as “monomer (A)”). A repeating unit comprising a repeating unit, a (meth) acrylic acid ester (B) having an alkyl group having 1 to 18 carbon atoms (hereinafter referred to as “monomer (B)”), (A) and (B) A repeating unit comprising at least one (C) (hereinafter referred to as “monomer (C)”) selected from the group consisting of a copolymerizable amine compound, dimethyl (meth) acrylamide, and acryloylmorpholine; A (meth) acrylic acid ester-based polymer.
本発明の感圧接着剤組成物は、従来の固体のリン酸エステルを難燃剤として添加した場合のように凝集物が生じることがなく、難燃性と透明性とを併有する感圧接着剤層を形成できるものである。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。 The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive that has both flame retardancy and transparency without the formation of aggregates as in the case of adding a conventional solid phosphate ester as a flame retardant. A layer can be formed. 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、単量体（Ａ）からなる繰返しユニットと、単量体（Ｂ）からなる繰返しユニットと、単量体（Ａ）及び単量体（Ｂ）と共重合可能である単量体（Ｃ）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、単量体（Ａ）と、単量体（Ｂ）と、単量体（Ａ）及び単量体（Ｂ）と共重合可能である単量体（Ｃ）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 includes a repeating unit composed of the monomer (A), a repeating unit composed of the monomer (B), the monomer (A) and the monomer ( B) and a repeating unit composed of the monomer (C) that can be copolymerized. This (meth) acrylic ester polymer is a monomer (A), a monomer (B), a monomer copolymerizable with the monomer (A) and the monomer (B). (C) may be copolymerized with other monomers, but other monomers may be copolymerized with those having a crosslinkable functional group in the molecule. Is preferred. 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.
本発明にかかる（メタ）アクリル酸エステル系重合体は、アミン系化合物を共重合させているため、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、塩基性であるアミン系化合物や特定のアミド系化合物からなる繰返しユニットがリン酸系化合物をトラップすることができる。これにより、経時的な粘着物性の低下が抑制される。このように、アミン系化合物や特定のアミド系化合物が共重合されているため、ブリードアウトをして被接着体の可塑化を招く虞がない。 Since the (meth) acrylic acid ester polymer according to the present invention is copolymerized with an amine compound, it is changed from a (meth) acrylic acid ester polymer having a phosphoric acid ester group over time to a phosphoric acid type. Even if the compound is eliminated, a repeating unit composed of a basic amine compound or a specific amide compound can trap the phosphate compound. Thereby, the fall of the adhesive physical property with time is suppressed. Thus, since the amine compound and the specific amide compound are copolymerized, there is no possibility of bleeding out and causing plasticization of the adherend.
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.
単量体（Ｃ）としては、単量体（Ａ）及び単量体（Ｂ）と共重合可能であるアミン系化合物、ジメチル（メタ）アクリルアミド、アクリロイルモルフォリンからなる群から選択される少なくとも１つである。単量体（Ｃ）からなる繰返しユニットを含むことにより、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、塩基性であるアミン系化合物や特定のアミド系化合物からなる繰返しユニットがリン酸系化合物をトラップすることができる。アミン系化合物としては、アミノエチル（メタ）アクリレート、モノメチルアミノエチル（メタ）アクリレート、モノエチルアミノエチル（メタ）アクリレート、モノメチルアミノプロピル（メタ）アクリレート、モノエチルアミノプロピル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ペンタメチルピペリジル（メタ）アクリレート、テトラメチルピペリジル（メタ）アクリレート、ビニルカルバゾール、１−ビニルイミダゾール等が挙げられる。時間の経過に伴いリン酸系化合物が脱離したとしても、塩基性であるアミン系化合物や特定のアミド系化合物からなる繰返しユニットが、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、ジメチル（メタ）アクリルアミド、アクリロイルモルフォリン、ジメチルアミノエチル（メタ）アクリレートが好ましい。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。 The monomer (C) is at least one selected from the group consisting of the monomer (A) and an amine compound copolymerizable with the monomer (B), dimethyl (meth) acrylamide, and acryloylmorpholine. One. By including a repeating unit composed of the monomer (C), even if the phosphate compound is eliminated from the (meth) acrylate polymer having a phosphate group with the passage of time, it is basic. A repeating unit composed of a certain amine compound or a specific amide compound can trap the phosphate compound. As amine compounds, aminoethyl (meth) acrylate, monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, vinylcarbazole, 1-vinylimidazole and the like can be mentioned. Even if the phosphate compound is eliminated over time, the repeating unit consisting of a basic amine compound or a specific amide compound has the ability to trap the phosphate compound generated by elimination. Dimethyl (meth) acrylamide, acryloylmorpholine, and dimethylaminoethyl (meth) acrylate are preferred because they are high and can suppress the change in adhesive properties over time. These may be used alone or in combination of two or more.
他の単量体としては、単量体（Ａ）、（Ｂ）、（Ｃ）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 monomers (A), (B), and (C), but a monomer having a crosslinkable functional group in the molecule is used. Copolymerization is preferred.
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；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; acrylic acid, methacrylic acid, crotonic acid, maleic acid, And ethylenically unsaturated carboxylic acids such as itaconic 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、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、イソプレンなどの共役ジエン系化合物等が挙げられる。 In the present invention, as another 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-methylstyrene; vinyl ether compounds such as vinyl glycidyl ether; nitrile compounds such as (meth) acrylonitrile; conjugated dienes such as butadiene and isoprene. System compounds and the like.
本発明にかかる（メタ）アクリル酸エステル系重合体は、（Ａ）、（Ｂ）及び（Ｃ）に加えて、さらに、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 addition to (A), (B) and (C), the (meth) acrylic acid ester polymer according to the present invention is further crosslinked with at least one of other monomers copolymerized as necessary. It is preferable to have a functional group. By having a crosslinkable functional group, it can react with a crosslinking agent to form a pressure sensitive adhesive layer.
本発明にかかる（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).
本発明にかかる（メタ）アクリル酸エステル系重合体は、（Ａ）を１０〜９４．９質量％、（Ｂ）を５〜７０質量％、（Ｃ）を０．１〜２０質量％の割合で共重合させたものであるのが好ましい。これにより、さらに、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を抑えたものとすることができる。リン酸エステル基を有する（メタ）アクリル酸エステル（Ａ）の割合が低くなりすぎると難燃性の効果が十分得られなくなる虞があり、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（Ｂ）の割合が低くなりすぎると粘着性が低くなる虞がある。また、（Ｃ）の割合が高くなりすぎると、得られる感圧接着剤組成物が黄変しやすくなったり、共重合が阻害され分子量が低下したりする虞がある。 The (meth) acrylic acid ester-based polymer according to the present invention has a ratio of (A) of 10 to 94.9% by mass, (B) of 5 to 70% by mass, and (C) of 0.1 to 20% by mass. It is preferable that the copolymer is copolymerized with. Thereby, while being excellent in a flame retardance, it is excellent in adhesiveness and transparency, and can suppress the fall of the adhesive physical property with time. If the proportion of the (meth) acrylic acid ester (A) having a phosphoric ester group is too low, the flame retardancy effect may not be sufficiently obtained, and the (meth) acrylic having a C 1-18 alkyl group If the ratio of the acid ester (B) is too low, the tackiness may be lowered. Moreover, when the ratio of (C) becomes too high, the resulting pressure-sensitive adhesive composition may be easily yellowed, or copolymerization may be inhibited and the molecular weight may be reduced.
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.
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（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、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. In the case where the pressure-sensitive adhesive composition contains a solvent, the concentration of the solid component (the (meth) acrylic acid ester-based polymer having a phosphate ester group according to the present invention, a crosslinking agent) is not particularly limited. Even if it is the density | concentration which can be applied to a base material as it is, 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を調整するのが好ましい。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.
本発明の感圧接着剤組成物は、単量体（Ａ）及び単量体（Ｂ）を共重合させているため、難燃性に優れると共に粘着性及び透明性に優れるものであり、さらに、単量体（Ｃ）を共重合させているため、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、塩基性であるアミン系化合物や特定のアミド系化合物からなる繰返しユニットがリン酸系化合物をトラップすることができ、経時的な粘着物性の低下が抑制されたものである。このように、本発明の感圧接着剤組成物は、（メタ）アクリル酸エステル系重合体にアミン系化合物や特定のアミド系化合物が共重合されているため、ブリードアウトをして被接着体の可塑化を招く虞がない。 Since the pressure-sensitive adhesive composition of the present invention is copolymerized with the monomer (A) and the monomer (B), it is excellent in flame retardancy and adhesiveness and transparency, Since the monomer (C) is copolymerized, even if the phosphate compound is eliminated from the (meth) acrylate polymer having a phosphate group with the passage of time, it is basic. A repeating unit composed of a certain amine compound or a specific amide compound can trap the phosphate compound, and the deterioration of the adhesive property over time is suppressed. As described above, the pressure-sensitive adhesive composition of the present invention has a (meth) acrylic acid ester polymer copolymerized with an amine compound or a specific amide compound. There is no risk of causing plasticization.
（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, product name: Coronate L, product name: Coronate L, product name: BHS-, manufactured by Nippon Polyurethane Industry Co., Ltd.) 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 pressure sensitive adhesive layer can be protected by the release sheet.
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、ポリプロピレン、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、フッ素樹脂やシリコーン樹脂、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. As a film, the film which consists of resin, such as a polyethylene terephthalate, a polypropylene, polyethylene, or those foamed films is mentioned, for example. 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。 A method for producing the pressure-sensitive adhesive laminate of the present invention will be described.
まず、感圧接着剤組成物を、有機溶剤等により希釈して感圧接着剤組成物塗工液を調製する。 First, the pressure sensitive adhesive composition is diluted with an organic solvent 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布して、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。感圧接着剤組成物塗工液を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、特に制限されず、用途に応じて適宜選定されるが、通常、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. After applying the adhesive composition coating liquid to form a pressure sensitive adhesive layer, this is applied to the base substrate, and the pressure sensitive adhesive layer is transferred to the base substrate or another release sheet. Also good. The method for applying the pressure-sensitive adhesive composition coating solution 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 in order to remove the solvent and promote cross-linking. , 50-150 ° C. The thickness of the pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition is not particularly limited and is appropriately selected depending on the application, but is usually preferably about 1 to 200 μm in a dry state, About 100 μm is more preferable.
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質量部及びアクリル酸２−ヒドロキシエチル３質量部、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、単量体（Ｃ）として、ジメチルアミノエチルメタクリレート０．５質量部、重合開始剤としてアゾビスイソブチロニトリル０．３質量部、溶媒として酢酸エチル１５０質量部を投入し、常温で１時間かけて窒素置換をした（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝４９．８質量％：４９．８質量％：０．４質量％）。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６００，０００であった。
Example 1
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet, and thermometer, as monomer (B), 47 parts by mass of n-butyl acrylate and 3 parts by mass of 2-hydroxyethyl acrylate, monomer As (A), 50 parts by mass of methacryloyloxyethyl diphenyl phosphate (manufactured by Daihachi Chemical Industry: MR-260), as monomer (C), 0.5 parts by mass of dimethylaminoethyl methacrylate, and as polymerization initiator, azobisiso 0.3 part by mass of butyronitrile and 150 parts by mass of ethyl acetate as a solvent were added, and nitrogen substitution was performed at room temperature for 1 hour (monomer (A): monomer (B): monomer (C ) = 49.8 mass%: 49.8 mass%: 0.4 mass%). Then, it heated up at 70 degreeC and superposition | polymerization was performed for 8 hours. When the obtained polymer was measured for molecular weight by GPC (polystyrene conversion), the weight average molecular weight (Mw) was 600,000.
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３７．５質量％）１．０質量部を加え、感圧接着剤組成物を得た。 To 100 parts by mass of the obtained polymerization solution, 1.0 part by mass of a tolylene diisocyanate-based crosslinking agent (Toyo Ink Manufacturing Co., Ltd .: BHS8515, solid content 37.5% by mass) is added, and a pressure-sensitive adhesive composition. Got.
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）
ジメチルアミノエチルメタクリレートの量を１０質量部とした以外は、実施例１と同様にして感圧接着性積層体を作製した（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝４５．５質量％：４５．５質量％：９質量％）。
(Example 2)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that the amount of dimethylaminoethyl methacrylate was changed to 10 parts by mass (monomer (A): monomer (B): monomer ( C) = 45.5% by mass: 45.5% by mass: 9% by mass).
（実施例３）
ジメチルアミノエチルメタクリレートの代わりに、ジメチルアクリルアミド０．５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（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝４９．８質量％：４９．８質量％：０．４質量％）。
(Example 3)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that 0.5 part by mass of dimethylacrylamide was used instead of dimethylaminoethyl methacrylate (monomer (A): monomer (B) : Monomer (C) = 49.8 mass%: 49.8 mass%: 0.4 mass%).
（実施例４）
ジメチルアミノエチルメタクリレートの代わりに、アクリロイルモルフォリン０．５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（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝４９．８質量％：４９．８質量％：０．４質量％）。
Example 4
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that 0.5 part by mass of acryloylmorpholine was used instead of dimethylaminoethyl methacrylate (monomer (A): monomer (B ): Monomer (C) = 49.8 mass%: 49.8 mass%: 0.4 mass%).
（実施例５）
メタクリロイルオキシエチルジフェニルホスフェートを３０質量部とし、ジメチルアミノエチルメタクリレートの代わりに、アクリロイルモルフォリンを１５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（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝３１．６質量％：５２．６質量％：１５．８質量％）。
(Example 5)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that 30 parts by mass of methacryloyloxyethyldiphenyl phosphate was used and 15 parts by mass of acryloylmorpholine was used instead of dimethylaminoethyl methacrylate (single amount). Body (A): Monomer (B): Monomer (C) = 31.6% by mass: 52.6% by mass: 15.8% by mass).
（実施例６）
ジメチルアミノエチルメタクリレートの代わりに、ペンタメチルピペリジルメタクリレート（日立化成工業社製：ＦＡ−７１１ＭＭ）０．５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（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝４９．８質量％：４９．８質量％：０．４質量％）。
(Example 6)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that 0.5 parts by mass of pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd .: FA-711MM) was used instead of dimethylaminoethyl methacrylate ( Monomer (A): Monomer (B): Monomer (C) = 49.8 mass%: 49.8 mass%: 0.4 mass%).
（実施例７）
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（単量体（Ａ）：単量体（Ｂ）：単量体（Ｃ）＝４９．８質量％：４９．８質量％：０．４質量％）。
(Example 7)
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 (monomer (A): monomer ( B): Monomer (C) = 49.8 mass%: 49.8 mass%: 0.4 mass%).
（実施例８）
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 8)
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９）
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２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 produced in the same manner as in Example 2 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１０）
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３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 produced in the same manner as in 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.
（実施例１１）
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４と同様にして、感圧接着性積層体を作製した。
(Example 11)
A pressure-sensitive adhesive laminate was prepared in the same manner as in Example 4 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１２）
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５と同様にして、感圧接着性積層体を作製した。
(Example 12)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 5 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１３）
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６と同様にして、感圧接着シートを作製した。
(Example 13)
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 6 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１４）
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７と同様にして、感圧接着シートを作製した。
(Example 14)
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 7 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.
（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。
(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.
この重合溶液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。 To 100 parts by mass of this polymerization solution, 1 part by mass of a tolylene diisocyanate crosslinking agent (Toyo Ink Manufacturing Co., Ltd .: BHS8515, solid concentration 37.5% by mass) and a phosphate ester flame retardant (bisphenol A bis) (Diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd .: CR-741, solid content 100% by mass) and 10 parts by mass were 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）
ジメチルアミノエチルメタクリレート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製した。
(Comparative Example 3)
A pressure-sensitive adhesive laminate was produced in the same manner as in Example 1 except that dimethylaminoethyl methacrylate was not used.
（比較例４）
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、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 (manufactured by 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、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 produced 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、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℃×Ｄｒｙ５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、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 5 days in accordance with 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 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 with a visible light transmittance measuring device (manufactured by Nippon Denshoku Industries Co., Ltd.). A 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１〜７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１．５％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 7 using a PET film as a base substrate have a flame retardancy evaluation determination of VTM-2, and are excellent in flame retardancy. It was less than 20%. Further, the haze value was 1.5% or less, and the transparency was excellent.
これに対し、アミン系化合物や所定のアミドからなる繰返しユニットを含まない比較例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。 On the other hand, the pressure-sensitive adhesive laminates of Comparative Example 3 and Comparative Example 6 that did not contain a repeating unit made of an amine compound or a predetermined amide had a large decrease in adhesive strength after the accelerating condition. This is presumably because the phosphate compound was eliminated from the repeating unit consisting of (meth) acrylic acid ester having a phosphate ester group.
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及びアミン系化合物や所定のアミドからなる繰返しユニットを含まず、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。また、難燃性評価判定でＶＴＭ不適合であり、十分な難燃性のないものであった。 Moreover, the comparative unit 1 which does not contain the repeating unit which consists of (meth) acrylic acid ester which has a phosphate ester group, and the repeating unit which consists of an amine compound and predetermined | prescribed amide, and there are few compounding quantities of a phosphate ester type flame retardant In Example 4, the decrease in the adhesive strength after the accelerating condition was large, and it is considered that the adhesive strength decreased due to the bleeding out of the phosphate ester flame retardant. Moreover, it was VTM nonconformity by flame-retardant evaluation determination, and there was no sufficient flame retardance.
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層中に局在化してしまい粘着力が低下し、使用できるものではなかった。 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 layer, the adhesive strength was lowered, 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８〜１４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った。 Moreover, the pressure-sensitive adhesive laminates of Examples 8 to 14 using a PI film as a base substrate were very excellent in flame retardancy and had no change in adhesive force.
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（単量体（Ａ））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（単量体（Ｂ））からなる繰返しユニットと、アミン系化合物、ジメチル（メタ）アクリルアミド、アクリロイルモルフォリンからなる群から選択される少なくとも１つ（単量体（Ｃ））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, the repeating unit which consists of (meth) acrylic acid ester (monomer (A)) which has a phosphate ester group, and the (meth) acrylic acid ester (monomer (C) which has a C1-C18 alkyl group. B)) and a repeating unit consisting of at least one (monomer (C)) selected from the group consisting of an amine compound, dimethyl (meth) acrylamide, and acryloylmorpholine (meta) It was found that the pressure-sensitive adhesive composition containing an acrylate polymer was excellent in flame retardancy, excellent in tackiness and transparency, and hardly deteriorated in adhesive properties over time.
Claims (5)
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（Ｂ）からなる繰返しユニットと、
前記（Ａ）及び前記（Ｂ）と共重合可能であるアミン系化合物、ジメチル（メタ）アクリルアミド、アクリロイルモルフォリンからなる群から選択される少なくとも１つ（Ｃ）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を含むことを特徴とする感圧接着剤組成物。 A repeating unit comprising a (meth) acrylic acid ester (A) having a phosphate ester group;
A repeating unit comprising a (meth) acrylic acid ester (B) having an alkyl group having 1 to 18 carbon atoms;
A repeating unit consisting of at least one (C) selected from the group consisting of amine compounds copolymerizable with (A) and (B), dimethyl (meth) acrylamide, and acryloylmorpholine;
A pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester-based polymer.
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| WO2021038348A1 (en) * | 2019-08-29 | 2021-03-04 | 3M Innovative Properties Company | Pressure sensitive adhesive having broad compatibility with non-halogenated flame retardants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013177577A (en) * | 2012-02-06 | 2013-09-09 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition for heat-resistant adhesive film, pressure-sensitive adhesive for heat-resistant adhesive film obtained by crosslinking the same, heat-resistant adhesive film for masking, having the pressure-sensitive adhesive, and method for using the heat-resistant adhesive film |
| JP2018501378A (en) * | 2014-12-30 | 2018-01-18 | スリーエム イノベイティブ プロパティズ カンパニー | Halogen-free flame retardant pressure sensitive adhesive and tape |
| JP2016188309A (en) * | 2015-03-30 | 2016-11-04 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
| WO2021038348A1 (en) * | 2019-08-29 | 2021-03-04 | 3M Innovative Properties Company | Pressure sensitive adhesive having broad compatibility with non-halogenated flame retardants |
| CN114364764A (en) * | 2019-08-29 | 2022-04-15 | 3M创新有限公司 | Pressure sensitive adhesives having broad compatibility with non-halogenated flame retardants |
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| JP5527881B2 (en) | 2014-06-25 |
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