GB2066270A - Hot-melt pressure-sensitive adhesive composition - Google Patents
Hot-melt pressure-sensitive adhesive composition Download PDFInfo
- Publication number
- GB2066270A GB2066270A GB8040993A GB8040993A GB2066270A GB 2066270 A GB2066270 A GB 2066270A GB 8040993 A GB8040993 A GB 8040993A GB 8040993 A GB8040993 A GB 8040993A GB 2066270 A GB2066270 A GB 2066270A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sensitive adhesive
- weight
- hot
- block copolymer
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000012943 hotmelt Substances 0.000 title claims abstract description 53
- 229920001400 block copolymer Polymers 0.000 claims abstract description 82
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 235000007586 terpenes Nutrition 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 150000003505 terpenes Chemical class 0.000 claims abstract description 20
- 239000004902 Softening Agent Substances 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 238000010057 rubber processing Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 abstract description 14
- 239000005062 Polybutadiene Substances 0.000 abstract description 13
- 239000004793 Polystyrene Substances 0.000 abstract description 9
- 229920002223 polystyrene Polymers 0.000 abstract description 9
- 229920001195 polyisoprene Polymers 0.000 abstract description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 16
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 16
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 16
- 239000002390 adhesive tape Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- -1 terpene hydrocarbons Chemical class 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 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 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- IUYLCJWINXWOFF-UHFFFAOYSA-N P(=O)(OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC.C(C=CC(=O)OCCCCCCCC)(=O)OCCCCCCCC Chemical compound P(=O)(OCCCCCCCC)(OCCCCCCCC)OCCCCCCCC.C(C=CC(=O)OCCCCCCCC)(=O)OCCCCCCCC IUYLCJWINXWOFF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A hot-melt pressure-sensitive adhesive composition comprising (a) 100 parts by weight of a material formed by the graft reaction of at least one block copolymer comprising at least one polybutadiene or polyisoprene block and at least two polystyrene blocks with at least one unsaturated carboxylic acid and/or derivative monomer, (b) 20 to 200 parts by weight of a terpene resin tackifier having a softening point of 60 DEG C or more, and (c) 5 to 200 parts by weight of a softening agent has been found to be well balanced between initial tack and holding power.
Description
SPECIFICATION
Hot-melt pressure-sensitive adhesive composition
The present invention relates to a hot-melt pressure-sensitive adhesive composition. More particularly, the invention relates to a hot-melt pressure-sensitive adhesive composition which comprises as the base polymer a modified block copolymer comprising at least one polybutadiene or polyisoprene block and at least two polystyrene blocks and grafted with at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof, and which is well balanced between initial tack and holding power.
Pressure-sensitive adhesive compositions have heretofore been widely used for the manufacture of various pressure-sensitive adhesive products such a pressure-sensitive adhesive tapes and pressure-sensitive adhesive label papers. The applicaton of a pressure-sensitive adhesive composition to a substrate such as a base tape or sheet has conventionally been carried out by rolling-coating or spraying of a solution or dispersion of the adhesive composition in a solvent.
However, the use of solvents in the manufacture of pressure-sensitive adhesive products such as pressure-sensitive adhesive tapes inevitably involves the risks of environmental pollution, breaking out of fire, deterioration of factory hygiene and the like, which have grown grave problems of social concern. Accordingly, solvent-free hot-melt pressure-sensitive adhesive compositions have recently attracted attention since they do not involve the above-mentioned risks. It is well known that block copolymers comprising one or more polybutadiene or
polyisoprene blocks and two or more polystyrene blocks are most suitable as a base polymer of such hot-melt pressure-sensitive adhesive compositions.However, pressure-sensitive adhesive tapes prepared using an adhesive composition comprising such a block copolymer are still too unsatisfactory from the viewpoint of balance between properties required of the pressuresensitive adhesive tapes to be put into practical use. As a hot-melt pressure-sensitive adhesive composition, there is disclosed in U.S. Patent No. 3,239,478 a composition comprising a block copolymer comprising one or more polybutadiene or polyisoprene blocks and two of more
polystyrene blocks, a tackifier and a rubber processing oil. There is also disclosed in Japanese
Patent Publication No. 21720/1972 a hot-melt pressure-sensitive adhesive composition com
prising a block copolymer comprising one or more polybutadiene or polyisoprene blocks and two or more polystyrene blocks, a tackifier, a rubber processing oil and atactic polypropyrene.When a block copolymer comprising one or more polybutadiene blocks and two or more polystyrene
blocks is used as the base polymer in the compositions of said U.S. Patent and said Japanese
Patent Publication, pressure-sensitive adhesive tapes prepared using any one of the compositions are good in holding power but poor in initial tack. On the other hand, when a block
copolymer comprising one or more polyisoprene blocks and two or more polystyrene blocks is
used in the compositions of said U.S. Patent and said Japanese patent Publicaton, pressuresensitive adhesive tapes prepared using any one of the compositions are good in initial tack but
poor in holding power. In any event, the compositions of said U.S. Patent and said Japanese
Patent Publication are poorly balanced between properties required when used in pressuresensitive adhesive tapes and the like.Further, there is disclosed in Japanese Patent Application
Laid-Open Specification No. 56427/1975 a hot-melt pressure-sensitive adhesive composition
comprising a block copolymer comprising one or more polybutadiene or polyisoprene blocks and two or more polystyrene blocks and modified with maleic anhydride, a metal oxide, a rubber
processing oil, a tackifier and a reinforcing resin. Since this adhesive composition is crosslinked
by means of ionic bondings between the maleic anhydride-modified block copolymer and the metal oxide, the composition is very excellent in holding power even at relatively high temperatures but very poor in initial tack. Accordingly, pressure-sensitive adhesive tapes
prepared using this composition are poorly balanced between the required properties.
With a view to developing a hot-melt pressure-sensitive adhesive composition which is suitably used for the production by hot-melt application technique of pressure-sensitive adhesive products such as pressure-sensitive adhesive tapes which are very well balanced between initial tack and holding power, we have intensive investigations to find to our great surprise that -excellent initial tack and excellent holding power can be consistently attained by a hot-melt pressure-sensitive adhesive composition comprising a combination of a specific block copolymer, a specific tackifier and a softening agent. We have now completed the present invention based on such a finding.
More specifically, in accordance with the present invention, there is provided a hot-melt pressure-sensitive adhesive composition comprising:
(a) 100 parts by weight of a grafted block copolymer material formed by the graft reaction of at last one block copolymer with at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof in an amount of 0.01 to 30% by weight based on the total of said at least one block copolymer and said at least one monomer, said at least one block copolymer being represented by the following formula::
A-B-A, (A-B),, B-(-A-B),, (A-B-),-A or (A-B),X wherein B stands for a block consisting substantially of butadiene or isoprene monomer units, A stands for a block consisting substantially of styrene monomer units n is an integer of from 2 to 10, X is the residue of a polyfunctional coupling agent to which m of (A-B) are bonded and m is an integer of from 2 to 7.
having a melt flow index of 0.1 to 40 g/10 minutes as measured in accordance with ASTM D 1 238 (condition G), and containing 5 to 50% by weight of styrene monomer units;
(b) 20 to 200 parts by weight of a terpene resin tackifier having a softening point of 60"C or more; and
(c) 5 to 200 parts by weight of a softening agent.
The foregoing and other features and advantages of the present invention will be apparent to those skilled in the art from the following detailed description taken in connection with the accompanying drawings in which:
Figure 1 is a diagrammatic perspective view showing corrugated boards having, stuck thereon, a pressure-sensitive adhesive tape sample to be subjected to the measurement of flap holding power as representing the holding power of the pressure-sensitive adhesive tape for the corrugated boards;
Figure 2 is a diagrammatic perspective view showing iron flaps having the corrugated boards fixed thereto with an adhesive and having, stuck thereon, the pressure-sensitive adhesive tape sample to be subjected to the measurement of flap holding power; and
Figure 3 is a diagrammatic side view illustrating the measurement of flap holding power of the pressure-sensitive adhesive tape for the corrugated boards.
The block copolymer of the above-mentioned formula that is used for the preparation of the grafted block copolymer material (a) used in the hot-melt pressure-sensitive adhesive composition of the present invention can be prepared, for example, according to the living anionic polymerization method in which an alkali metal-containing organometallic initiator such as sec-or n- butyl lithium is used (see, for example, U.S. Patent No. 3,265,765).More specifically, the block copolymer is prepared by the aiternate polymerization in sequence of each of two different monomers in the presence of the above-mentioned initiator and the subsequent inactivation of the resulting living block copolymer anion radicals with an inactivating agent such as water, phenol or an alcohol, by the polymerization of two monomers differing in monomer reactivity ratio and charged simultaneously into a reactor and the subsequent inactivation of the resulting living block copolymer anion radicals with an inactivating agent such as water, phenol or an alcohol, or by the polymerization in sequence of each of two different monomers in the presence of the above-mentioned initiator and the subsequent coupling of the resulting living block copolymer anion radicals with a polyfunctional coupling agent such as tin dichloride, tin tetrachloride, silicon tetrachloride, trichloromethylsilane or a polyepoxy compound [AB':e(AB)mX].
The block copolymer that is used for the preparation of the grafted block copolymer material (a) used in the hot-melt pressure-sensitive adhesive composition of the present invention has a melt flow index of 0.1 to 40 g/10 minutes, preferably 1 to 20 g/10 minutes, as measured in accordance with ASTM D 1 238 (Condition G). If the melt flow index is lower than 0.1 g/ 1 0 minutes, the resulting hot-melt pressure-sensitive adhesive composition has too high a melt viscosity to be supplied to a hot-melt applicator. If the melt flow index is higher than 40 g/10 minutes, the resulting hot-melt pressure-sensitive adhesive composition is poor in holding power. The styrene monomer unit content of the block copolymer is in the range of from 5 to 50% by weight, preferably in the range of from 1 5 to 45% by weight.If the styrene monomer unit content falls outside the range of from 5 to 50% by weight, the resulting hot-melt pressuresensitive adhesive composition has too poor pressure-sensitive adhesive characteristics to be used in pressure-sensitive adhesive tapes and the like. The block copolymer may be of any one of the five formulae mentiond before, i.e. A-B-A, (A-B)n, B-(-A-B)n, (A-B-)n-A and (A-B)mX, but is preferably of (A-B)mX wherein m is preferably an integer of from 3 to 7 since the resulting hot-melt pressure-sensitive adhesive composition is better in holding power than those in the cases of the other four formulae and with the same melt viscosity as that of the above-mentiond composition. It is noted that the melt viscosity has substantially direct relation to the processability of the composition.
The grafted block copolymer material (a) to be used in the hot-melt pressure-sensitive adhesive composition of the present invention is prepared from at least one block copolymer as described above and at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof according to the graft reaction method. As the unsaturated carboxylic acid monomer that may be grafted on the block copolymer, there can be mentioned, for example, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid, cis-4 cyclohexene-l, 3-dicarboxylic acid and endo-cis-bicyclo C2:2, ll-5-heptene-2, 3-dicarboxylic acid.
Examples of the derivative monomer of the above-mentioned unsaturated carboxylic acid monomer include those in the form of acid anhydride, ester, acid amide or acid imide.
Dicarboxylic anhydrides are preferred. More preferred is maleic anhydride.
The amount of at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof grafted on at least one block copolymer of the aforementioned formula in forming a grafted block copolymer material (a) to be used in the hot-melt pressure-sensitive adhesive composition of the present invention is in the range of from 0.01 to 30% by weight, preferably in the range of from 0.05 to 10% by weight, and most preferably in the range of from 0.1 to 3% by weight. When the above-mentioned amount is smaller than 0.01 % by weight, the effect of grafting for improving the balance between initial tack and holding power in the resulting hotmelt pressure-sensitive adhesive composition is not substantially recognizable.Even if the abovementioned amount is increased to more than 30% by weight, no substantial increase in the above-mentioned effect is recognizable.
The grafted block copolymer material (a) is prepared by grafting at least one block copolymer of the aforementioned formula with at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof in the presence or absence of a radical reaction initiator while keeping the reaction system in the molten state of the materials or in the dissolved state of the materials in a solvent. Any way of carrying out the graft reaction may be adopted in so far as the resulting grafted block copolymer dos not contain lumps of gel or other unfavorable substances and does not have so much reduced melt viscosity owing to some thermal degradation as to be poor in processability.According to one preferred way of carrying out the graft reaction, at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof is reacted with at least one block copolymer of the aforementioned formula in an extruder while keeping the reaction system in the molten state of the materials mixed in the absence of a radical reaction initiator. In the graft reaction, if desired, in antioxidizing agent such as phenothiazine or 2,5-di-tert-butylhydroquinone may be used for minimizing the thermal oxidation of the block copolymer. The grafted block copolymer material (a) thus prepared preferably has a melt flow index of 0.1 to 50 g/10 minutes, more preferably 1 to 25 g/10 minutes, as measured in accordance with ASTM D 1 238 (Condition G).
In the hot-melt pressure-sensitive adhesive composition of the present invention, a terpene resin tackifier having a softening point of 60"C or more is used as the component (b). When other type of a tackifier such as rosin or a derivative thereof, a petroleum resin, a phenolic resin, a styrene resin-, a xylene resin or a coumarone-indene resin is used, the resulting hot-melt pressure-sensitive adhesive composition is too poorly balanced between initial tack and holding power to be of practical utility. The terpene resin tackifier (b) is used in an amount of 20 to 200 parts by weight, preferably 50 to 1 50 parts by weight, per 100 parts by weight of the grafted block copolymer material (a).If the amount of the terpene resin tackifier is outside the range of from 20 to 200 parts by weight per 100 parts by weight of the grafted block copolymer material (a), the resulting hot-melt pressure-sensitive adhesive composition is poorly balanced betweeen initail tack and holding power.
As materials of the terpene resin tackifier (b), there can be mentioned, for example, homopoíymers of oL-pinene, P-pinene or dipentene; copolymers of at least two terpene hydrocarbons selected from pinene, fi-pinene and dipentene; and copolymers of at least one terpene hydrocarbon selected from a-pinene, fi-pinene and dipentene with phenol, and/or a C5 fraction and/or a C5 fraction of a naphtha-cracked oil. They may be used either alone or in mixture. Of them, a homopolymer of a-pinene and copolymers of pinene with phenol and/or a C5 fraction of a naphtha-cracked oil and with an a-pinene monomer unit content of at least 50% by weight are preferred.Especially preferred is a homopolymer of & inene.
As materials of the softening agent (c) to be used in the hot-meit pressure-sensitive adhesive composition of the present invention, there can be mentioned, for example, rubber processing oils such a naphthenic oils, aromatic oils and paraffinic oils; plasticizers such as esters of phthalic acid, esters of fumaric acid, adipic acid or sebacis acid, and esters of phosphoric acid; tackifier resins having a softening point of 30"C or less, such as terpene oligomers or resins, rosin derivatives such as methyl ester of rosin and hydrogenated methyl ester of rosin, coumarone-indene resins, styrene resins and petroleum resins formed by the polymerization of a Cb and/or Cg fraction of a naphtha-cracked oil; and liquid rubbers such as liquid polybutadiene.
They may be used either alone or in mixture. Rubber processing oils, ester type plasticizers and tackifier resins having a softening point of 30"C or less are preferred. Th softening agent (c) especially preferably comprises at leat 50% by weight of a terpene oligomer or resin having a softening point of 30"C or less. The softening agent (c) is used in an amount of 5 of 200 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the grafted block copolymer material (a). If the amount of the softening agent is outside the range of from 5 to 200 parts by weight per 100 parts by weight of the grafted block copolymer material (a), the resulting hot-melt pressure-sensitive adhesive composition is poorly balanced between initial tack and holding power.
Other type of at least one tackifier with a softening point of 60"C or more such as rosin or a derivative thereof, a petroleum resin, a phenolic resin, a styrene resin, a xylene resin or a coumarone-inder)e resin may additionally be incorporated in the hot-melt pressure sensitive adhesive composition of the present invention in so far as the balance between initial tack and holding power is good or at least permissible. Examples of rosin derivatives include hydrogenated rosin, polymerized rosin, glycerol or pentaerythritol esters of rosin or hydrogenated rosin.
Examples of petroleum resins include homopolymers or hydrogenated homoolymers of dicyclopentadiene, or a C5 fraction or a C9 fraction of a naphtha-cracked oil, and copolymers or hydrogenated copolymers of at least two monomers selected from dicyclopentadiene, and a C5 fraction and a C9 fraction of a naphtha-cracked oil. Examples of styrene resins include a homopolymer of styrene and copolymers of (x-methylstyrene and vinyltoluene.Further, at least one ordinary rubber such as natural rubber, polyisoprene rubber, polybutadiene rubber, styrenebutadiene copolymer rubber or styrene-conjugated diene block copolymer rubber, and/or a fielder may be added to the hot-melt pressure-sensitive adhesive composition of the present invention in so far as the properties required of the hot-melt pressure-sensitive adhesive composition are not spoiled. If desired, an antioxidizing agent, an ultraviolet absorbing agent, a coloring agent, etc. may be added to the hot-melt pressure-sensitive adhesive composition of the present invention.
The hot-melt pressure-sensitive adhesive composition of the present invention preferably comprises least 70% by weight, more preferably as least 80% by weight, of the total of the components (a), (b) and (c).
The preparation of the hot-melt pressure-sensitive adhesive composition of the present invention may be carried out using, for example, a melting vessel, a kneader, a mixing roll, an extruder or an internal mixer.
The hot-melt pressure-sensitive adhesive composition of the present invention, which is excellently balanced between initial tack and holding power, can advantageously be used for the manufacture of pressure-sensitive adhesive products such as pressure-sensitive adhesive tapes and labels.
In the specification, properties mentioned below are measured according to the following methods.
(1) Softening Point:
This is measured in accordance with JIS (Japanese Industrial Standard) K 2531 (ring and ball softening point method).
(2) Initial Tack:
This is measured in accordance with JIS Z 0237 (ball rolling method of J. Dow). More specifically, a pressure-sensitive adhesive tape is fixed to a plate inclined at an angle of 30 with the horizon and the ball number of a largest ball capable of stopping on the tacky surface of the pressure-sensitive adhesive tape is determined. The larger the ball number of a largest ball capable of stopping on the tacky surface of the pressure-sensitive adhesive tape, the larger the initial tack. The measurement of the tack is carried out at 20"C.
(3) Flap Holding Power:
A sample 1 of 52 mm in length and 20 mm in width is cut out from a pressure-sensitive adhesive tape. As shown in Fig. 1, two corrugated boards 2 and 3 of 70 mm in length, 50 mm in width and 5 mm in thickness are placed so that the lateral sections of the boards confront each other with a spacing of 2 mm therebetween. The pressure-sensitive adhesive tape sample 1 of 20 mm in width and 52 mm in length is pressed 2 times onto the middle portions of the surfaces of the corrugated boards 2 and 3 (as depicted in Fig. 1) by means of a roller having a weight of 20 g to effect adhesion therebetween. The area of contact of each board with the adhesive tape sample 1 stuck thereon is 20 mm X 25 mm.
As shown in Fig. 2, the corrugated boards 2 and 3 having the sample 1 stuck thereon is fixed to iron flaps 4 and 5 of 70 mm in length and 50 mm in width by using an adhesive. The flaps 4 and 5 each has a bearing 6 or 7 (other pair cannot be seen in Fig. 2) at the center of each of the longitudinal edges.
As shown in Fig. 3, two loads 10 each having a weight of 500 g are hung through the 2 mm spacing in the central portion thereof by using respective rectangular parallelepipeds 8 of 6 mm in length, 4 mm in width and 4 mm in thickness and respective strings 9 not contacted with the sample 1 so that turning moments act on both the flaps 4 and 5 with the centers of shaft 11 and 1 2 being the centers and said turning moments (each one of the loads 10, the rectangular parallelepipeds 8, the strings 9 and the bearings 6 and 7 is hidden by the other in Fig. 3). The period of time till the loads 10 fall is measured under a temperature of 40"C.
The following Examples illustrate the present invention in more detail but should not be construed as limiting the scope of the invention.
Example 1
1.5 Parts by weight of maleic anhydride and 0.2 part by weight of phenothiazine were added to 100 parts by weight of a (polystyrene-polybutadiene)4-silicon block copolymer having a melt flow index of 8 g/10 minutes as measured in accordance with ASTM D 1238 (Condition G) and a styrene monomer unit content of 30% by weight, and they were mixed by a mixer to form an intimate mixture.
The mixture was supplied to a 40 mm extruder having a single, full-flighted type screw with a length/diameter ratio of 24, and the maleic acid-graft reaction as carried out at a cylinder temperature of 200"C. After completion of the reaction, the maleic anhydride remaining unreacted was removed under reduced pressure to obtain a grafted block copolymer having a melt flow index of 5.2 g/10 minutes as measured in accordance with ASTM D 1238 (Condition G), a toluene-insoluble matters content of 0.05% by weight and a maleic anhydride-graft content of 0.70% by weight (hereinafter referred to as "grafted block copolymer A").
A melting vessel provided with a stirrer was charged with 100 parts by weight of the grafted block copolymer A, 100 parts by weight of an a-pinene polymer (YS Resin A1150 manufactured and sold by Yasuhara Yushi K.K., Japan and having a softening point of 115"C), 60 parts by weight of a terpene oligomer (YS Oil D manufactured and sold by Yasuhara Yushi K.K.,
Japan and having a softening point lower than 20"C) and 3 parts by weight of 2,5-di-tertbutylhydroquinone (Nocrac NS-7 manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd.,
Japan), and the mixture was molten and kneaded at about 180"C for 1 hour to obtain a transparent, smoothly-flowable, homogeneous composition.
Part of the hot-melt pressure-sensitive adhesive composition so obtained was molten and coated at 170C at a thickness of about 501l on a kraft paper (75 g/m2) having a polyethylene layer laminated on the back surface thereof and treated with a silicone. The initial tack and flap holding power of the pressure-sensitive adhesive kraft paper tape obtained were measured. The results were as shown in Table 1.
Examples 2 through 12
Using ingredients shown together with their amounts in Table 1, hot-melt pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes therefrom were prepared in substantially the same manner as in Example 1. The properties of these adhesive tapes were as shown in Table 1.
Comparative Examples 1 and 2
Using ingredients shown together with their amounts in Table 1, hot-melt pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes therefrom were prepared in substantially the same manner as in Example 1. It is noted that in these Comparative Examples 1 and 2 a non-grafted (polystyrene-polybutadiene)4-silicon block copolymer as used in Example 1 was used instead of the grafted block copolymer A. The properties of these adhesive tapes were as shown in Table 1.
Comparative Examples 3 through 9
Using ingredients shown together with their amounts in Table 1, hot-melt pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes therefrom were prepared in substantially the same manner as in Example 1. The properties of these adhesive tapes were as shown in Table 1.
Table 1
Example No.
Ingredients (parts by weight) 1 2 3 4 5 6 7 8 9 10 11 12 grafted block copolymer A 100 100 100 100 100 100 100 100 100 100 100 100 non-grafted (polystyrenepolybutadiene)4 Si block copolymer as used in Example 1 α-pinene polymer 100 100 150 100 100 100 100 120 120 120 α-pinene-phenol copolymer 100 α;-pinene-ss-pinene-dipentene
C9 fraction copolymer 100 glycerol ester of partially hrdrogenated rosin alicyclic saturated hydrocarbon resin terpene oligomer 60 100 40 40 45 45 60 60 hydrogenated methyl ester of rosin 60 20 naphthenic oil 50 15 dioctyl fumarate 40 15 trioctyl phosphate 40 2, 5-di-tert-butylhydroquinone 3 3 3 3 3 3 3 3 3 3 3 3
Properties of Adhesive Tape initial tack (ball number) at 20 C 17 26 16 18 20 20 25 18 21 24 18 16 flap holding power (minutes) at 40 C 120 < 96 120 < 42 57 51 36 63 68 83 76 51 Table 1 (continued)
Comparative Example No.
Ingredients (parts by weight) 1 2 3 4 5 6 7 8 9 grafted block copolymer A 100 100 100 100 100 100 100 non-grafted (polystyrenepolybutadiene)4Si block copolymer as used in Example 1 100 100 α-pinene polymer 100 100 100 100 250 α-pinene-phenol copolymer α-pinene-ss-pinene-dipentene
C9 fraction copolymer glycerol ester of partially hydrogenated rosin 100 100 alicyclic saturated hydrocarbon resin 100 100 terpene oligomer 60 60 60 250 80 hydrogenated methyl ester of rosin naphthenic oil 50 50 50 dioctyl fumarate trioctyl phosphate 2, 5-di-tert-butylydroquinone 3 3 3 3 3 3 3 3 3
Properties of Adhesive Tape initial tack (ball number) at 20 C 20 9 16 6 12 5 > 5 > 12 18 flap holding power (minutes) at 40 C 15 40 14 1 18 2 1 1 > 3 Note a-pinene polymer:YS Resin A1150 manufactured by Yasuhara Yushi K.K., Japan and having a softening point of 11 5 C.
a-pine-phenol copolymer: YS Polystar T1 1 5 manufactured by Yasuhara Yushi K.K., Japan and having a softening point of 11 5 C and an a-pinene monomer unit content of 74% by weight.
a-pinene-ss-pinene-dipentene-Cg fraction copolymer: YS Resin Z1 1 5 manufactured by Yasuhara
Yushi K.K., Japan and having a softening point of 11 5 C and a C9 fraction monomer unit content of 20% by weight.
glycerol ester of partially hydrogenated rosin: Ester Gum H manufactured by Arakawa Kagaku
K.K., Japan and having a softening point of 68"C.
alicyclic saturated hydrocarbon resin: Arkon M90 manufactured by Arakawa Kagaku K.K.,
Japan and having a softening point of 90'C.
terpene oligomer: YS Oil D manufactured by Yasuhara Yushi K.K., Japan and having a softening point lower than 20'C.
hydrogenated methyl ester of rosin: Hercolyn D manufactured by Hercules, Inc., U.S.A. and having a softening point lower than 20"C.
naphthenic oil: Sonic Process Oil R-200 manufactured by Nihon Kogyo K.K., Japan.
2,5-di-tert-butylhydroquinone: Nocrac NS-7 manufactured by Ouchi-Shinko Chemical Industrial
Co., Ltd., Japan.
Example 13
A grafted block copolymer having a melt flow index of 6.1 g/10 minutes as measured in accordance with ASTM D 1 238 (Conditon G), a toluene-insoluble matters content of 0.02% by weight and a maleinimide-graft content of 0.20% by weight (hereinafter referred to as "grafted block copolymer B") was prepared in substantially the same manner as described in Example 1 except that maleinimide was used instead of maleic anhydride.
A pressure-sensitive adhesive tape was prepared in the same manner as in Example 1 except that the grafted block copolymer B was used instead of the grafted block copolymer A. The properties of the adhesive tape were as shown in Table 2.
Example 14
A grafted block copolymer having a melt flow index of 16 g/10 minutes as measured in accordance with ASTM D 1 238 (Condition G), a toluene-insoluble matters content of 0.04% by weight and a maleic anhydride-graft content of 2.6% by weight (hereinafter referred to as "grafted block copolymer C") was prepared in substantially the same manner as in Example 1 except that a (polystyrene-polybutadiene)4-silicon block copolymer having a melt flow index of
18 g/10 minutes as measured in accordance with ASTM D 1238 (Conditon G) and a styrene monomer unit content of 40% by weight was used instead of the (polystyrene-polybutadiene)4silicon block copolymer used in Example 1 and maleic anhydride was used in an amount of 5 parts by weight instead of 1.5 parts by weight.
A pressure-sensitive adhesive tape was prepared in substantially the same manner as in
Example 1 except that the grafted block copolymer C was used instead of the grafted block copolymer A. The properties of the adhesive tape were as shown in Table 2.
Example 15
A grafted block copolymer having a melt flow index of 2.6 g/10 minutes as measured in accordance with ASTM D 1 238 (Condition G), a toluene-insoluble matters content of 0% by weight and a maleic anhydride-graft content of 1.6% by weight (hereinafter referred to as "grafted block copolymer D') was prepared in substantially the same manner as in Example 1 except that a polystyrene-polyisoprene-polystyrene block copolymer having a melt flow index of 2.0 g/10 minutes as measured in accordance with ASTM D 1238 (Condition G) and a styrene
monomer unit content of 16% by weight was used instead of the (polystyrene-polybutadiene)4silicon block copolymer and maleic anhydride was used in an amount of 3 parts by weight instead of 1.5 parts by weight.
A pressure-sensitive adhesive tape was prepared in substantially the same manner as in
Example 1 except that the grafted block copolymer D was used instead of the grafted block copolymer A. The properties of the adhesive tape were as shown in Table 2.
Example 16
A pressure-sensitive adhesive tape was prepared in substantially the same manner as in
Example 1 except that the grafted block copolymer A was used after it had been subjected to a
hot water treatment at 80"C for 3 hours. The properties of the adhesive tape were as shown in
Table 2.
Table 2
Ingredients (parts by weight) Example 1 3 Example 1 4 Example 1 5 Example 1 6 grafted block copolymer B 100 grafted block copolymer C 100 grafted block copolymer D 100 hot water-treated grafted copolymer A 100 a-pinene polymer 100 100 100 100 terpene oligomer 60 60 60 60 2,5-di-tert-butylhydroquinone 3 3 3 3
Properties of Adhesive Tape initial tack (ball number) at 20"C 1 8 1 9 25 1 6 flap holding power (minutes) at 40"C 83 97 92 120 <
Note a-pinene polymer: YS Resin Awl 150 terpene oligomer: YS Oil D 2,5-di-tert-butylhydroquinone: Nocrac NS-7
Claims (7)
1. A hot-melt pressure-sensitive adhesive composition comprising:
(a) 100 parts by weight of a grafted block copolymer material formed by the graft reaction
of at least one block copolymer with at least one unsaturated carboxylic acid monomer and/or
derivative monomer thereof in an amount of 0.01 to 30% by weight based on the total of said
at least one block copolymer and said at least one monomer, said at least one block copolymer
being represented by the following formula::
A-B-A, (A-B),, B-(-A-B),, (A-B-),-A or (A-B),X wherein B stands for a block consisting substantially of butadiene or isoprene monomer units, A
stands for a block consisting substantially of styrene monomer units, n is an integer of from 2 to
10, X is the residue of a polyfunctional coupling agent to which m of (A-B) are bonded and m
is an integer of from 2 to 7,
having a melt flow index of 0.1 to 40 g/10 minutes as measured in accordance with ASTM D 1 238 (Condition G), and containing 5 to 50% by weight of styrene monomer units;
(b) 20 to 200 parts by weight of a terpene resin tackifier having a softening point of 60"C or more; and
c) 5 to 200 parts by weight of a softening agent.
2. A hot-melt pressure-sensitive adhesive composition as claimed in claim 1, wherein said terpene resin tackifier is at least one tackifier selected from a homopolymer of lx-pinene and
copolymers of a-pinene with phenol and/or a C9 fraction of a naphtha-cracked oil and with an a
pinene monomer unit content of at least 50% by weight.
3. A hot-melt pressure-sensitive adhesive composition as claimed in claim 2, wherein said
terpene resin tackifier is a homopolymer of a-pinene.
4. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
3, wherein the amount of said terpene resin tackifier is in the range of from 50 to 1 50 parts by
weight per 100 parts by weight of the grafted block copolymer material.
5. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
4, wherein said softening agent is at least one softening agent selected froming of rubber
processing oils, ester type plasticizers and tackifier resins having a softening point of 30"C or
less.
6. A hot-melt pressure-sensitive adhesive composition as claimed in claim 5, wherein said
softening agent comprises at least 50% by weight of a terpene oligomer or resin having a
softening point of 30"C or less.
7. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
6, wherein the amount of said softening agent is in the range of from 20 to 100 parts by
weight per 100 parts by weight of the grafted block copolymer material.
7. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
6, wherein the amount of said softening agent is in the range of from 20 to 100 parts by
weight per 100 parts by weight of the grafted block copolymer material.
8. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
7, wherein the styrene monomer unit content of said at least one block copolymer is in the
range of from 1 5 to 45% by weight.
9. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
8, wherein the melt flow index of said at least one block copolymer is in the range of from 1 to 20 g/10 minutes as measured in accordance with ASTM D 1238 (Condition G).
10. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to 9, wherein said at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof is maleic anhydride.
11. A hot-melt pressure-sensitive adhesive composition as claimed in any one of claims 1 to
10, wherein the amount of said at least one unsaturated carboxylic acid monomer and/or derivative monomer thereof grafted on said at least one block copolymer is in the range of from .0.1 to 3% by weight based on the total of said at least one block copolymer and said at least one monomer.
1 2. A hot-melt pressure-sensitive adhesive composition according to claim 1 substantially as described in any one of Examples 1 to 1 2.
CLAIMS 16th Feb 1981
6. A hot-melt pressure-sensitive adhesive composition as claimed in claim 5, wherein said softening agent comprises at least 50% by weight of a terpene oligomer or resin having a softening point of 30"C or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16820679A JPS5692978A (en) | 1979-12-26 | 1979-12-26 | Hot-melt adhesive composition |
| JP4804980A JPS56145963A (en) | 1980-04-14 | 1980-04-14 | Hot-melt adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2066270A true GB2066270A (en) | 1981-07-08 |
| GB2066270B GB2066270B (en) | 1983-08-03 |
Family
ID=26388269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8040993A Expired GB2066270B (en) | 1979-12-26 | 1980-12-22 | Hot-melt pressure-sensitive adhesive composition |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3048859C2 (en) |
| FR (1) | FR2472599A1 (en) |
| GB (1) | GB2066270B (en) |
| IT (1) | IT1134871B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394915A (en) * | 1982-04-12 | 1983-07-26 | Findley Adhesives Inc. | Hot melt adhesive compositions and bottle assemblies using said compositions |
| EP0251507A2 (en) * | 1986-06-03 | 1988-01-07 | ARCO Chemical Technology, L.P. | Carbonamide modified thermoplastic elastomer-polyoxazoline molding compositions |
| US5093430A (en) * | 1988-03-24 | 1992-03-03 | Shell Internationale Research Maatschappij B.V. | Block copolymer compositions and process for the preparation thereof |
| GB2288177A (en) * | 1994-03-16 | 1995-10-11 | Atochem Elf Sa | Coextrusion binder compositions and coextruded multilayer composites using them |
| EP0857758A1 (en) * | 1997-02-10 | 1998-08-12 | Mitsubishi Chemical Corporation | Adhesive resin compositions, laminates, production method thereof and oriented films |
| FR2759379A1 (en) * | 1997-10-06 | 1998-08-14 | Urgo Laboratoires | Hydrophilic adhesive for dressing wounds |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4404955A1 (en) * | 1994-02-17 | 1995-08-24 | Beiersdorf Ag | Adhesive material with post-crosslinking reserve |
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| US3239478A (en) * | 1963-06-26 | 1966-03-08 | Shell Oil Co | Block copolymer adhesive compositions and articles prepared therefrom |
| GB1252604A (en) * | 1968-06-28 | 1971-11-10 | ||
| GB1260897A (en) * | 1968-09-12 | 1972-01-19 | Shell Int Research | A novel block copolymer adduct |
| GB1405786A (en) * | 1971-09-22 | 1975-09-10 | Shell Int Research | Adhesive composition |
| GB2019416A (en) * | 1978-04-19 | 1979-10-31 | Minnesota Mining & Mfg | Contamination-tolerant pressure sensitive adhesive tape |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137130A (en) * | 1974-09-25 | 1976-03-29 | Kyowa Kk |
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1980
- 1980-12-22 GB GB8040993A patent/GB2066270B/en not_active Expired
- 1980-12-23 IT IT26893/80A patent/IT1134871B/en active
- 1980-12-23 DE DE3048859A patent/DE3048859C2/en not_active Expired
- 1980-12-24 FR FR8027534A patent/FR2472599A1/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3239478A (en) * | 1963-06-26 | 1966-03-08 | Shell Oil Co | Block copolymer adhesive compositions and articles prepared therefrom |
| GB1252604A (en) * | 1968-06-28 | 1971-11-10 | ||
| GB1260897A (en) * | 1968-09-12 | 1972-01-19 | Shell Int Research | A novel block copolymer adduct |
| GB1405786A (en) * | 1971-09-22 | 1975-09-10 | Shell Int Research | Adhesive composition |
| GB2019416A (en) * | 1978-04-19 | 1979-10-31 | Minnesota Mining & Mfg | Contamination-tolerant pressure sensitive adhesive tape |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394915A (en) * | 1982-04-12 | 1983-07-26 | Findley Adhesives Inc. | Hot melt adhesive compositions and bottle assemblies using said compositions |
| EP0251507A2 (en) * | 1986-06-03 | 1988-01-07 | ARCO Chemical Technology, L.P. | Carbonamide modified thermoplastic elastomer-polyoxazoline molding compositions |
| EP0251507A3 (en) * | 1986-06-03 | 1989-10-11 | Arco Chemical Technology Inc. | Carbonamide modified thermoplastic elastomer-polyoxazoline molding compositions |
| US5093430A (en) * | 1988-03-24 | 1992-03-03 | Shell Internationale Research Maatschappij B.V. | Block copolymer compositions and process for the preparation thereof |
| GB2288177A (en) * | 1994-03-16 | 1995-10-11 | Atochem Elf Sa | Coextrusion binder compositions and coextruded multilayer composites using them |
| GB2288177B (en) * | 1994-03-16 | 1998-10-14 | Atochem Elf Sa | Coextrusion binders and coextruded multilayer composites using them |
| AU702814B2 (en) * | 1994-03-16 | 1999-03-04 | Elf Atochem S.A. | Coextrusion binder compositions and coextruded multilayer composites using them |
| EP0857758A1 (en) * | 1997-02-10 | 1998-08-12 | Mitsubishi Chemical Corporation | Adhesive resin compositions, laminates, production method thereof and oriented films |
| US6214476B1 (en) | 1997-02-10 | 2001-04-10 | Mitsubishi Chemical Corporation | Adhesive resin compositions, laminates, production method thereof and oriented films |
| FR2759379A1 (en) * | 1997-10-06 | 1998-08-14 | Urgo Laboratoires | Hydrophilic adhesive for dressing wounds |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3048859C2 (en) | 1985-03-21 |
| FR2472599A1 (en) | 1981-07-03 |
| FR2472599B1 (en) | 1983-05-27 |
| GB2066270B (en) | 1983-08-03 |
| IT1134871B (en) | 1986-08-20 |
| IT8026893A0 (en) | 1980-12-23 |
| DE3048859A1 (en) | 1981-10-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951222 |