JPH01213380A - Tacky agent composition - Google Patents
Tacky agent compositionInfo
- Publication number
- JPH01213380A JPH01213380A JP4028088A JP4028088A JPH01213380A JP H01213380 A JPH01213380 A JP H01213380A JP 4028088 A JP4028088 A JP 4028088A JP 4028088 A JP4028088 A JP 4028088A JP H01213380 A JPH01213380 A JP H01213380A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogenated
- aromatic vinyl
- isoprene
- liquid diene
- diene rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 150000001993 dienes Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims description 29
- 239000000853 adhesive Substances 0.000 claims description 27
- 229920003244 diene elastomer Polymers 0.000 claims description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 abstract description 8
- 229920001971 elastomer Polymers 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 7
- -1 diene compound Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000032843 Hemorrhage Diseases 0.000 description 3
- 208000034158 bleeding Diseases 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PPWGXYXJMQAWSX-UHFFFAOYSA-N 2-methylhexa-1,3,5-triene Chemical compound CC(=C)C=CC=C PPWGXYXJMQAWSX-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920006164 aromatic vinyl copolymer Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は優れた粘着性能を有し、耐熱耐候性に優れた粘
着剤組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an adhesive composition having excellent adhesive performance and excellent heat and weather resistance.
（従来の技術）
省エネルギー、省資源、脱公害という観点から、天然ゴ
ムなどを有機溶剤に溶解して使用する溶剤型の粘着剤・
接着剤に代わり、ホットメルト型の粘着剤・接着剤が広
く使用されるようになった。(Conventional technology) From the viewpoints of energy saving, resource saving, and pollution prevention, solvent-based adhesives and adhesives that use natural rubber etc. dissolved in organic solvents have been developed.
Hot-melt adhesives and adhesives have become widely used in place of adhesives.
このホットメルトａの粘着剤・接着剤のペースＩリマー
として芳香族ビニル−イソプレン−芳香族ビニルからな
るブロック共重合体が使用されている。しかし、それら
は不飽和化合物であるイソプレンを含んでいるため紫外
線や熱による劣化が激しく、そのような環境では使用出
来なじゅその点を改良したものに、イソグレンの不飽和
部分く水素添加を行ない、不飽和結合を減少させること
がある。しかし、一般にイソグレン部分を水添すると未
水添物に比べて粘着性能、特に低温での粘着力ばか）で
なく常温での粘着力、／ ＩＪオレフィン類への接着性
が著しく低下する。さらＫ、高温での溶融粘度が高く作
業性が低下する。その結果、粘着性能面でも、加工性と
いう面でも、使用は著しく限定される。それらの問題点
を解決するためにプロセスオイルなどの可塑剤あるいは
軟化剤が使用され、これＫよりて低温及び常温での粘着
力、高温での加工性は改良されるものの、ポリオレフィ
ン類への接着性は改善さ牡ず、比較的高温での凝集力が
著しく低下し、また添加したオイルなどが粘着剤からブ
リードし、粘着剤の基材あるいは被着体を汚染する。そ
の結果粘着剤の性能の経時変化が大きいという障害が生
じる。これらの理由で上記の粘着剤はその利用範囲が限
定されているのが現状である。A block copolymer consisting of aromatic vinyl-isoprene-aromatic vinyl is used as the paste I remer of the pressure-sensitive adhesive/adhesive of this hot melt a. However, since they contain isoprene, an unsaturated compound, they are subject to severe deterioration due to ultraviolet rays and heat, so they cannot be used in such environments.In order to improve this point, the unsaturated parts of isogrene are hydrogenated. , may reduce unsaturated bonds. However, in general, when the isogrene moiety is hydrogenated, the adhesive performance (particularly the adhesive strength at low temperatures), the adhesive strength at room temperature, and the adhesion to IJ olefins are significantly reduced compared to unhydrogenated products. Furthermore, the melt viscosity at high temperatures is high and workability is reduced. As a result, its use is severely limited both in terms of adhesive performance and processability. To solve these problems, plasticizers or softeners such as process oils are used, and although they improve adhesion at low and room temperatures and processability at high temperatures, they do not adhere well to polyolefins. However, the cohesive strength at relatively high temperatures is significantly reduced, and the added oil etc. bleed from the adhesive and contaminate the base material of the adhesive or the adherend. As a result, a problem arises in that the performance of the adhesive changes significantly over time. For these reasons, the range of use of the above-mentioned pressure-sensitive adhesives is currently limited.
（発明が解決しようとする課題）
本発明の目的は、芳香族ビニル−イソプレン−芳香族ビ
ニルからな夛、イソプレ７部分が水素添加されたトリブ
ロック共重合体からなるホットメルト型粘着剤において
、このものが本来有している優れた性能を損なうことな
く、かつブリードする恐九がなく、低温特性、粘着力、
加工性を改善し、さらに接着力に優詐る粘着剤組成物を
提供することにある。(Problems to be Solved by the Invention) The object of the present invention is to provide a hot-melt pressure-sensitive adhesive comprising a triblock copolymer of aromatic vinyl-isoprene-aromatic vinyl, in which 7 portions of isoprene are hydrogenated. This product does not lose its original excellent performance, has no fear of bleeding, has low-temperature properties, adhesive strength,
The object of the present invention is to provide a pressure-sensitive adhesive composition that has improved processability and superior adhesive strength.
（課題を解決するための手段）
本発明によれば上記目的は、芳香族ビニル−イソプレン
−芳香族ビニル共重合体の単位からなシ、イソプレ７部
分が水素添加されたトリブロック共重合体と水素添加液
状ジエン系コ９ムを含有する粘着剤組成物によシ達成さ
れる。すなわち本発明は（ａ） 芳香ｉヒニルーイソ
プレンー芳香族ビニルの単位からなシ、共役ジエン部分
が水素添加されたトリブロック共重合体と
（ｂ） 液状ジエン系ゴムを水素添加して得られる水
素化率が４０〜１００％の水素添加液状ジエン系コ９ム
を含有することを特徴とする粘着剤組成物に関する。(Means for Solving the Problems) According to the present invention, the above object is achieved by forming a triblock copolymer in which a unit of an aromatic vinyl-isoprene-aromatic vinyl copolymer is hydrogenated at 7 portions of isoprene. This is achieved by a pressure-sensitive adhesive composition containing a hydrogenated liquid diene system. That is, the present invention is obtained by hydrogenating (a) a triblock copolymer consisting of units of aromatic isoprene-aromatic vinyl, in which the conjugated diene moiety is hydrogenated, and (b) a liquid diene rubber. The present invention relates to an adhesive composition containing a hydrogenated liquid diene compound having a hydrogenation rate of 40 to 100%.
本発明において使用さｎる芳香族ビニル−イソプレン−
芳香族ビニルトリブロック共重合体はスチレン−イソプ
レン−スチレン共重合体、α−メチルスチレンーイソゾ
レンーα−メチルスチレン共重合体などであり、分子量
がｓ ｏ、ｏ ｏ ｏから４００．０００、イソグレン
と芳香族ビニルとの重量比が９５１５から６０／４０、
水添率が４０〜Ｚｏｏ％、好ましくは７０〜１００％の
範囲内のものが好適に使用される。Aromatic vinyl isoprene used in the present invention
Aromatic vinyl triblock copolymers include styrene-isoprene-styrene copolymers, α-methylstyrene-isozolene-α-methylstyrene copolymers, and have molecular weights ranging from so, o o o to 400.000. , the weight ratio of isogrene to aromatic vinyl is 9515 to 60/40,
Those having a hydrogenation rate of 40 to Zoo%, preferably 70 to 100% are preferably used.
本発明において用いらｎる水素添加液状ジエン系ゴムの
水素化率は、液状ジエン系ゴム中の炭素−炭素不飽和二
重結合が水素化されている割合を意味し、４０〜１００
％、好ましくは７０〜１００鴨の範囲内にあることが必
要である。水素化率が小さ過ぎると、水素添加物自体の
耐熱性が低下し得られた粘着剤組成物の耐熱劣化性、耐
候性を低下させ好ましくない、なお、上記水素化率は水
素添加前のヨウ素価と水素添加後のヨウ素価を求め、前
者に対する後者の百分率を算出することＫよって求めら
れる。The hydrogenation rate of the hydrogenated liquid diene rubber used in the present invention refers to the proportion of carbon-carbon unsaturated double bonds in the liquid diene rubber that is hydrogenated, and is from 40 to 100.
%, preferably within the range of 70 to 100%. If the hydrogenation rate is too small, the heat resistance of the hydrogenated material itself will decrease, resulting in a decrease in the heat deterioration resistance and weather resistance of the resulting pressure-sensitive adhesive composition, which is undesirable. It is obtained by determining the iodine value and the iodine value after hydrogenation, and calculating the percentage of the latter relative to the former.
本発明において重要な成分である水素添加液状ジエン系
ゴムはイソグレン、ブタジェンなどの共役ジエンの単独
重合体または二種類以上の共重合物であシ、１，４結合
量が７０％以上であシ、七の分子量がａＯＯＯから５０
，０００のものが好適に用いられる。１．４結合量が上
記範囲よシ小さい場合、ガラス転移温度が上り低温特性
が悪化することがある。水素添加液状ジエン系ゴムの分
子量が上記範囲よシも小さすぎると凝集力、接着力など
得られる粘着性能が低いものになり、またブリードする
恐れもある。逆に上記範囲よシ大きすぎると初期粘着力
効果、加工性向上効果が乏しく、更に低温特性の改良に
は至らない。The hydrogenated liquid diene rubber, which is an important component in the present invention, is a homopolymer or a copolymer of two or more conjugated dienes such as isogrene and butadiene, and the amount of 1,4 bonds is 70% or more. , the molecular weight of seven is aOOOO to 50
,000 is preferably used. If the 1.4 bond amount is smaller than the above range, the glass transition temperature may rise and the low-temperature properties may deteriorate. If the molecular weight of the hydrogenated liquid diene rubber is too small within the above range, the resulting adhesive properties such as cohesive force and adhesive force will be low, and there is also a risk of bleeding. On the other hand, if it is too large than the above range, the initial adhesion effect and processability improvement effect will be poor, and furthermore, the low temperature properties will not be improved.
なお、かかる水素添加液状ジエン系ゴムは分子鎖中に、
分子末端にカルぎキシル基、水酸基、酸無水物などの官
能基を含有してもよい。あるいは本発明の主旨を損なわ
なり程度に少量のスチレンなどの芳香族ビニルが共重合
して込てもよい。In addition, such hydrogenated liquid diene rubber has in its molecular chain,
The molecular terminal may contain a functional group such as a carboxyl group, a hydroxyl group, or an acid anhydride. Alternatively, a small amount of aromatic vinyl such as styrene may be copolymerized without detracting from the spirit of the present invention.
このような水素添加液状ジエン系コ９ムは公知の方法に
よシ得ることができ、その合成原料である液状ジエン系
ゴムはアニオン重合により容易に得られる。液状ジエン
系ゴムの合成の例として、ブチルリチウムなどのアルキ
ルリチウムを触媒として用い、ヘキサン、９シクロヘキ
サンなどの飽和炭化水素からなる溶媒中で共役ジエン系
単量体を重合する方法が例示される。Such a hydrogenated liquid diene rubber can be obtained by a known method, and the liquid diene rubber, which is a raw material for its synthesis, can be easily obtained by anionic polymerization. An example of synthesis of liquid diene rubber is a method in which a conjugated diene monomer is polymerized in a solvent consisting of a saturated hydrocarbon such as hexane or 9-cyclohexane using an alkyl lithium such as butyl lithium as a catalyst.
液状ジエン系ゴムの水素添加の例としては、ニッケル、
ノ等ラジウム、白金、ルテニウムもしくはロジウム等の
金属をカー？ンやアルミナ等に担持させたもの、ラネー
ニッケル、漆原ニッケル等の不均一系触媒または遷移金
属ハライドとアルミニウム、アルカリ土類金属もしくは
アルカリ金属などのアルキル化物との組合せＫよるチー
グラー触媒等の均一系触媒を吊込、常温〜２００℃で、
常圧〜２００に９／ｃｒｎ”の水素がスと０．１〜１０
０時間接触させる方法、あるいはｐ−）ルエンスルホニ
ルヒドラジドによって還元する方法が挙げられる。Examples of hydrogenation of liquid diene rubber include nickel,
Is it possible to use metals such as radium, platinum, ruthenium or rhodium? Heterogeneous catalysts such as Raney nickel, Urushihara nickel, etc., or homogeneous catalysts such as Ziegler catalysts made of combinations of transition metal halides and alkylated substances such as aluminum, alkaline earth metals, or alkali metals. Suspended at room temperature to 200℃,
At normal pressure ~ 200 9/crn" hydrogen is 0.1~10
Examples include a method of contacting for 0 hours, and a method of reducing with p-)luenesulfonyl hydrazide.
これらの方法のうち、前者の接触水素添加法が反応の容
易さの点から好ましく採用される。Among these methods, the former catalytic hydrogenation method is preferably employed from the viewpoint of ease of reaction.
水素添加反応は、液状ジエン系ゴムを加熱溶融下または
反応溶媒に溶解し溶液状態で行なわれるが、反応の制御
の点から溶液状態で行なうのが好ましい。反応溶媒は水
素添加反応に対して不活性なものであｎぽいずれでもよ
いが、ヘキサン、ヘプタン等の脂肪族炭化水素またはシ
クロヘキサン等の脂環族炭化水素が最も好ましく用いら
れる。The hydrogenation reaction is carried out in a solution state by heating and melting the liquid diene rubber or by dissolving it in a reaction solvent, but from the viewpoint of reaction control it is preferably carried out in a solution state. The reaction solvent may be any solvent inert to the hydrogenation reaction, but aliphatic hydrocarbons such as hexane and heptane or alicyclic hydrocarbons such as cyclohexane are most preferably used.
また、反応条件によってはベンゼン、トルエン等の芳香
族炭化水素も好ましく使用しうる。Furthermore, aromatic hydrocarbons such as benzene and toluene may also be preferably used depending on the reaction conditions.
水素添加反応後、常法により反応生成物から触媒を分離
、除去することにより液状ジエン系ゴムの水素添加物が
得られる。該水素添加物はそのまま使用してもよいが、
水素添加物をさらに変性して分子末端または側鎖に水酸
基、カルがキシル基、ハロゲン等の極性基を含有させて
使用してもよい。After the hydrogenation reaction, a hydrogenated liquid diene rubber is obtained by separating and removing the catalyst from the reaction product using a conventional method. The hydrogenated product may be used as is, but
The hydrogenated product may be further modified to contain a polar group such as a hydroxyl group, a xyl group, or a halogen at the molecular end or side chain.
本発明の粘着剤組成物において芳香族ビニル−イソグレ
ン−芳香族ビニルの共役ジエン部分が水素添加さｎたト
リブロック共重合体と水素添加液状ジエン系ゴムとの使
用割合は後者に対する前者の重量比で９７／３〜４０／
６０、よシ好適には８０／２０〜５０１５０であるのが
よい。水素添加液状ジエン系ゴムの使用割合が３％未満
（重量比）であると、本発明の効果が発現せず、６０％
（重量比）を超えると比較的高温での粘着剤としての凝
集力が著しく低下する。In the pressure-sensitive adhesive composition of the present invention, the ratio of the aromatic vinyl-isogrene-aromatic vinyl triblock copolymer in which the conjugated diene moiety is hydrogenated and the hydrogenated liquid diene rubber is the weight ratio of the former to the latter. 97/3-40/
60, more preferably 80/20 to 50,150. If the proportion of hydrogenated liquid diene rubber used is less than 3% (weight ratio), the effect of the present invention will not be achieved, and
(weight ratio), the cohesive force as an adhesive at relatively high temperatures will be significantly reduced.
本発明の粘着剤組成物は、溶融状態で紙、セロハン、ポ
リプロピレン、ポリエステル等の基材に塗工して用いら
れる。場合によっては配合物をトルエン等の溶剤に溶解
、混合し、溶液状態で塗工して粘着剤を得ることももち
ろん可能である。The adhesive composition of the present invention is used by coating it on a substrate such as paper, cellophane, polypropylene, polyester, etc. in a molten state. In some cases, it is of course possible to obtain an adhesive by dissolving and mixing the compound in a solvent such as toluene and applying it in a solution state.
以下に実施例をもって本発明をさらに詳細に説明する。The present invention will be explained in more detail with reference to Examples below.
参考例
ｎ−ブチルリチウムを触媒として用い、イソプレンを重
合することＫよシ平均分子量７，８００．１．４結合量
８２％の液状ポリイソグレンゴムを得た。この液状ポリ
イソデレンコ０ムをオートクレーブ中でシクロヘキサン
に溶解し、２０重量らの溶液とし念。この溶液にノ臂ラ
ジウム（５重量％）−カーダン担持触媒を２重量％添加
、分散させ、水素によシ５０ ｋｌ／ｃｘ” Ｋ加圧し
、５０℃で水素添加反応を行なった。９反応終了後、触
媒を濾過によ部分離し、真空乾燥することによシ液状ポ
リイングレンゴムの水素添加物を得た。ヨウ素価を測定
することＫよシ求めた水素化率は９５％であった。Reference Example A liquid polyisogrene rubber having an average molecular weight of 7,800.1.4 and a bond content of 82% was obtained by polymerizing isoprene using n-butyllithium as a catalyst. This liquid polyisoderene comb was dissolved in cyclohexane in an autoclave to form a solution with a weight of 20%. To this solution, 2% by weight of radium (5% by weight)-cardan supported catalyst was added and dispersed, and the mixture was pressurized with hydrogen at 50 kl/cx''K to perform a hydrogenation reaction at 50°C. 9 Reactions completed Thereafter, the catalyst was partially separated by filtration and vacuum dried to obtain a hydrogenated liquid polyurethane rubber.The hydrogenation rate was 95% as determined by measuring the iodine value.
同様にして分子量と水添率の異なる液状、ｌｅ ＩＪイ
ソグレンの水素添加物を調整した。また、Ｓ−ブチルリ
チウムを触媒としてスチレン、イソグレン、スチレンを
逐次重合し平均分子量１００，０００スチレン含量２０
重量％のスチレン・イソグレン・スチレン） ＩＪブロ
ック共重合体を得た。上と同じ方法で水素添加し９８％
の水素添加物を得た。結果を表１に示す。In the same manner, liquid hydrogenated products of le IJ isogren having different molecular weights and hydrogenation rates were prepared. In addition, styrene, isogrene, and styrene are sequentially polymerized using S-butyllithium as a catalyst, and the average molecular weight is 100,000 and the styrene content is 20.
An IJ block copolymer (% by weight of styrene, isogrene, styrene) was obtained. Hydrogenate to 98% using the same method as above.
A hydrogenated product was obtained. The results are shown in Table 1.
実施例１〜５および比較例１〜６
表ＩＫ示す水添スチレン・イソグレン・スチレントリブ
ロック共重合体と液状ジエン系ゴムの水素添加物を表２
４Ｃ示す配合で２ｏｏ℃溶融混合して粘着剤組成物を作
成し、４０μｍのコーターでポリエステルフィルムにコ
ーティングして粘着テープを作成し、その粘着特性の評
価を行なった。結果を表２に示す。Examples 1 to 5 and Comparative Examples 1 to 6 Table 2 shows the hydrogenated styrene/isogrene/styrene triblock copolymer and liquid diene rubber shown in Table IK.
A pressure-sensitive adhesive composition was prepared by melt-mixing the composition shown in 4C at 200° C., and the pressure-sensitive adhesive composition was coated on a polyester film using a 40 μm coater to prepare a pressure-sensitive adhesive tape, and its pressure-sensitive adhesive properties were evaluated. The results are shown in Table 2.
粘着性能の評価はＪＩＳ−２０２３７に従って行なった
。Evaluation of adhesive performance was performed according to JIS-20237.
低温特性は１０℃におけるが一ルタックを測定すること
Ｋよシ評価した。ブリード状態は粘着テープと上質紙を
貼り合わせ、これを７０℃で２週間加熱した後上質紙へ
のしみ出しの有無にょシ評価した。また、加工性はコー
ティング時のしやすさで評価し次。The low-temperature properties were evaluated by measuring one lu tack at 10°C. The state of bleeding was evaluated by pasting adhesive tape and high-quality paper together, heating this at 70° C. for 2 weeks, and then evaluating whether or not there was any seepage into the high-quality paper. In addition, processability was evaluated based on ease of coating.
以下会白
表 １
以下余白
（発明の効果）
本発明によれば、低温特性、粘着力、加工性などが改善
され、さらに接着力に優れる粘着剤組成物が提供される
。Table 1 below: Margin (Effects of the Invention) According to the present invention, a pressure-sensitive adhesive composition is provided that has improved low-temperature properties, adhesive strength, processability, etc., and also has excellent adhesive strength.
特許出願人 株式会社り ラ し
代 理 人 弁理士 本 多 堅手続補正書
（自発）
１、事件の表示
特願昭６３−４０２８０号
２、発明の名称
粘着剤組成物
３、補正をする者
事件との関係 特許出願人
倉敷市酒本１６２１番地
（１０８）株式会社 り ラ し
代表取締役 中村尚夫
４、代理人
倉敷市酒津２０４５の１
株式会社 り ラ し 内
電話 倉敷０８６４（２５）９３２５（直通）（６７４
７）弁理士 本 多 竪叢 ２′：株式
会社 クラレ特許部
５、補正の対象
明細書の発明の詳細な説明の欄
６、補正の内容
明細書第８頁第１１行の「著しく低下する。」のあとに
下記を加入する。Patent Applicant RiRa Co., Ltd. Attorney Patent Attorney Hondada Procedural Amendment (Voluntary) 1. Indication of the case Japanese Patent Application No. 1983-40280 2. Name of the invention Adhesive composition 3. Case of the person making the amendment Relationship with Patent Applicant: 1621 Sakamoto, Kurashiki City (108) Rira Shi Co., Ltd. Representative Director: Naoo Nakamura 4, Agent: 2045-1 Sakazu, Kurashiki City Rira Shi Co., Ltd. Phone: Kurashiki 0864 (25) 9325 (direct) (674
7) Patent Attorney Honta Verso 2': Kuraray Patent Department 5, Column 6 of Detailed Description of the Invention of the Specification Subject to Amendment, Section 6 of the Specification Subject to Amendment, page 8, line 11 of the Specification Subject to Amendment: ``Remarkably deteriorates.'' ” and then add the following.
［本発明の粘着剤組成物は粘着付与樹脂その他の配合剤
を必要に応じて含有していてもよい。[The adhesive composition of the present invention may contain a tackifier resin and other compounding agents as necessary.
配合剤の例として酸化防止剤、紫外線吸収剤、炭酸カル
シウム、酸化チタンなどのフィラーを挙げることができ
る。ｔ７ｔ１本発明の趣旨を損なわない程度に少量のプ
ロセスオイルを可塑剤として併用することも可能である
。この場合、これらの使用量は、本発明で用いられる水
素添加液状ジエン系プムの平蓋以下にするのが望ましい
・ 」Examples of compounding agents include fillers such as antioxidants, ultraviolet absorbers, calcium carbonate, and titanium oxide. t7t1 It is also possible to use a small amount of process oil as a plasticizer without detracting from the spirit of the present invention. In this case, it is desirable that the amount of these used be less than the amount of the hydrogenated liquid diene pump used in the present invention.
Claims (1)
からなり、共役ジエン部分が水素添加されたトリブロッ
ク共重合体と （ｂ）液状ジエン系ゴムを水素添加して得られる水素化
率が４０から１００％の水素添加液状ジエン系ゴムを含
有することを特徴とする粘着剤組成物[Scope of Claims] (a) A triblock copolymer composed of aromatic vinyl-isoprene-aromatic vinyl units and having a conjugated diene moiety hydrogenated, and (b) obtained by hydrogenating a liquid diene rubber. An adhesive composition comprising a hydrogenated liquid diene rubber having a hydrogenation rate of 40 to 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040280A JP2647414B2 (en) | 1988-02-22 | 1988-02-22 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63040280A JP2647414B2 (en) | 1988-02-22 | 1988-02-22 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01213380A true JPH01213380A (en) | 1989-08-28 |
| JP2647414B2 JP2647414B2 (en) | 1997-08-27 |
Family
ID=12576204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63040280A Expired - Lifetime JP2647414B2 (en) | 1988-02-22 | 1988-02-22 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2647414B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210147A (en) * | 1991-05-20 | 1993-05-11 | Shell Oil Company | 100% Triblock hydrogenated styrene-isoprene-styrene block copolymer adhesive composition |
| JPH05194923A (en) * | 1991-01-31 | 1993-08-03 | Sekisui Chem Co Ltd | Self-adhesive composition, and self-adhesive tape or sheet or surface-protecting film prepared therefrom |
| US5242984A (en) * | 1991-07-29 | 1993-09-07 | Shell Oil Company | Sequentially polymerized styrene-isoprene-styrene block copolymer adhesive composition |
| EP0670864A4 (en) * | 1992-11-17 | 1995-07-25 | Korpman Ralf Ass | Pressure sensitive adhesives comprising liquid and solid rubbers. |
| JP2002069405A (en) * | 2000-08-28 | 2002-03-08 | Nitto Denko Corp | Adhesive composition and adhesive tape or sheet |
| WO2003020825A1 (en) * | 2001-08-29 | 2003-03-13 | Zeon Corporation | Elastomer composition and pressure-sensitive adhesives made by using the same |
| WO2007148729A1 (en) * | 2006-06-21 | 2007-12-27 | Hitachi Kasei Polymer Co., Ltd. | Thermally conductive thermoplastic adhesive composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337741A (en) * | 1976-09-20 | 1978-04-07 | Nitto Electric Ind Co Ltd | Pressure-sensitive adhesive composition |
| JPS5852379A (en) * | 1981-09-22 | 1983-03-28 | Nichiban Co Ltd | Thermosensitive self-adhesive tape for use in tying |
-
1988
- 1988-02-22 JP JP63040280A patent/JP2647414B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337741A (en) * | 1976-09-20 | 1978-04-07 | Nitto Electric Ind Co Ltd | Pressure-sensitive adhesive composition |
| JPS5852379A (en) * | 1981-09-22 | 1983-03-28 | Nichiban Co Ltd | Thermosensitive self-adhesive tape for use in tying |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05194923A (en) * | 1991-01-31 | 1993-08-03 | Sekisui Chem Co Ltd | Self-adhesive composition, and self-adhesive tape or sheet or surface-protecting film prepared therefrom |
| US5210147A (en) * | 1991-05-20 | 1993-05-11 | Shell Oil Company | 100% Triblock hydrogenated styrene-isoprene-styrene block copolymer adhesive composition |
| US5242984A (en) * | 1991-07-29 | 1993-09-07 | Shell Oil Company | Sequentially polymerized styrene-isoprene-styrene block copolymer adhesive composition |
| EP0670864A4 (en) * | 1992-11-17 | 1995-07-25 | Korpman Ralf Ass | Pressure sensitive adhesives comprising liquid and solid rubbers. |
| EP0670864A1 (en) * | 1992-11-17 | 1995-09-13 | Ralf Korpman Associates | Pressure sensitive adhesives comprising liquid and solid rubbers |
| JP2002069405A (en) * | 2000-08-28 | 2002-03-08 | Nitto Denko Corp | Adhesive composition and adhesive tape or sheet |
| WO2003020825A1 (en) * | 2001-08-29 | 2003-03-13 | Zeon Corporation | Elastomer composition and pressure-sensitive adhesives made by using the same |
| US7674856B2 (en) | 2001-08-29 | 2010-03-09 | Zeon Corporation | Elastomer composition and pressure-sensitive adhesives made by using same |
| WO2007148729A1 (en) * | 2006-06-21 | 2007-12-27 | Hitachi Kasei Polymer Co., Ltd. | Thermally conductive thermoplastic adhesive composition |
| EP2071002A1 (en) * | 2006-06-21 | 2009-06-17 | Hitachi Kasei Polymer Co., Ltd. | Thermally conductive thermoplastic adhesive composition |
| EP2071002A4 (en) * | 2006-06-21 | 2009-11-18 | Hitachi Kasei Polymer Co Ltd | Thermally conductive thermoplastic adhesive composition |
| JPWO2007148729A1 (en) * | 2006-06-21 | 2009-11-19 | 日立化成ポリマー株式会社 | Thermally conductive thermoplastic adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2647414B2 (en) | 1997-08-27 |
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