JPH0496982A - Polychloroprene adhesive composition - Google Patents
Polychloroprene adhesive compositionInfo
- Publication number
- JPH0496982A JPH0496982A JP21490390A JP21490390A JPH0496982A JP H0496982 A JPH0496982 A JP H0496982A JP 21490390 A JP21490390 A JP 21490390A JP 21490390 A JP21490390 A JP 21490390A JP H0496982 A JPH0496982 A JP H0496982A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polychloroprene
- indene
- resin
- hydrocarbon
- 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
- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract 3
- 238000005336 cracking Methods 0.000 claims abstract 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 36
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 8
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 4
- 229910015900 BF3 Inorganic materials 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000003878 thermal aging Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 31
- 229920005989 resin Polymers 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- -1 boron trifluoride dialkyl ether Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規なポリクロロプレン系接着剤に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel polychloroprene adhesive.
さらに詳しくは、本発明は、特定の粘着付与樹脂を配合
することにより長時間のタックの保持、接着力、凝集力
および特に耐熱老化性にすぐれＩ；性能を発揮するポリ
クロロプレン接着剤組成物に関するものである。More specifically, the present invention relates to a polychloroprene adhesive composition that exhibits excellent long-term tack retention, adhesive strength, cohesive strength, and especially heat aging resistance by incorporating a specific tackifying resin. It is something.
（従来技術と問題点）
各種のゴム系接着剤うち、クロロプレンゴムをベースと
するポリクロロプレン接着剤は、広範囲の用途に用いら
れている。(Prior Art and Problems) Among various rubber adhesives, polychloroprene adhesives based on chloroprene rubber are used in a wide range of applications.
通常、ポリクロロプレン接着剤には、粘着付与樹脂とし
て高温での接着力および凝集力を付与することのできる
酸化マグネシウムで金属塩化したアルキルフェノール樹
脂が用いられる。しかし、金属塩化アルキルフェノール
樹脂は、高軟化点であるため、前記のように高温特性は
優れるものの、タックの保持時間が短かく、そのため基
材を短時間のうちに接着しなければならず、現場施行で
の作業性に問題がある。また、被着体間の接着力が、８
０℃以上の高温雰囲気下では数日で極端に低下する欠点
を有している。タックの保持時間の調整にテルペンフェ
ノール樹脂、−射的な石油樹脂、クマロンインデン樹脂
等を用いることは公知であるが、この場合には、接着力
および凝集力が、金属塩化アルキルフェノール樹脂を用
いた場合によりも低下する。またテルペンフェノール樹
脂は、室温および高温雰囲気下では数日で接着力が極端
に低下する欠点もある。Typically, polychloroprene adhesives use an alkylphenol resin metallized with magnesium oxide, which can provide adhesive strength and cohesive strength at high temperatures, as a tackifying resin. However, metal chloride alkylphenol resin has a high softening point, so although it has excellent high-temperature properties as mentioned above, it has a short tack retention time, so the base material must be bonded in a short period of time, and on-site There are problems with workability during enforcement. In addition, the adhesive strength between adherends is 8
It has the disadvantage that it drops dramatically in a few days in a high temperature atmosphere of 0°C or higher. It is well known that terpene phenol resin, acetic petroleum resin, coumaron indene resin, etc. are used to adjust the retention time of tack, but in this case, the adhesive strength and cohesive force are higher than that of metal chloride alkyl phenol resin. It will be lower than if it were. Terpene phenol resin also has the disadvantage that its adhesive strength decreases extremely in a few days at room temperature or in a high-temperature atmosphere.
（発明が解決しようとする問題点）
本発明は、従来の金属塩化アルキルフェノール樹脂の長
所すなわち、高温での接着力および凝集力を損なうこと
なく、その欠点であるタックの保持時間および熱老化性
を改良することを目的とするものである。(Problems to be Solved by the Invention) The present invention solves the disadvantages of tack retention time and heat aging properties without impairing the advantages of conventional metal chloride alkylphenol resins, namely adhesive strength and cohesive force at high temperatures. The purpose is to improve.
（問題点を解決するための手段）
本発明者らは、前記の問題を解決すべく鋭意研究を行っ
た結果、ポリクロロプレンに特定の粘着付与樹脂を配合
することにより、前記問題点を解決し得ることを見出し
、本発明を完成するに至りｌこ 。(Means for Solving the Problems) As a result of intensive research to solve the above problems, the present inventors have solved the above problems by blending a specific tackifier resin into polychloroprene. The present invention was completed based on this discovery.
すなわち、本発明は、（ａ）ポリクロロプレンオヨび（
ｂ）インデンとメチルインデンの合計含有率が８０重量
％以上である炭化水素を７リーデルクラフツ型触媒によ
り重合して得た軟化点が１４０℃以上で、かつ重量平均
分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比Ｍ ｗ／
Ｍ ｎが３，０以下である炭化水素樹脂を主成分とする
、ポリクロロプレン系接着剤組成物を提供する。That is, the present invention provides (a) polychloroprene and (
b) Hydrocarbons having a total content of indene and methylindene of 80% by weight or more are polymerized using a 7-Riedel-Crafts type catalyst, and have a softening point of 140°C or higher, and have a weight average molecular weight (Mw) and a number average molecular weight. (Mn) ratio M w/
Provided is a polychloroprene adhesive composition containing as a main component a hydrocarbon resin having an Mn of 3.0 or less.
本発明で用いる（ｂ）成分の炭化水素樹脂の原料として
は、インデンとメチルインデンの合計含有率か８０重量
％以上のものを使用することか特徴であり、高純度のイ
ンデンおよび／またはメチルインデンを使用することも
できる。しかし、これらは工業的に入手し難いので、イ
ンデンおよび／またはメチルインデンを比較的多く含む
炭化水素類を例えば蒸留することにより取得することか
有利である。インデンおよび／またはメチルインデンを
比較的多く含む炭化水素類としては、一つには、石油類
を熱分解、水蒸気分解する際に得られる沸点】４０〜２
８０℃の留分かあり、他は、コークス炉等からの石炭乾
留により得られるタールまたはこれらの分留などにより
得られる沸点１４０〜２８０℃の留分があり、これらの
留分をさらに蒸留してインデンとメチルインデンの合計
含有率が８０重量％以上としたものを用いることが有利
である。これら蒸留により得られるものには、インデン
、メチルインデン以外の炭化水素類、含酸素化合物等が
含まれるが、本発明においては、インデンとメチルイン
デンとの合計含有率が８０重量％以上であればよい。The raw material for the hydrocarbon resin of component (b) used in the present invention is characterized in that the total content of indene and methylindene is 80% by weight or more, and high purity indene and/or methylindene is used. You can also use However, since these are difficult to obtain industrially, it is advantageous to obtain hydrocarbons containing relatively large amounts of indene and/or methylindene, for example, by distilling them. Hydrocarbons containing a relatively large amount of indene and/or methylindene include boiling points of 40 to 2, which are obtained when petroleum is thermally decomposed or steam decomposed.
There is a fraction with a boiling point of 80℃, and others with a boiling point of 140 to 280℃ obtained from tar obtained by carbonization of coal from a coke oven, etc., or fractional distillation of these.These fractions are further distilled. It is advantageous to use one in which the total content of indene and methylindene is 80% by weight or more. Those obtained by distillation include indene, hydrocarbons other than methylindene, oxygen-containing compounds, etc. In the present invention, if the total content of indene and methylindene is 80% by weight or more, good.
本発明で云うインデンとメチルインデンとの合計含有率
（Ｒ）は、次式で表わす。The total content (R) of indene and methylindene as used in the present invention is expressed by the following formula.
ここで、重合可能成分と量は、フリーデルクラフッ型触
媒により重合性を示す炭素、炭素二重結合を有する化合
物の量であり、インデン、メチルインデンおよびスチレ
ン、アルキルスチレン、クロロン、ジシクロペンタジェ
ン等の合計量（Ｉｉ量％）である。Here, the polymerizable components and amounts are the amounts of compounds having carbon and carbon double bonds that are polymerizable with Friedel-Krauch type catalysts, such as indene, methylindene, styrene, alkylstyrene, chlorone, dicyclopentane, etc. The total amount (Ii amount %) of Jen et al.
インデンとメチルインデンとの合計含有率が８０重量％
より少ない原料を使用した場合は、Ｍｗ／ Ｍ ｎを３
．０以下にすると、得られる樹脂の軟化点が低く、ポリ
クロロプレン接着剤に配合した場合高温特性が低下し好
ましくない。Total content of indene and methylindene is 80% by weight
If less raw material is used, Mw/Mn should be reduced to 3
．． If it is less than 0, the resulting resin will have a low softening point, and when blended into a polychloroprene adhesive, its high-temperature properties will deteriorate, which is undesirable.
本発明では、上記原料を７リーデルクラフツ型触媒を用
いて重合する。フリーデルクラフッ型触媒としては、三
弗化ホウ素、塩化アルミニウム、三弗化ホウ素フェノー
ル錯化合物、三弗化ホウ素ジアルキルエーテル錯化合物
等が使用され、添加量は、通常０．０５〜５重量％、好
ましくは０．１〜３重量％である。また重合温度は、通
常＋１００Ｃ〜＋９０℃、重合時間は、０．５〜５時間
程度である。In the present invention, the above raw materials are polymerized using a 7-Riedel-Crafts type catalyst. Boron trifluoride, aluminum chloride, boron trifluoride phenol complex compounds, boron trifluoride dialkyl ether complex compounds, etc. are used as Friedel-Kraf type catalysts, and the amount added is usually 0.05 to 5% by weight. , preferably 0.1 to 3% by weight. Further, the polymerization temperature is usually +100C to +90C, and the polymerization time is about 0.5 to 5 hours.
重合後、カセイソーダ、炭酸ソーダ等のアルカリで触媒
を分解し水洗除去した後、未反応物および低重合物を蒸
留等の操作で分離することにより本発明の炭化水素樹脂
を得る。After polymerization, the catalyst is decomposed with an alkali such as caustic soda or soda carbonate, washed away with water, and unreacted substances and low polymerized substances are separated by distillation or the like to obtain the hydrocarbon resin of the present invention.
本発明の炭化水素樹脂は、軟化点が１４０℃以上、好ま
しくは１５０〜２００℃で、かつ重量平均分子量（Ｍｗ
）と数平均分子量（Ｍｎ）の比Ｍｗ／ Ｍ ｎが３．０
以下、好ましくは２．８以下である。The hydrocarbon resin of the present invention has a softening point of 140°C or higher, preferably 150 to 200°C, and a weight average molecular weight (Mw
) and number average molecular weight (Mn) Mw/Mn is 3.0
It is preferably 2.8 or less.
該樹脂の軟化点が１４０℃未満であると、Ｍｗ／ Ｍ
ｎが３．０以下であっても、ポリクロロプレン接着剤に
配合した場合に十分な接着力、凝集力および耐熱老化性
が得られず、２００℃を越えると、Ｍ ｗ ／ Ｍ ｎ
が３．０以下であっても、タックの保持時間が短くなる
。またＭ ｗ ／ Ｍ ｎの比が３．０を越えると、軟
化点が１４０℃〜２００℃であっても、クロロプレンゴ
ムとの相溶性か悪化し、ポリクロロプレン接着剤に配合
した場合に十分な接着力および凝集力が得られない。When the softening point of the resin is less than 140°C, Mw/M
Even if n is 3.0 or less, sufficient adhesive strength, cohesive force and heat aging resistance cannot be obtained when blended with polychloroprene adhesive, and when it exceeds 200°C, M w / M n
Even if it is 3.0 or less, the tack retention time will be shortened. Furthermore, if the ratio of M w / M n exceeds 3.0, even if the softening point is 140°C to 200°C, the compatibility with chloroprene rubber will deteriorate, and when it is blended into a polychloroprene adhesive, it will not be sufficient. Adhesion and cohesion cannot be obtained.
本発明で使用するポリクロロプレン（ａ）は、特に限定
するものではなく、クロロプレンを重合して得られる一
般的なポリクロロプレンを始めその変性物でよい。The polychloroprene (a) used in the present invention is not particularly limited, and may be general polychloroprene obtained by polymerizing chloroprene or modified products thereof.
本発明で得られた炭化水素樹ＢＹｉ（ｂ）の配合量は、
特に限定されないが、通常の粘着付与樹脂と同様に、ポ
リクロロプレン１００部に対し１０〜１００重量部か好
ましく、さらに２０〜８０重量部かより好ましい。The blending amount of the hydrocarbon tree BYi (b) obtained in the present invention is:
Although not particularly limited, it is preferably 10 to 100 parts by weight, and more preferably 20 to 80 parts by weight, based on 100 parts of polychloroprene, as in the case of ordinary tackifying resins.
炭化水素樹脂（ｂ）の配合量か１０重量部より少ないと
、十分な接着力が得られず、また高温雰囲気下での接着
力や凝集力が低下する。また、炭化水素樹脂（ｂ）が１
００重量部を越えると、タックの保持時間が短かくなる
ため、作業性が低下したり、接着剤が弾性を失ってもろ
くなる。If the blending amount of the hydrocarbon resin (b) is less than 10 parts by weight, sufficient adhesive strength will not be obtained, and the adhesive strength and cohesive strength in a high temperature atmosphere will decrease. Further, the hydrocarbon resin (b) is 1
If the amount exceeds 0.00 parts by weight, the tack retention time will be shortened, resulting in decreased workability or the adhesive will lose its elasticity and become brittle.
本発明の接着剤組成物は、（ａ）成分および（ｂ）成分
の他に、酸化マグネシウム、酸化亜鉛等の金属酸化物や
、−射的なゴムの老化防止剤や、チオカルバニリド等の
加硫剤などが添加されたものも含まれる。また必要に応
して、公知のアルキルフェノール樹脂およびその金属塩
化物、テルペンフェノール樹脂、クスロンインデン樹脂
、石油樹脂等の粘着付与樹脂を併用してもさしつかえな
い。In addition to the components (a) and (b), the adhesive composition of the present invention also contains metal oxides such as magnesium oxide and zinc oxide, anti-aging agents for radioactive rubber, and vulcanizates such as thiocarbanilide. This also includes those to which agents have been added. Further, if necessary, tackifier resins such as known alkylphenol resins and their metal chlorides, terpenephenol resins, xuronindene resins, petroleum resins, etc. may be used in combination.
この場合、公知の粘着付与樹脂は、本発明で得られた炭
化水素樹脂（ｂ）の５０％以下の量で併用することがで
きる。配合量が５０％を越えると、タンクの保持時間、
高温雰囲気下での接着力や凝集力が低下する。In this case, a known tackifying resin can be used in combination in an amount of 50% or less of the hydrocarbon resin (b) obtained in the present invention. If the blending amount exceeds 50%, the tank retention time
Adhesive force and cohesive force decrease in high temperature atmosphere.
本発明の接着剤組成物は、通常有機溶媒に溶解して用い
る。有機溶媒としては、特に限定するものでなく、通常
のポリクロロプレン系接着剤に用いられるトルエン、ア
セトンヘキサン、酢酸エチル等の有機溶媒を巣独又は混
合して用いることができる。The adhesive composition of the present invention is usually used after being dissolved in an organic solvent. The organic solvent is not particularly limited, and organic solvents used in ordinary polychloroprene adhesives such as toluene, acetonehexane, and ethyl acetate can be used alone or in combination.
更に本発明の組成物は、−成型に限定するものでなく、
インシアネート等の架橋剤を用いる二液型として用いる
こともできる。Furthermore, the composition of the present invention is not limited to -molding,
It can also be used as a two-part type using a crosslinking agent such as incyanate.
以下に実施例を挙げて本発明を具体的に説明するが、本
発明は、これらに限定されるものではない。The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.
（参考例１）
ナフサのスチームクランキングにより得られる分解油か
ら、蒸留により沸点１７０〜２１０℃の留分を得た。こ
の留分は、インデンとメチルインデンとの合計４２．２
重量％、その他の重合可能成分９．０重量％を含んでい
た。(Reference Example 1) A fraction with a boiling point of 170 to 210°C was obtained by distillation from cracked oil obtained by steam cranking naphtha. This fraction has a total of 42.2 indene and methyl indene.
% by weight, and 9.0% by weight of other polymerizable components.
すなわちインデンとメチルインデンとの合計含有率が８
２．４重量％であった。That is, the total content of indene and methylindene is 8
It was 2.4% by weight.
この留分１００重量％に市販のクレゾール酸０゜５重量
部を加えたものに、触媒として三弗化ホウ素フェノール
錯化合物０．４８重量部を添加し、３０℃で３時間重合
させた後、カセイソーダ水溶液で触媒を分解し、水洗後
、減圧蒸留により未反応油および低重合体を除去し樹Ｂ
′ｆ１５０ｇを得た。To 100% by weight of this fraction and 0.5 parts by weight of commercially available cresylic acid was added 0.48 parts by weight of a boron trifluoride phenol complex compound as a catalyst, and after polymerization at 30°C for 3 hours, The catalyst was decomposed with an aqueous solution of caustic soda, washed with water, and unreacted oil and low polymers were removed by vacuum distillation.
'f150g was obtained.
この樹脂の軟化点は、１６２℃、ＦｖＬｗ／Ｍｎは２゜
０であった。The softening point of this resin was 162°C, and the FvLw/Mn was 2°0.
（参考例２）
石炭タールから得られるタール軽油を蒸留して、沸点１
７０〜２０５℃の留分も得た。この留分は、インデンと
メチルインデンとの合計６２．３８重量％、その他の重
合可能成分４．０３重量％を含んでした。すなわちイン
デンとメチルインデンとの合計含有率が９３．９重量％
であった。(Reference Example 2) Tar light oil obtained from coal tar is distilled to have a boiling point of 1
A fraction between 70 and 205°C was also obtained. This fraction contained a total of 62.38% by weight of indene and methylindene and 4.03% by weight of other polymerizable components. That is, the total content of indene and methylindene is 93.9% by weight.
Met.
この留分１００重量部に市販のクレゾール酸２゜５重量
部を加えたものに、触媒として三弗化ホウ素フェノール
錯化合物０．６４重量部を添加し、６０℃で３時間重合
させた後、カセイソーダ水溶液で触媒を分解し、水洗後
、減圧蒸留により未反応油および低重合体を除去し、樹
脂６５ｇを得た。To 100 parts by weight of this fraction and 2.5 parts by weight of commercially available cresylic acid was added 0.64 parts by weight of a boron trifluoride phenol complex compound as a catalyst, and after polymerization at 60°C for 3 hours, The catalyst was decomposed with an aqueous solution of caustic soda, washed with water, and unreacted oil and low polymers were removed by distillation under reduced pressure to obtain 65 g of resin.
この樹脂の軟化点は１８０℃、Ｍｗ／Ｍｎは２．６であ
った。The softening point of this resin was 180°C, and the Mw/Mn was 2.6.
（実施例および比較例）
（１） クロロブレン接着剤配合
クロロブレンゴム１１ １００
酸化マグネシウム ８
酸化亜鉛 ４．８
老防（非汚染） ” １．６粘着付与樹脂
４４．８
溶媒 ３６４０
１）昭和ネオブレンＡＤ
２）穴内新興 ノックラック ＮＳ−６３）トルエン：
アセトン二〇−ヘキサン−１＋１＋１（２）接着剤試験
（塗布量： ３００ ｇ／ｍ”）タックの保持時間（オ
ーブンタイム）：１０号キャンパスおよびステンレス板
に塗布し、所定の時間後両方を貼り合せ、１０分後に２
３℃での接着力を測定した。(Examples and Comparative Examples) (1) Chloroprene rubber containing chloroprene adhesive 11 100 Magnesium oxide 8 Zinc oxide 4.8 Anti-aging (non-staining) 1.6 Tackifying resin 44.8 Solvent 3640 1) Showa Neobrene AD 2) Shinko Anauchi Knock Rack NS-63) Toluene:
Acetone 20-Hexane-1+1+1 (2) Adhesive test (coating amount: 300 g/m") Tack retention time (oven time): Apply to No. 10 campus and stainless steel plate, and bond both together after a specified time. , after 10 minutes 2
Adhesion strength was measured at 3°C.
常態接着カニ１０号キャンパスに塗布し、１時間後にキ
ャンパス同志を貼り合せ、２３℃で１日および１５日養
生後、２３℃での接着力を測定しＩこ 。It was applied to normally adhesive Crab No. 10 campus, and after 1 hour, the campuses were pasted together, and after curing at 23°C for 1 and 15 days, the adhesive strength at 23°C was measured.
せん断剥離カニＩＯ号キャンパスおよびステンレス板に
塗布し、１時間後に両方を貼り合せ、２３℃で５日養生
後、２３℃でのせん断剥離力を測定した。It was applied to the shear peeling Crab IO campus and a stainless steel plate, and after 1 hour, both were bonded together. After curing for 5 days at 23°C, the shear peeling force at 23°C was measured.
耐熱クリープ：１０号キャンパスおよびステンレス板に
塗布し、１時間後に両方を貼り合せ、２３℃で５日養生
後、６０℃での耐熱クリープを測定した。Heat-resistant creep: It was applied to a No. 10 campus and a stainless steel plate, and after 1 hour, both were bonded together. After curing at 23°C for 5 days, the heat-resistant creep at 60°C was measured.
熱老化試験：１０号キャンパスおよびステンレス板に塗
布し、１時間後にキャンパス同志およびキャンパスとス
テンレス板を貼り合せ、２３℃で１日養生後、１０５℃
のギヤオーブン中で熱老化を行ない、１５日および３０
日後の接着力、せん断力を測定した。Heat aging test: Coated on No. 10 campus and stainless steel plate, 1 hour later, the campus and stainless steel plate were bonded together, and after curing at 23℃ for 1 day, 105℃
Heat aging was carried out in a gear oven for 15 days and 30 days.
After several days, the adhesive strength and shear strength were measured.
（実施例１）
参考例１で得た樹脂を粘着付与樹脂として（１）の配合
のポリクロロブレン接着剤を調製し、（２）の要領で接
着剤試験を行った。結果を表１ないし４に示す。(Example 1) A polychloroprene adhesive having the formulation (1) was prepared using the resin obtained in Reference Example 1 as the tackifying resin, and an adhesive test was conducted in the manner described in (2). The results are shown in Tables 1 to 4.
（実施例２）
参考例２で得た樹脂を粘着付与樹脂として用いた以外は
、実施例１と同様に接着剤を調製し、試験を行った。(Example 2) An adhesive was prepared and tested in the same manner as in Example 1, except that the resin obtained in Reference Example 2 was used as the tackifying resin.
（比較例１および２）
市販の芳香族石油樹脂を粘着付与樹脂として用いた以外
は、実施例１と同様に接着剤を調製し、試験を行った。(Comparative Examples 1 and 2) An adhesive was prepared and tested in the same manner as in Example 1, except that a commercially available aromatic petroleum resin was used as the tackifying resin.
（比較例３）
金属塩化アルキルフェノール樹脂を粘着付与樹脂として
用いた以外は、実施例１と同様に接着剤の調製と試験を
行った。(Comparative Example 3) An adhesive was prepared and tested in the same manner as in Example 1, except that a metal chloride alkylphenol resin was used as the tackifying resin.
（比較例４）
テルペンフェノール樹脂を粘着付与樹脂として用いた以
外は、実施例１と同様に接着剤の調製と試験を行った。(Comparative Example 4) An adhesive was prepared and tested in the same manner as in Example 1, except that a terpene phenol resin was used as the tackifying resin.
（結果）
表１ 粘着付与樹脂の性状
表２
オーブンタイムと接着力
（ｋｇ／２
５ ｍｍ）
表３
常態接着力および凝集力
２５Ｘ２５ｍｍ、 ６０℃１
２００ｇ、 ２４ｈ
かでき、さらに金属塩化フェノール樹脂の最大の欠点で
ある耐熱老化性を大幅に改良することかできる。(Results) Table 1 Properties of tackifying resin Table 2 Oven time and adhesive strength (kg/2 5 mm) Table 3 Normal adhesive strength and cohesive strength 25 x 25 mm, 60°C 1 200 g, 24 h baking, and maximum of metal chloride phenolic resin It is possible to significantly improve heat aging resistance, which is a disadvantage of conventional methods.
Claims (1)
チルインデンとの合計含有率が８０重量％以上である炭
化水素をフリーデルクラフツ型触媒により重合して得た
軟化点が１４０℃以上で、かつ重量平均分子量（Ｍｗ）
と数平均分子量（Ｍｎ）の比Ｍｗ／Ｍｎが３．０以下で
ある炭化水素樹脂を主成分とする、ポリクロロプレン系
接着剤組成物。 ２、インデンとメチルインデンとの合計含有率が８０重
量％以上である炭化水素が、ナフサのクラッキングおよ
びタール蒸留により得られる留分のうち、１４０〜２４
０℃の範囲内の沸点を有する留分から調製したものであ
る、特許請求の範囲第１項記載のポリクロロプレン系接
着剤組成物。[Claims] 1. A hydrocarbon having a softening point obtained by polymerizing (a) polychloroprene and (b) a hydrocarbon having a total content of indene and methylindene of 80% by weight or more using a Friedel-Crafts catalyst. 140°C or higher, and weight average molecular weight (Mw)
A polychloroprene-based adhesive composition containing as a main component a hydrocarbon resin having a ratio Mw/Mn of 3.0 or less. 2. Hydrocarbons with a total content of indene and methyl indene of 80% by weight or more are found in 140 to 24 fractions of fractions obtained by naphtha cracking and tar distillation.
The polychloroprene adhesive composition according to claim 1, which is prepared from a fraction having a boiling point within the range of 0°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21490390A JP2841785B2 (en) | 1990-08-16 | 1990-08-16 | Polychloroprene adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21490390A JP2841785B2 (en) | 1990-08-16 | 1990-08-16 | Polychloroprene adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0496982A true JPH0496982A (en) | 1992-03-30 |
| JP2841785B2 JP2841785B2 (en) | 1998-12-24 |
Family
ID=16663474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21490390A Expired - Lifetime JP2841785B2 (en) | 1990-08-16 | 1990-08-16 | Polychloroprene adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841785B2 (en) |
-
1990
- 1990-08-16 JP JP21490390A patent/JP2841785B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2841785B2 (en) | 1998-12-24 |
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