JPH0147509B2 - - Google Patents
Info
- Publication number
- JPH0147509B2 JPH0147509B2 JP55167132A JP16713280A JPH0147509B2 JP H0147509 B2 JPH0147509 B2 JP H0147509B2 JP 55167132 A JP55167132 A JP 55167132A JP 16713280 A JP16713280 A JP 16713280A JP H0147509 B2 JPH0147509 B2 JP H0147509B2
- Authority
- JP
- Japan
- Prior art keywords
- methacrylate
- adhesive
- odor
- tensile shear
- shear strength
- 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.)
- Expired
Links
- 239000000853 adhesive Substances 0.000 claims description 31
- 230000001070 adhesive effect Effects 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- -1 alkoxyalkyl methacrylate Chemical compound 0.000 claims description 13
- 229920002681 hypalon Polymers 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 239000012190 activator Substances 0.000 description 10
- 238000001879 gelation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- HVBADOTWUFBZMF-UHFFFAOYSA-N 1-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOC(C)OC(=O)C(C)=C HVBADOTWUFBZMF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000010959 steel 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
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- HJKXLQIPODSWMB-UHFFFAOYSA-N 4-(4-chlorosulfonylphenoxy)benzenesulfonyl chloride Chemical compound C1=CC(S(=O)(=O)Cl)=CC=C1OC1=CC=C(S(Cl)(=O)=O)C=C1 HJKXLQIPODSWMB-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
本発明は接着剤の改良に関する。実質的に溶剤
を含まず、モノマー成分の重合により硬化して、
多種類の被着材を強力に接着する反応型の接着剤
は公知である。例えば二成分型接着剤であり、第
一の成分はアクリル単量体またはメタクリル単量
体とパーオキサイドまたはハイドロパーオキサイ
ドからなり、第二の成分は常温においてアクリル
またはメタクリル単量体の重合を開始させる活性
化剤からなる。ここで活性化剤は、単量体に対し
て非化学量論的な量でも充分に接着強度がでるも
のが好都合である。DETAILED DESCRIPTION OF THE INVENTION This invention relates to improvements in adhesives. It contains virtually no solvent and is cured by polymerization of monomer components.
Reactive adhesives that strongly bond various types of adherends are known. For example, it is a two-component adhesive, where the first component consists of an acrylic or methacrylic monomer and a peroxide or hydroperoxide, and the second component initiates polymerization of the acrylic or methacrylic monomer at room temperature. It consists of an activator that causes Here, the activator is preferably one that can provide sufficient adhesive strength even in a non-stoichiometric amount relative to the monomer.
米国特許第3890407号にはクロロスルホン化し
たポリエチレンおよび塩化スルホニルと塩素化ボ
リエチレンとの混合物よりなる群からえらばれた
含硫黄組成物をアクリル単量体およびメタクリル
単量体よりなる群からえらばれた少なくとも１種
の重合可能な単量体に溶解した溶液ならびに遊離
基生成剤よりなる接着剤組成物が示されている。 U.S. Pat. No. 3,890,407 describes a sulfur-containing composition selected from the group consisting of chlorosulfonated polyethylene and a mixture of sulfonyl chloride and chlorinated polyethylene, and a sulfur-containing composition selected from the group consisting of acrylic monomers and methacrylic monomers. Adhesive compositions are shown comprising a solution of at least one polymerizable monomer as well as a free radical generator.
しかし、この種の接着剤組成物はすぐれた接合
を与えるものであるが、臭気及び人体に対する有
害性の点において改良が必要である。接着剤の実
際の使用に対して接着性能（接着速度とか接着
力）がすぐれていることが重要な要因であるが、
接着剤の臭気とか人体に対する有害性の問題もい
ずれ劣らぬ重要な問題である。いくら接着性能が
すぐれていても臭気とか有害性が大きければ使用
困難である。 However, although this type of adhesive composition provides excellent bonding, it requires improvement in terms of odor and toxicity to the human body. An important factor in the actual use of adhesives is that they have excellent adhesive performance (adhesion speed and adhesive strength).
Issues such as the odor of adhesives and their toxicity to the human body are equally important. No matter how good the adhesive performance is, if it has a strong odor or is harmful, it will be difficult to use.
本発明者らはこの問題に対し、いろんな角度か
ら検討した結果、アルコキシアルキルアクリレー
トまたはアルコキシアルキルメタクリレートから
選ばれた少くとも１種の単量体をつかえば、臭気
および人体に対する有害性の点においてすぐれ、
かつ接着硬化速度および接着強度がきわめて良好
であることを見出した。 The present inventors investigated this problem from various angles and found that using at least one monomer selected from alkoxyalkyl acrylates and alkoxyalkyl methacrylates is superior in terms of odor and toxicity to the human body. ,
It was also found that the adhesive curing speed and adhesive strength were extremely good.
米国特許第3890407には重合性単量体の具体例
として多くの単量体が記載されているが、特に好
適な単量体は低級アルキルアクリレートおよびメ
タクリレートであつて、具体例としてメチルメタ
クリレート、エチルメタクリレート、ｎ−ブチル
メタクリレート、２−エチルヘキシルメタクリレ
ート等が記載されているが、これらのうちメチル
メタクリレート、エチルメタクリレートおよびｎ
−ブチルメタクリレートは臭気が強く人体に対す
る有害性もかなりある。２−エチルヘキシルメタ
クリレートは比較的臭気が弱いがやはりアクリル
系単量体特有の臭気がありかつ、２−エチルヘキ
シルメタクリレート単独で接着剤にしたものは接
着速度および接着強度の面で不満足である。 Although many monomers are described as specific examples of polymerizable monomers in U.S. Pat. No. 3,890,407, particularly preferred monomers are lower alkyl acrylates and methacrylates. Methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc. are described, but among these, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate are described.
-Butyl methacrylate has a strong odor and is quite harmful to the human body. Although 2-ethylhexyl methacrylate has a relatively weak odor, it still has an odor characteristic of acrylic monomers, and adhesives made from 2-ethylhexyl methacrylate alone are unsatisfactory in terms of adhesion speed and adhesive strength.
これに対し本発明のアルコキシアルキルメタク
リレートおよびアルコキシアルキルアクリレート
は臭気は無臭に近く、かつ有害性も小さく極めて
実用上有益である。さらにこの単量体の優れてい
る点は接着速度および接着強度が大きいことであ
る。 In contrast, the alkoxyalkyl methacrylates and alkoxyalkyl acrylates of the present invention are nearly odorless, less harmful, and extremely useful in practical terms. Another advantage of this monomer is its high adhesion speed and high adhesive strength.
本発明に用いられるアルコキシメタクリレート
およびアルコキシアルキルアクリレートは次の一
般式であらわされる。 The alkoxy methacrylate and alkoxyalkyl acrylate used in the present invention are represented by the following general formula.
ここにR1は水素かメチル基である。R2はエチ
レン、プロピレン、トリメチレン、１，２−ブチ
レン、２，３−ブチレン基である。R3はメチル、
エチル、プロピル、イソプロピル、ブチル、イソ
ブチル、sec−ブチル、アミル、ヘキシル、２−
エチルヘキシル基である。 Here R 1 is hydrogen or a methyl group. R2 is an ethylene, propylene, trimethylene, 1,2-butylene, or 2,3-butylene group. R 3 is methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, hexyl, 2-
It is an ethylhexyl group.
本発明のアルコキシアルキルメタクリレート及
びアクリレート以外に使用し得る単量体として
は、補助的に強度を向上させる作用のあるメタク
リル酸またはアクリル酸、耐熱性を向上させる作
用のあるエチレングリコールジメタクリレート、
トリメチロールプロパントリメタクリレート等の
ジまたはトリ（メタ）アクリレート、さらにその
他の一般の（メタ）アクリレート単量体でもその
使用比率が小さくてグルーにしたときの臭気がさ
ほど影響しない範囲に於て、使用可能である。こ
の範囲内におけるこれらの単量体の使用量は接着
性能を損なわないものであることはいうまでもな
い。 Monomers that can be used in addition to the alkoxyalkyl methacrylate and acrylate of the present invention include methacrylic acid or acrylic acid, which has an auxiliary effect of improving strength, ethylene glycol dimethacrylate, which has an effect of improving heat resistance,
Di- or tri(meth)acrylates such as trimethylolpropane trimethacrylate, as well as other general (meth)acrylate monomers, may be used as long as the proportion used is small and the odor when made into a glue is not significantly affected. It is possible. It goes without saying that the amount of these monomers used within this range does not impair adhesive performance.
本発明に使用するクロルスルホン化ポリエチレ
ンは重合体100g当り25〜75重量％の塩素および
３〜160ミリモルの塩化スルホニル部分を含み且
つ、４〜500の溶融係数を有するポリエチレンか
らつくられたものである。塩化スルホニルは、例
えばトルエンスルホニルクロリド、ジフエニルエ
ーテル−４，4′−ジスルホニルクロリド等が適し
ている。クロロスルホン化ポリエチレンと重合可
能な単量体との比率は重合体100重量部当り単量
体50〜500重量部である。塩素化ポリエチレンの
場合も同様である。 The chlorosulfonated polyethylene used in the present invention is made from polyethylene containing 25 to 75% by weight of chlorine and 3 to 160 mmol of sulfonyl chloride moieties per 100 g of polymer and having a melting coefficient of 4 to 500. . Suitable sulfonyl chlorides include, for example, toluenesulfonyl chloride, diphenyl ether-4,4'-disulfonyl chloride, and the like. The ratio of chlorosulfonated polyethylene to polymerizable monomer is from 50 to 500 parts by weight of monomer per 100 parts by weight of polymer. The same applies to chlorinated polyethylene.
また本発明で遊離基生成剤として有機パーオキ
サイド及びハイドロパーオキサイドを使用する。
有機過酸化物の量は全組成物の0.01〜10重量部で
ある。また保存安定性を良くするために安定剤を
添加する。最も好ましい安定剤は２，６−ジ−ｔ
−ブチル−４−メチルフエノールである。安定剤
の好ましい量は全組成物の0.01〜10重量部であ
る。 The present invention also uses organic peroxides and hydroperoxides as free radical generators.
The amount of organic peroxide is from 0.01 to 10 parts by weight of the total composition. A stabilizer is also added to improve storage stability. The most preferred stabilizer is 2,6-di-t
-butyl-4-methylphenol. The preferred amount of stabilizer is 0.01 to 10 parts by weight of the total composition.
本発明において用いられる活性化剤化合物は、
例えば第三級アミン（例えばＮ，N′−ジメチル
アニリン、Ｎ，N′−ジイソプロピル−Ｐ−トル
イジン）またはアルデヒドと第一級もしくは第二
級アミンとの縮合生成物（例えばブチルアルデヒ
ドとアニリンもしくはブチルアミンとの縮合生成
物であり、これらの例示化合物にはデユポン社の
活性化剤808および833が含まれる。 The activator compound used in the present invention is
For example, tertiary amines (e.g. N,N'-dimethylaniline, N,N'-diisopropyl-P-toluidine) or condensation products of aldehydes with primary or secondary amines (e.g. butyraldehyde and aniline or butylamine) Exemplary compounds include DuPont's Activators 808 and 833.
本発明に従がえば接着硬化速度を大ならしめる
ために活性化剤とともに促進剤を用いる。好適な
促進剤としては遷移金属の酸化性化合物が含まれ
る。例えばナフテン酸銅、ナフテン酸コバルト、
ナフテン酸鉄、ナフテン酸ニツケル、またはアセ
チルアセトンと鉄、銅、コバルトもしくはバナジ
ウムの錯化合物が含まれる。 According to the present invention, an accelerator is used in conjunction with an activator to increase the speed of adhesive curing. Suitable promoters include oxidizing compounds of transition metals. For example, copper naphthenate, cobalt naphthenate,
Included are complexes of iron naphthenate, nickel naphthenate, or acetylacetone with iron, copper, cobalt, or vanadium.
実施例 １
エトキシエチルメタクリレート 120g、クロ
ルスルホン化ポリエチレン注１）
60g、メタク
リル酸 15g、エチレングリコールジメタクリレ
ート 3g、キユメンハイドロパーオキサイド
1g、２，６−ジ−ｔ−ブチル−４−メチルフエ
ノール 0.6g
注１）塩素43％、硫黄1.1％、を含み、ムーニ
ー粘度が30のクロルスルホン化ポリエチレンを使
用。Example 1 Ethoxyethyl methacrylate 120g, chlorosulfonated polyethylene Note 1) 60g, methacrylic acid 15g, ethylene glycol dimethacrylate 3g, kyumene hydroperoxide
1g, 2,6-di-t-butyl-4-methylphenol 0.6g Note 1) Use chlorosulfonated polyethylene containing 43% chlorine, 1.1% sulfur, and a Mooney viscosity of 30.
からなる均一な接着剤組成物をつくつた。このも
のはメタクリル酸のわずかな酸臭のみで、殆んど
苦になる臭はなかつた。A uniform adhesive composition was prepared. This product had only a slight sour odor of methacrylic acid, and had almost no unpleasant odor.
100×25×1.6mm寸法の冷間圧延鋼板をAA−150
のサンドペーパーで研摩し、アセトン−トルエン
１：１の混合液で脱脂した試験片の一方にデユポ
ン社活性化剤808をうすく塗布し、もう一方の試
験片に本例の接着剤組成物を塗布して両面を２〜
３回すり合わせ、接着面積が25×12.5mmになるよ
うに重ね合わせて約１Kgｆの力で圧着し５分経過
後および24時間経過後の引張剪断強度を測定し
た。 AA−150 cold rolled steel plate with dimensions of 100×25×1.6mm
A thin layer of Dupont Activator 808 was applied to one of the specimens, which had been polished with sandpaper and degreased with a 1:1 mixture of acetone and toluene, and the adhesive composition of this example was applied to the other specimen. and both sides 2~
They were rubbed together three times, stacked so that the adhesive area was 25 x 12.5 mm, and pressed together with a force of about 1 Kgf, and the tensile shear strength was measured after 5 minutes and 24 hours.
５分後の引張剪断強度 157Kg／cm2 24時間後の引張剪断強度 262Kg／cm2。 Tensile shear strength after 5 minutes: 157Kg/cm 2 Tensile shear strength after 24 hours: 262Kg/cm 2 .
本接着剤組成物の保存安定性は次の通りおこな
つた。10mlガラスビン中に約8g試料を入れ、密
栓して80℃のオーブン中に入れてゲル化するまで
の時間を測定する。本組成物のゲル化時間は約16
時間で充分な安定性を有していることがわかつ
た。 The storage stability of this adhesive composition was tested as follows. Place approximately 8 g of sample in a 10 ml glass bottle, seal it tightly, and place it in an oven at 80°C to measure the time it takes to gel. The gelation time of this composition is approximately 16
It was found to have sufficient stability over time.
実施例 ２
エトキシエチルメタクリレート 120g、クロ
ルスルホン化ポリエチレン注２）
55g、メタクリ
ル酸 20g、エチレングリコールジメタクリレー
ト 3g、キユメンハイドロパーオキサイド 1g、
２，６−ジ−ｔ−ブチル−４−メチルフエノール
0.8g
注２）塩素29％および硫黄1.4％を含み、ムー
ニー粘度30のクロルスルホン化ポリエチレンを使
用。Example 2 Ethoxyethyl methacrylate 120g, chlorosulfonated polyethylene Note 2) 55g, methacrylic acid 20g, ethylene glycol dimethacrylate 3g, kyumene hydroperoxide 1g,
2,6-di-t-butyl-4-methylphenol
0.8g Note 2) Contains 29% chlorine and 1.4% sulfur, and uses chlorosulfonated polyethylene with a Mooney viscosity of 30.
からなる均一な接着剤組成物をつくつた。実施例
１と同様臭いは極めてマイルドであつた。A uniform adhesive composition was prepared. Similar to Example 1, the odor was extremely mild.
実施例１と同様の鋼板の試験片の一方に活性化
剤808に銅分として0.05％含有したプライマーを
うすく塗布し、もう一方の面に実施例２の接着剤
組成物を塗布して圧締し、５分後および24時間後
の引張剪断強度を測定した。 A primer containing activator 808 with a copper content of 0.05% was applied thinly to one side of the same steel plate test piece as in Example 1, and the adhesive composition of Example 2 was applied to the other side, followed by pressing. The tensile shear strength was measured after 5 minutes and 24 hours.
５分後の引張剪断強度 165Kg／cm2
24時間後の引張剪断強度 272Kg／cm2
実施例１と同様80℃オーブン中でゲル化するま
での時間を測定したところ、約23時間で極めて安
定性が良好であつた。 Tensile shear strength after 5 minutes: 165 Kg/cm 2 Tensile shear strength after 24 hours: 272 Kg/cm 2 As in Example 1, the time until gelation was measured in an oven at 80°C revealed that it was extremely stable after about 23 hours. was good.
実施例 ３
実施例２のエトキシエチルメタクリレート
120gのかわりにブトキシエチルメタクリレート
120gを用いたほかは全て実施例２と同じ接着
剤組成物をつくつた。このものは臭いはマイルド
であつた。Example 3 Ethoxyethyl methacrylate of Example 2
butoxyethyl methacrylate instead of 120g
The same adhesive composition as in Example 2 was prepared except that 120 g was used. This product had a mild odor.
実施例２と同様鋼板の一方に活性化剤808に銅
分として0.05％含有したプライマーを塗布し、も
う一方に実施例３の接着剤組成物を塗布して圧締
し、５分後および24時間後の引張剪断強度を測定
した。 As in Example 2, a primer containing 0.05% copper in activator 808 was applied to one side of the steel plate, and the adhesive composition of Example 3 was applied to the other side and pressed together, and after 5 minutes and 24 The tensile shear strength after the time was measured.
５分後の引張剪断強度 125Kg／cm2 24時間後の引張剪断強度 235Kg／cm2 また80℃でのゲル化時間は21時間であつた。 The tensile shear strength after 5 minutes was 125 Kg/cm 2 The tensile shear strength after 24 hours was 235 Kg/cm 2 and the gelation time at 80°C was 21 hours.
実施例 ４
実施例１のエトキシエチルメタクリレート
120gのかわりにエトキシエチルメタクリレート
65gと２−エチルヘキシルメタクリレート
55gとを用いたほかは全て実施例１と同じ接着剤
組成物をつくつた。このものは実施例１の接着剤
組成物の臭いとほぼ類似で殆んど苦になる臭いは
なかつた。Example 4 Ethoxyethyl methacrylate of Example 1
Ethoxyethyl methacrylate instead of 120g
65g and 2-ethylhexyl methacrylate
An adhesive composition was prepared in the same manner as in Example 1 except that 55 g of the same adhesive composition was used. This product had almost the same odor as the adhesive composition of Example 1, and had almost no unpleasant odor.
実施例１と同様にデユポン社活性化剤808をつ
かつて５分後および24時間後の引張剪断強度を測
定した。 In the same manner as in Example 1, the tensile shear strength was measured after 5 minutes and 24 hours using DuPont Activator 808.
５分後の引張剪断強度 150Kg／cm2
24時間後の引張剪断強度 253Kg／cm2
また80℃でのゲル化時間は15時間で十分な安定
性を有していた。 Tensile shear strength after 5 minutes: 150 Kg/cm 2 Tensile shear strength after 24 hours: 253 Kg/cm 2 In addition, the gelation time at 80° C. was 15 hours, indicating sufficient stability.
比較例
実施例１のエトキシエチルメタクリレート
120gのかわりに、メチルメタクリレート 120g
を用いたほかは全て実施例と同じ接着剤組成物を
つくつた。このものはメチルメタクリレート特有
の臭いが非常につよかつた。実施例１と同様にデ
ユポン社活性化剤808をつかつて５分後および24
時間後の引張剪断強度を測定した。Comparative Example Ethoxyethyl methacrylate of Example 1
Methyl methacrylate 120g instead of 120g
An adhesive composition was prepared in the same manner as in the example except that the same adhesive composition was used. This product had a very strong odor characteristic of methyl methacrylate. After 5 minutes and 24 hours using Dupont Activator 808 in the same manner as in Example 1.
The tensile shear strength after the time was measured.
５分後の引張剪断強度 35Kg／cm2 24時間後の引張剪断強度 229Kg／cm2 また80℃でのゲル化時間は10時間であつた。 The tensile shear strength after 5 minutes was 35 Kg/cm 2 The tensile shear strength after 24 hours was 229 Kg/cm 2 and the gelation time at 80°C was 10 hours.
このようにメチルメタクリレートを使つたもの
は臭いがつよく、５分後の強度も弱かつた。 The product using methyl methacrylate had a strong odor and was weak in strength after 5 minutes.
Claims (1)
アルコキシアルキルアクリレートから選ばれた少
なくとも１種の単量体、(2)アクリル単量体または
メタクリル単量体から成る群から選ばれた少くと
も１種の単量体、(3)クロルスルフオン化ポリエチ
レンまたは塩化スルホニルと塩素化ポリエチレン
との混合物、(4)有機過酸化物、(5)安定剤からなる
接着剤組成物。1. (1) At least one monomer selected from alkoxyalkyl methacrylate or alkoxyalkyl acrylate, (2) At least one monomer selected from the group consisting of acrylic monomers or methacrylic monomers. , (3) a mixture of chlorosulfonated polyethylene or sulfonyl chloride and chlorinated polyethylene, (4) an organic peroxide, and (5) an adhesive composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16713280A JPS5790073A (en) | 1980-11-26 | 1980-11-26 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16713280A JPS5790073A (en) | 1980-11-26 | 1980-11-26 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5790073A JPS5790073A (en) | 1982-06-04 |
| JPH0147509B2 true JPH0147509B2 (en) | 1989-10-13 |
Family
ID=15844016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16713280A Granted JPS5790073A (en) | 1980-11-26 | 1980-11-26 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5790073A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61225269A (en) * | 1985-03-29 | 1986-10-07 | Taoka Chem Co Ltd | Wood adhesive composition |
| IT1233880B (en) * | 1988-03-25 | 1992-04-21 | Mini Ricerca Scient Tecnolog | ADHESIVE COMPOSITIONS. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49132119A (en) * | 1972-07-20 | 1974-12-18 | ||
| JPS517040A (en) * | 1974-06-05 | 1976-01-21 | Du Pont |
-
1980
- 1980-11-26 JP JP16713280A patent/JPS5790073A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49132119A (en) * | 1972-07-20 | 1974-12-18 | ||
| JPS517040A (en) * | 1974-06-05 | 1976-01-21 | Du Pont |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5790073A (en) | 1982-06-04 |
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