WO2000077108A1 - Composition adhesive anaerobie - Google Patents

Composition adhesive anaerobie Download PDF

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Publication number
WO2000077108A1
WO2000077108A1 PCT/KR1999/000285 KR9900285W WO0077108A1 WO 2000077108 A1 WO2000077108 A1 WO 2000077108A1 KR 9900285 W KR9900285 W KR 9900285W WO 0077108 A1 WO0077108 A1 WO 0077108A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
anaerobic adhesive
acid
metha
oligomers
Prior art date
Application number
PCT/KR1999/000285
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English (en)
Inventor
In Hwan Park
Sang Chul Che
Original Assignee
Korea Research Institute Of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Korea Research Institute Of Chemical Technology filed Critical Korea Research Institute Of Chemical Technology
Priority to PCT/KR1999/000285 priority Critical patent/WO2000077108A1/fr
Publication of WO2000077108A1 publication Critical patent/WO2000077108A1/fr

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    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to an anaerobic adhesive composition and more particularly, to the anaerobic adhesive composition which blends a difunctional carboxylic acid, expressed by the following formula I, to the anaerobic adhesive composition comprising monomers, oligomers, inhibitors, oxidizers, reducers and thickening agents, showing some useful characteristics; a)the rapid velocity in a hardening reaction, b)the good stability in long-term storage, and c)the break-loose torque which is sufficiently applied in the assembly of bolt-nuts, precision apparatuses or electric/ electronic parts:
  • the anaerobic adhesive composition of common type was prepared by chemicals such as monomers, oligomers, inhibitors, peroxide- typed oxidizers(e.g., hydrogen peroxide and cumene hydroperoxide) and reducers(e.g., amines and imides) as disclosed in the following conventional methods[European Patent Appln. No. 446,144(1991), 443,916(1991); 499,483(1992); and Japanese Patent Kokai No. Pyeong2-187,401].
  • chemicals such as monomers, oligomers, inhibitors, peroxide- typed oxidizers(e.g., hydrogen peroxide and cumene hydroperoxide) and reducers(e.g., amines and imides) as disclosed in the following conventional methods[European Patent Appln. No. 446,144(1991), 443,916(1991); 499,483(1992); and Japanese Patent Kokai No. Pyeong2-187,401].
  • an oxidizer and a reducer were used together m the preparation of anaerobic adhesive composition, as described in the following methods: Hung. Telies Hu 44, 280(1988) as a method using a complex alkaline solution, US Patent No. 4,731,146 as a method using a copper compound, and closed German Patent No. 3,611,307 as a method using a phosphate compound, etc.
  • the anaerobic adhesive composition in its initial development stage was prepared in such a method that an inhibitor was added to a mixture of monomers and oligomers: the oligomers are derived from multi-functional (metha)acrylates (Japanese Patent Kokai No. Sho43-6545, Sho44-852). Then, the inhibitor was used as a scavenger for radicals which can spontaneously generate in the state of preparation or storage.
  • Japanese Patent Kokai No. Sho46-3160, Sho57-83572 and Pyeong6-66308 disclosed the anaerobic adhesive composition containing acrylic acid, methacrylic acid or thiosalicylic acid in order to increase its break-loose torque.
  • glycerol dimethacrylate esterified by succinic acid anhydride was used as a component of the anaerobic adhesive composition, as described by closed German Patent No. 3,527,717.
  • Japanese Patent Kokai No. Sho62-184,076 disclosed that methylsulfamic acid was added to the anaerobic adhesive composition, but it brought about corrosion on the surface of metallic materials.
  • an anaerobic adhesive composition when used to assemble parts into a complete whole, the enhancement of adhesive force as well as workability is powerfully required toward higher productivity.
  • a reducer containing the groups like imides, mercaptos or amines is concurrently used with a peroxide-typed initiator, where it is very important to select a useful reducer/ oxidizer catalyst.
  • the anaerobic adhesive composition is very unstable under its coexistence and can be easily initiated by radicals spontaneously produced between them. Although it is extremely difficult that a hardening reaction in progress is stopped or controlled the reaction in storage at room temperature was generally controlled by the addition of inhibitor above-mentioned. Therefore, it is previously added to a mixture of monomers and oligomers in the preparation of anaerobic adhesive composition.
  • the anaerobic adhesive composition always requires access to the proper regulation of physical properties like strength and flexibility by way of the enhancement of both the rapid velocity in hardening and the stability in storage.
  • a difunctional carboxylic acid is essentially added to an anaerobic adhesive composition in this invention.
  • An object of this invention is to provide the anaerobic adhesive composition with the stability in storage as well as the rapid hardening in fastening by mixing the difunctional carboxylic acid, where the anaerobic adhesive composition as a product shows useful break-loose torque.
  • This invention relates to an anaerobic adhesive composition which blends 0.0001 - 10 parts in weight of a difunctional carboxylic acid, expressed by the following formula I, in proportion to 100 parts in weight of a mixture of monomers and oligomers, to the anaerobic adhesive composition comprising monomers, oligomers, inhibitors, oxidizers, reducers and thickening agents:
  • the anaerobic adhesive composition applicable to prevent a bolt which is jointed nuts from releasing requires the rapid hardening in fastening as well as the stability in storage, thereby enhancing its break-loose torque and workability.
  • the difunctional carboxylic acid expressed by formula I is largely mixed to a mixture of monomers and oligomers.
  • Table 1 in this invention the values of pK a (acid dissociation constant) of aliphatic difunctional carboxylic acids gradually increased with increasing the values of n above-mentioned, and then slightly decreased with increasing the values of n above 2. Then, the values of pK ⁇ in non-aliphatic difunctional carboxylic acids were less than those of aliphatic difunctional carboxylic acids.
  • pKj was the lowest value in various difunctional carboxylic acids.
  • the anaerobic adhesive composition containing a difunctional carboxylic acid brings about a rapid hardening reaction as well as the stability in storage: as the value of n gradually increases, the acidity of difunctional carboxylic acid decreases.
  • the break-loose torque of the anaerobic adhesive composition also increases with shortening the hardening time, and then its molecular weight grows bigger.
  • n is limited as an integer in the range of 2-10 according to this invention, and then the difunctional carboxylic acid is in the range of 1-5 of pKa.
  • carboxylic acid scarcely give any effects on the acidity of an oxidizer like cumene hydroperoxide, the stability in storage of the anaerobic adhesive composition gets better.
  • the anaerobic adhesive composition showed useful break-loose torque caused by a rapid hardening reaction in the presence of difunctional carboxylic acid. When a bolt and a nut are jointed, the small quantity of air solubilized in the anaerobic adhesive composition is excluded, and at the same time a hardening reaction is initiated. The reaction proceeds of itself under the condition.
  • anaerobic adhesive composition of this invention In the preparation of anaerobic adhesive composition of this invention, first of all, monomers, oligomers and inhibitors are mixed and agitated under oxygen atmosphere. Subsequently, each of reducers and oxidizers is added to the mixture, followed by the addition of difunctional carboxylic acid. Thereafter, in order to increase the viscosity of the anaerobic adhesive composition, polyethylene resin(particle size: belowlO ⁇ ) and fumed silica(particle size: below 5 ⁇ ) as thickening agents are added.
  • Monomers used in this invention are one or more selected from ethyleneglycol di(metha)acrylate, diethyleneglycol di(metha)acrylate, triethyleneglycol di(metha)acrylate, tetraethyleneglycol di(metha)acrylate, trimethylolpropane tri(metha)acrylate, styrene, chlorostyrene, vinyltoluene, a- methylstyrene, vinylacetate, methylacrylate, ethylacrylate, butylacrylate and methy lmethacry late .
  • oligomers used in this invention are one or more selected from mono or poly(metha)acrylate oligomer of bisphenolic compound, a , ⁇ -diacryloyl-(bisethyleneglycol)-phthalate and a , ⁇ - tetraacryloyl-(bistrimethylolpropane)-tetrahydrophthalate, and the acrylic oligomers containing aliphatic and aromatic urethane groups or poly ether groups.
  • a difunctional carboxylic acid represented by formula I is used in this invention.
  • the difunctional carboxylic acid is one or more selected from malonic acid, succinic acid, adipic acid, itaconic acid, pimelic acid, terephthalic acid and decanoic acid.
  • the quantity of difunctional carboxylic acid can be blended within 0.0001-10 parts in weight in proportion to 100 parts in weight of a mixture of monomers and oligomers. If the amount is less than 0.0001 part in weight, the promotion of a hardening reaction may be negligible, but may be possible in the quantity more than 10 parts in weight: the storage stability of the anaerobic adhesive composition may be lowered, so that the composition of the carboxylic acid should be properly controlled within above range.
  • an inhibitor is one or more selected from hydroquinone, methylhydroquinone, hydroquinone monomethylether, naphthoquinone, penanthraquinone, anthraquinone, sebenzoquinone, catechol, t-butylcatechol, 2,6-t-butyl-4-methylphenol, phenothiazine, picric acid phenothiazine and hydroxydiphenylamine.
  • a metal ion chelating agent is used one or more selected from ethylenediamine tetraacetic acid and its salt.
  • the quantity of inhibitor can be added 0.0001-3 parts in weight in proportion to 100 parts in weight of a mixture of monomers and oligomers. If the quantity is less than 0.0001 part in weight, the effect of inhibition may be insufficient, finally lowering the stability in storage, but in the quantity more than 3 parts in weight, the break-loose torque may be lowered, as the hardening time lengthened.
  • an oxidizer is one or more selected from t-burylhydroperoxide, cumenhydroperoxide, di-t-butylhydroperoxide, methylethylketoneperoxide, dicumylperoxide, 2 ⁇ -di ⁇ ethylhexyl-2 ⁇ -dihydroperoxide, d ⁇ sopropylbenzene hydroperoxide, t-butylbenzoate and t-butylperoxyacetate.
  • a reducer is one or more selected from phenyl- a -naphthylamine, N,N'- dimethy 1-p-toluidine, N, N'-dimethy laniline, triethy lenetetramine, diethylenetriamine, tri-N-butylamine, o-benzoic sulfimide, acetylthiourea, ethylene thiourea and 2-mercaptobenzothiazole.
  • An initiator is used as the form combined one or more.
  • the quantity of initiator can be added 0.001-10 parts in weight in proportion to 100 parts in weight of a mixture of monomers and oligomers. If the quantity is less than 0.001 part in weight, the effect of initiation is insufficient, but in the quantity more than 10 parts in weight, the storage stability of the anaerobic adhesive composition may be lowered, so that the composition of the initiator should be properly controlled within above range.
  • anaerobic adhesive compositions containing difuctional carboxylic acids were prepared and briefly estimated: it was found that the anaerobic adhesive composition without a difunctional carboxylic acid exhibited longer hardening time and less break-loose torque, whereas the anaerobic adhesive composition with it exhibited a hardening time less than 15 min. and the break-loose torque after 24 hr was also very useful.
  • the anaerobic adhesive composition (Table 2a, run ® ⁇ 12) was prepared as follows. That is, lOg of ethyleneglycol dimethacrylate, lOg of ' 2-hydroxyethyl methacrylate and lOg of tetraetyleneglycol dimethacrylate as components of monomers and oligomers were added to a reactor with reflux condenser and agitated at 120rpm under 120cc/min of oxygen flow. Then, 0.05g of hydroquinone methylether as an inhibitor was added and agitated for lOmins, followed by the addition of 3g of cumene hydroperoxide as an oxidizer.
  • Viscosity the value is measured by RVDVI+ viscometer.
  • An anaerobic adhesive composition was prepared in the same methods as described in Examples ⁇ l-13.
  • CD examples; ® : comparative examples; M ⁇ : ethyleneglycol dimethacrylate; M 2 : 2-hydroxyethyl methacrylate; M 3 : tetraethyleneglycol dimethacrylate; M 4 : urethaneacrylate (Aronics M-1100, Dong-A Synthetic Industrial Co., Japan); HQ : hydroquinone methylether; QH : cumene hydroperoxide; A t : o-benzoic sulfimide; A 2 : N,N'-dimethyl-p-toluidine; A 3 : titanium dioxide; CA X : oxalic acid; CA 2 : adipic acid; each of CA j and CA 2 : calculated by mol concentration; Tj : polyethylene powder(5 ⁇ m of average diameter); T 2 : fumed silica(5 ⁇ m of average diameter).
  • ⁇ and ® represent examples and comparative ones, respectively.
  • anaerobic adhesive compositions using an hardening promoter without difunctional carboxylic acid groups (comparative examples ⁇ l-7); the anaerobic adhesive compositions using titanium dioxide as an auxiliary oxidizer(comparative examples ⁇ 4,5); the anaerobic adhesive composition using oxalic acid (comparative example ⁇ 7); the anaerobic adhesive compositions containing an excessive quantity of reducer and oxidizer as an initiator(comparative examples ⁇ 8,9); the anaerobic adhesive composition using an excessive quantity of urethaneacrylate(comparative example ⁇ 9); the anaerobic adhesive composition containing an excessive quantity of cumene hydroperoxide(comparative example ⁇ 10); the anaerobic adhesive composition using an insufficient quantity of difunctional carboxylic acid(comparative example ⁇ 11) showed relatively longer hardening time and less break-loose torque.
  • the anaerobic adhesive composition using an excessive quantity of difunctional carboxylic acid or fumed silica(comparative examples ⁇ -12-14) showed the increase of acidity in solution, followed by the poor stability in storage. Also, the anaerobic adhesive composition containing an excessive quantity of thickening agent (comparative example ⁇ 15) showed a great difficulty in mixing. On the other hand, comparative examples ⁇ 4 , 5, 8-15 showed the poor stability in storage.
  • the break-loose torque of anaerobic adhesive compositions using a thickening agent was better than that without a thickening agent (examples ® ⁇ 1-11).
  • the anaerobic adhesive composition comprising monomers, oligomers, inhibitors, oxidizers, reducers and thickening agents in the presence of difunctional carboxylic acid exhibited the rapid velocity in a hardening reaction, the good stability in storage, and the good strength in break-loose torque.
  • the anaerobic adhesive composition according to this invention is applicable to the fastening between a bolt and a nut, and the assembly of precision apparatuses and electric/ electronic parts.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Cette invention se rapporte à une composition adhésive anaérobie et, plus particulièrement, à une composition adhésive anaérobie qui mélange un acide carboxylique bifonctionnel, exprimé par la formule (I), à une composition adhésive anaérobie comprenant des monomères, des oligomères, des inhibiteurs, des oxydants, des réducteurs et des agents d'épaississement, possédant certaines propriétés physiques utiles telles que: a) une vitesse de réaction de durcissement élevée, b) une bonne stabilité lors de la conservation sur de longues périodes, et c) un couple de décollement suffisant lors de l'assemblage d'écrous à boulons, d'appareils de précision et de pièces électriques/électroniques. Dans la formule (I), R représente (CH2)n ou CH2C(=CH2) et n est égal à un nombre entier compris entre 2 et 10.
PCT/KR1999/000285 1999-06-10 1999-06-10 Composition adhesive anaerobie WO2000077108A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7595352B2 (en) * 2003-11-24 2009-09-29 Samsung Electronics Co., Ltd. Photo-curable adhesive composition, optical pick-up device using the same, and optical recording/reproducing drive including the optical pick-up device
US10968310B1 (en) 2015-04-28 2021-04-06 Adhesive R&D, Inc. Polymerizable materials, anaerobically curable compositions, and related methods and products
CN117965112A (zh) * 2024-04-01 2024-05-03 广东粤港澳大湾区黄埔材料研究院 耐高温厌氧胶及其使用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6210179A (ja) * 1985-07-09 1987-01-19 Nippon Shokubai Kagaku Kogyo Co Ltd 嫌気性接着剤組成物
DD290776A7 (de) * 1988-10-17 1991-06-13 Kolloidchemie Gmbh,De Acrylatklebstoffsystem

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6210179A (ja) * 1985-07-09 1987-01-19 Nippon Shokubai Kagaku Kogyo Co Ltd 嫌気性接着剤組成物
DD290776A7 (de) * 1988-10-17 1991-06-13 Kolloidchemie Gmbh,De Acrylatklebstoffsystem

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Database WPI, Derwent Publications Ltd., London, GB, DW198708, Acc. No. 1987-053881, & JP 62 010 179 A (JAPC) 19.01.1987 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7595352B2 (en) * 2003-11-24 2009-09-29 Samsung Electronics Co., Ltd. Photo-curable adhesive composition, optical pick-up device using the same, and optical recording/reproducing drive including the optical pick-up device
US10968310B1 (en) 2015-04-28 2021-04-06 Adhesive R&D, Inc. Polymerizable materials, anaerobically curable compositions, and related methods and products
US12024586B2 (en) 2015-04-28 2024-07-02 Adhesive R&D, Inc. Polymerizable materials, anaerobically curable compositions, and related methods and products
CN117965112A (zh) * 2024-04-01 2024-05-03 广东粤港澳大湾区黄埔材料研究院 耐高温厌氧胶及其使用方法
CN117965112B (zh) * 2024-04-01 2024-06-11 广东粤港澳大湾区黄埔材料研究院 耐高温厌氧胶及其使用方法

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