JPS58191775A - Anaerobic curable adhesive having thixotropic property - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anaerobic curable adhesive in which the composition itself has thixotropy without the addition of a modifying agent.

Many anaerobic adhesives have been known that are liquid in the air, but when the air is blocked, they undergo a polymerization reaction and harden, destroying their adhesive properties. It is used in place of mechanical methods in fields such as fixing bearings and motor shafts, filling and repairing piping soles and pinholes in castings, and is useful for improving production efficiency and saving labor.

However, since this anaerobic layer agent is generally a fluid liquid, it has the disadvantage of being limited in terms of use. 1
For example, the adhesive must be applied immediately before assembling the parts because it flows or moves, and the spilled liquid can move and adhere to other moving parts, causing it to stick to parts that should not be stuck. Sometimes I end up doing it. In the case of parts with large gaps, the filling effect of the adhesive may be insufficient and the original adhesive strength may not be achieved.

Various methods have been tried in the past to solve these problems. For example, there is a method of adding a polymer compound to an adhesive and heating and dissolving it to increase the viscosity. High viscosity adhesives can be suppressed to some extent from flowing out to areas other than the surface to which they are applied, but on the other hand, their permeability deteriorates, making it difficult to work with wall coverings, and spillage cannot be prevented simply by applying adhesives. In that song,
There is a method of imparting aX properties to the adhesive by adding an organic group or a non-permanent preference imparting agent. This is obtained by adding a sufficient amount of favorability imparting agent to a liquid adhesive and stirring it vigorously at high speed, and it exhibits virtually no fluidity unless external force is applied. The above problem is solved because it flows and penetrates only when force is applied to remove the chips. However, this preference-imparting agent often has a negative impact on the performance of the adhesive. In other words, long-term storage of inorganic preference-imparting agents may cause deterioration in adhesion speed, and depending on the composition, the thixotropy index may gradually change or the preference-imparting agent may separate1. In the case of favoritism-imparting agents, they generally have polar groups such as hydroxyl, carboxyl, carboxylate, and amide groups in their molecules, so when used in polyviolets, they have poor storage stability,
This may have an adverse effect on adhesion speed and adhesive strength. In addition, since both of them are difficult to dissolve in the adhesive or dissipate, in order to disperse them uniformly and stably, a three-roll mill,
It is necessary to stir under high shear force using special equipment such as a kneader or homogenizer, which is a major hindrance in the manufacturing process.

The present inventors focused on this point and as a result of intensive research, they found that when they used urethane polymethacrylate having a specific m structure as a part of the polymerizable monomer, they found that It was discovered that it was possible to create a composition with anti-prejudice properties without using any of the above, and by adding a special stabilizer and a catalyst that imparts an anaerobic curing effect to this composition, the composition was found to be able to produce a pre-preparation composition that is liquid-based and has good storage stability. The inventors have discovered that a anaerobic curable adhesive can be easily obtained, leading to the present invention. That is, the present invention provides: a) Hexamethylene diinocyanate, glycol, and a polymerizable methacrylate having one or more hydroxyl groups in the molecule are blended so that the OH groups and NCO groups are approximately equivalent,
5 to 95 parts by weight of urethane polymethacrylate obtained by addition reaction b) 95 to 5 parts by weight of other subplastic methacrylic acid ester C) Aminopolycarbon rR having chelate forming ability or a salt thereof o, o o o The present invention relates to an anaerobically curable adhesive comprising i to o, i parts by weight d) aqueous ammonia or organic amine o, ooi to 5 parts by weight e) 0.1 to 10 parts by weight of a catalyst imparting an anaerobic curing effect.

The urethane polymethacrylate of the present invention can be obtained by any known method.
It can be easily produced by subjecting hexamethylene diisocyanate to an addition reaction with glycol and a polymerizable methacrylate having one or more hydroxyl groups in the molecule at 00°C. Glycols include ethylene glycol,
Examples include diethylene glycol, triethylene glycol, globylene glycol, butanediol, bentanediol, hexanediol, decanediol, and the like.

There is no particular restriction on the amount of glycol to be added, but it is suitably about 0.1 to 0.5 mol per 1 mol of hexamethylene diisocyanate. Examples of polymerizable methacrylates having one or more hydroxyl groups in the molecule include hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxydodecyl methacrylate, polyethylene glycol monomethacrylate, and polyethylene glycol monomethacrylate. These methacrylates containing hydrogenated groups are preferably added in such a proportion that the reaction product has methacrylate groups at both ends. The obtained urethane polymethacrylate is solid or jelly-like at room temperature, but when mixed with other liquid polymerizable methacrylic esters using an ordinary stirring device, it easily becomes a picky-eater composition. In this case, only liquid or solid compositions can be obtained from systems that do not use glycol or systems that use isocyanates other than hexamethylene diisocyanate, and picky eating only occurs when the urethane polymethacrylate of the present invention is used.

The degree of picky eating of other summer-promoting methacrylic modified esthetics L to be mixed with urethane polymethacrylate can be freely changed by changing the blending amount. The greater the content of urethane polymethacrylate, the greater the thixotropy index, and conversely, the greater the content of other polymerizable methacrylic esters, the lower the thixotropy index. Examples of polymerizable methacrylic acid esters include dimethacrylate of polyalkylene glycol, polymethacrylate of polygonal alcohol,
Alkyl methacrylate, alkoxyalkyl methacrylate, dimethacrylate of alkylene oxide adduct of bisphenol A, epoxy methacrylate obtained by adding methacrylic acid to bis-oxide, liquid polyester methacrylate obtained by esterifying dibasic acid with glycol and methacrylic acid. Examples include methacrylate-terminated products of rubber.The preferred blending ratio is 5 to 95 parts by weight of the urethane polymethacrylate to 95 to 5 parts by weight of other polymerizable methacrylic esters.Urethane polymethacrylate is If the amount exceeds the range, the viscosity becomes too high, which is undesirable, and if the amount decreases, the tendency to eat poorly.

The present inventors prepared a one-component adhesive by adding a catalyst that imparts an anaerobic curing effect to the thus obtained single-lid mixture with pickling properties, but it gelled in a very short time. I could only get what I wanted.

In addition, attempts have been made to stabilize this thread by adding large amounts of commonly used gelling stabilizers such as hydroquinone monomethyl ether, pentuquinone silage, and malonic acid, but none of these methods resulted in gelling in a short period of time. However, only those with extremely poor adhesion properties were obtained, and those with good adhesion and stability were not obtained. Therefore, the present inventors investigated other stabilization methods and found that the monomer mixture 100
0.0001 to 0.1 parts by weight of aminopolycarboxylic acid or its salt having chelate-forming ability and 0.001 to 5 parts by weight of aqueous ammonia or organic amine are added, and further anaerobic curing action is performed. It was discovered that when an adhesive was prepared by adding a catalyst that imparts , a one-component adhesive with very good storage stability could be obtained.

The reason for this stabilization is not clear, but the action of ammonia or amine increases the chelate-forming ability of amines, polycarbonates, or their salts, and extremely reduces the influence of gelation caused by heavy metals in the device. Neutralization of unnecessary acid components that cause gelation may be considered. Therefore, partial addition of aminopolycarbonate or its salt does not exhibit a stabilizing effect, and becomes effective only when combined with ammonia or amine. In this case, if there is too much ammonia or amine violet, the alkalinity of the composition becomes strong and the layering speed tends to be slow, so it is necessary to determine the amount added depending on the composition. In addition, the present inventors have found that when excessive ammonia or amine is added, unnecessary alkali can be removed from the system by stirring under normal pressure or reduced pressure and heating at a temperature below 150°C as necessary. It has been found that the pH of the composition can be adjusted appropriately by removing the adhesive, and that an adhesive with good performance can always be obtained. The stirring time is set so that the pH of the volatile components distilled out of the yarn is 9 or less, preferably 3.
~8 is sufficient. The amine preferably has a boiling point of 250° C. or less and can be easily distilled out of the thread. This method is advantageous in that it is more stable and always has better adhesion than the one in which ammonia or amine is simply added.

Examples of aminopolycarboxylic acids with chelate-forming ability include ethylenediamine@4'suryu, diethylenetriamine,
5-acetic acid, imino-2-acetic acid, cyclohexanediamine-4-acetic acid, nitrilo-3-acetic acid, glycol ether diamine-4-acetic acid, etc. Organic amines are primary and secondary.

Any tertiary amine can be used, and examples include monomethylamine, monoethylamine, n-butylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, di-n-butylamine, tributylamine, n-hexylamine, etc. .

Any known catalyst can be used as a catalyst that imparts an anaerobic curing action, but for example, hydrocarbon oxides such as cumenohydrobor oxide, diisopropylbenzene hydroperoxide, and t-butylhydrobor oxide are effective. The amount added is 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the polymerizable monomer mixture. Furthermore, a small amount of a curing accelerator such as an organic sulfimide, an organic peramide, an organic phosphite, etc. can be added as required. The present inventors have published Japanese Patent Publication No. 53-39480. 53-472
66, No. 54-28176 and No. 55-1958, O.benzoic sulfur (in the formula Rs, R
2ri Indicates hydrogen or methyl group. ) was shown to be effective as a catalyst for imparting anaerobic curing action.
The composition of the present invention having thixotropy was also found to be very effective. This amine salt-catalyzed system not only has superior adhesive performance compared to the organic perplate-containing system mentioned above, but also has organic peroxide-based systems. I! The problems of skin irritation and bad results caused by IK are eliminated, and it is also advantageous in terms of occupational health. The amine of general formula (1) is 1.2-3.4-
Examples include tetrahydroquinoline, 1.2.3.4-tetrahydroquinaldine and 6-methyl-1.2.3.4-tetrahydroquinoline.

The amount added is 0.00 parts by weight per 100 parts by weight of the polymerizable monomer mixture.
It is 1 to 10 parts by weight, preferably 0.5 to 5.00 parts by weight.

As described above, the present invention provides an anaerobic curable composition that is one-component, has good storage stability, and has thixotropy without using an organic or inorganic predilection imparting agent. This invention largely solves the manufacturing problems of conventional products and also improves adhesive performance, greatly contributing to the development of this industry. This will be explained in more detail using a comparative example. However, all parts represent parts by weight, and ppm represents parts by weight of 1 million parts of the polymerizable monomer mixture.

Kumazoinu Urethane polymethacrylate production stirring equipment,
A fourth flask equipped with a condenser equipped with salt and a thermometer was charged with the following amounts of hydroxyl group-containing methacrylate and glycol as shown in il, and 0.01 mol/initial addition of diptyltin dilaurate was added as a catalyst. While stirring at room temperature, a predetermined amount of sameethylene diisocyanate is added dropwise. The dropping is carried out gradually so that the reaction temperature due to heat generation does not exceed 80°C. After the reaction was completed at 90° C. for 1 hour, the infrared absorption spectrum was measured. The obtained urethane polymethacrylate is solid to jelly-like.

Example 1 Urethane polymethacrylate and trimethylolpropane trimethacrylate obtained in Production Example and ethylenediamine-4-acetic acid-2-ammonium were mixed in the amount shown in :Sfl, and 6 parts of 28 thiammonium water θ was added while stirring. did. An opening was provided to allow volatile vapor to exit the yarn, and the mixture was stirred at 80° C., and the pH was measured by occasionally applying a PH test tube moistened with water to the vapor. After about 1 hour, the pH of the steam removed from the thread became 9 or less, so it was cooled to room temperature and 0.
A solution of 1.5 parts of 1,2,3,4-tetrahydroquinoline salt of benzoic sulfimide dissolved in 1 part of dimethylformamide was added to prepare an adhesive.

The composition is shown in Omoteda. The following physical properties of the obtained adhesive were measured and the results are shown in Table 3. As is clear from the table, in all cases, the favorability index was 3 or more -F, ranging from a relatively low viscosity to a high viscosity putty-like one, and the adhesive performance was also good.

1. Viscosity and Predilection Index ■ Using a Tokyo Keiki GE type viscometer, 2.5 rotation and 200 rotation viscosity were measured at 23°C. The partiality index was calculated as follows.

If the viscosity decreases as the number of rotations increases, it can be said that the composition has thixotropy and has a large partiality index.

Depending on the composition, some adhesives were obtained that had a large thixotropy and could not be measured with a viscometer, but in such cases only the appearance was shown.

2. Set time Apply adhesive to a JIS grade 2 MIO-bolt that has been degreased at 23°C, screw in a nut of the same type, leave it to stand, and determine the time it takes for the nut to stop moving by hand (torque of approximately 10 Kf-cm). The set time was determined by measuring the time when The set time represents the start time of adhesion, and the shorter the set time, the more distantly hardening the adhesive.

3. Glue the bolts and nuts using the same return torque F, and after standing at 23℃ for 24 hours, use a torque wrench to tighten 1/4 and 1/2.

3/4, the torque at one rotation was measured, and the average value was taken as the return torque.

4. Gelation stability The prepared adhesive was placed in a 100ml low-density polyethylene container and left in a dryer at 50°C, and the number of days until gelation or thickening was observed was measured. If there are no abnormalities for 10 days or more, it can be said that the adhesive is stable at room temperature for 6 months to 1 year or more.

For adhesives that were stable for more than 10 days, 71)
The setting time and return torque are measured to determine the deterioration of adhesive performance due to long-term storage.

Example 2 The urethane polymethacrylate of Production Plane 5 in Production Example, other polymerizable methacrylic esters, and ethylenediamine 4-acetic acid 2-ammonium were mixed in the amounts shown in Table 1, and while stirring, 0.6 part of 28 thiammonium water was added. After adding and performing the same treatment as in Example 1, the mixture was cooled to room temperature.

Next, 1.5 parts of a salt of O.benzoic sulfimide and the amine of general formula (1) and 1.0 parts of dimethylformamide were added.
Example 1
The physical properties were measured in the same manner. The results are shown in Table V.

(r2) Example 3 25 parts of urethane polymethacrylate, 75 parts of trimethylolpropane trimethacrylate, and an aminopolycarboxylic acid having chelate-forming ability and aqueous ammonia or amine in the production example were prepared in the amounts shown in Table 2. The blended mixtures having AI 8 to Ken 27 were stirred at 80° C. in the same manner as in Example 1 until the pH became 9 or less. Next, a bath solution prepared by adding 1.5 parts of 1,2,3,4-tetrahydroquinoline salt of 0-benzoic sulfimide to 1.0 part of dimethylformamide was added to prepare an adhesive, and the physical properties were determined in the same manner as in Example 1. was measured. The results are shown in Table ■. The viscosity and thixotropy index were all almost the same as that of Adhesive Nogashi 11 in Example 1, and the number of days for gelation at 50° C. was 10 days or more in all cases.

Comparative Example 1 20 parts of urethane polymethacrylate from Manufacturer 5 in Production Example, 8 parts of trimethylolpropane trimethacrylate
After performing the stabilization treatment shown in Table 1 on 0 part, it was cooled to room temperature and 1112.3 of 0.benzoic sulfimide was added.
- An adhesive was prepared by adding a solution of 4-tetrahydroquinoline salt to 1.0 part of dimethylformamide, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 2. still,
The viscosity and thixotropy index were both as follows.

Viscosity 2.5 rotations 2355.2 cpThixotropy index 3.5
420 rotations 665.6 cp As is clear from the table <430, the adhesion speed of A31 is significantly slowed down due to deterioration at 50°C, and even when A32 without aminopolycarboxylic acid and aminopolycarboxylic acid are used, ammonia Alternatively, A33 without amine treatment has a problem in gelation stability.

Comparative Example 2 200 ppm of p-benzoquinone was added to 100 parts of trimethylolpropane trimethacrylate, and the mixture was heated at -80°C.
Dissolved by heating for an hour. After cooling to room temperature, a solution of 1.5 parts of 1,2,3,4-tetrahydroquinoline salt of 0.benzoic sulfimide dissolved in 1.0 part of dimethylformamide was added to prepare an adhesive, and the mixture was heated in a homogenizer at room temperature. ~8
Table (2) shows the results of measuring the physical properties of the thin anaerobic adhesive obtained by uniformly dispersing the organic or inorganic picky-feeding agent shown in Table (3) at 5°C. As is clear from the table, 435 and 37.38 have poor gelation stability and adhesion, and 434.36 has good gelation stability, but
The adhesion speed was significantly slowed down by deterioration at 50°C.

t19r (“) Comparative Example 3 An adhesive was prepared in the same manner as adhesive agent 3 in Example IK using hexaurethane polymethacrylate synthesized in the same manner as in the production example with the composition shown in Table ■, and the viscosity was measured. The results are in the table■
It was as follows.

Table ■ As is clear from the table, thixotropy is not affected even when glycol is used, and when inocyanate is not hexamethylene diinocyanate, and when glycol is not used even when hexamethylene diinocyanate is used. It was.

Procedural amendment (voluntary amendment) June 2, 1980 Haruki Shimada, Commissioner of the Patent Office1, Indication of case Patent application No. 7.5, No. 7, No. 7, 1982 Title of the invention Anaerobic curing adhesive with thixotropy a.Relationship with the case of the person making the amendment.Applicant Address: 7313 Nakatsu-cho, Marugame City, Kagawa Prefecture Name: Okura Kogyo Co., Ltd. 4, Agent G Contents of the amendment (li) Two lines from the top of page 73 of the specification: ``θ! ~ i0J is corrected as 1θ child ~oθ''.

Claims (1)

[Claims] 1.a) Hexamethylene diisocyanate, glycol, and a polymerizable methacrylate having one or more hydroxyl groups in the molecule are blended so that the OH groups and NCO groups are approximately equivalent, and the mixture is subjected to an addition reaction. Obtained urethane polymethacrylate 5-95 parts by weight b) Other polymerizable methacrylic esters 95-5 parts by weight C) Aminopolycarboxylic acid or its salt having chelate-forming ability 0.0001-0. IN amount part d) Aqueous ammonia or organic amine 0.001 to 5 parts e) Catalyst imparting anaerobic curing effect Anaerobic curing adhesive 2 having thixotropy consisting of 0.1 to 10 parts of suboxygen acid, anaerobic curing The anaerobic curable adhesive according to claim 1, wherein the catalyst imparting the action is a salt of O-benzoic sulfimide and an amine represented by the following general formula (where R+, RzFi water or methyl The anaerobic curable adhesive HO-(-CI-L2-)- according to claim 1 or 2, wherein the 3 glycol (representing a group) is a compound represented by the following general formula. a OH (in the formula, n represents an integer of 2 to 10)