JPS5863771A - Stable cyanoacrylate adhesive composition and manufacture - 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]

This invention relates to compositions of cyanoacrylate adhesives, the compositions having a p.p.
Incorporating acid gases combined with acids in the ea range K
Stability is thus improved. Liquid cyanoacrylate compositions have been well known in the prior art for many years as adhesives of choice. Alpha cyanoacrylates are represented by the general formula, where R is cl-16 alkyl, cycloalkyl, alkenyl, cycloalkenyl, phenyl, or a heterocyclic group, which forms a thin film. It is well known that anionic polymerization occurs in a short period of time due to moisture present in the surrounding environment. Alpha cyanoacrylate is widely used in many debonding materials to bond and seal all kinds of organic and inorganic materials. However, one of the traditional drawbacks is the following. That is, when storing monomers,
Self-polymerization occurs in a relatively short time even in a closed container with relatively no atmospheric dams. This is primarily due to residual water impurities left in the monomer manufacturing process. During this time, when the storage temperature rises, q! It even becomes shorter. Therefore, what is needed is to incorporate anionic polymerization stabilizers into adhesive compositions. The following is known from the prior art: That is, adhesive compositions containing alpha cyanoacrylic acid are prepared by incorporating within the composition a small amount of an acid gas, most commonly sulfur dioxide, and a free radical inhibitor, most commonly hydroquinone. , it is possible to stabilize it. This technique is applicable, for example, to US LJA Co., Ltd., No. 2, 765, 3.
No. 32, and US Pat. No. 2,794,788. It is important to note the following: That is, acidic gases such as sulfur dioxide are present in the monomeric ester during the depolymerization stage of its production. This method is
Well known, inter alia, in U.S. Patent No. 2.765,3
No. 32, No. 3.335,482, No. 2,467.92
No. 7, No. 3,221,745, No. 3,178,399
No. 2.926.188, Federal Republic of Germany 1 Patent 1
11E 1.807.895, French Patent No. 1
, 504.240, and British Patent No. 1,159.
It is described in the specification of No. 548. In these known directions, sulfur dioxide is added to about 0.00% by weight of the adhesive composition.
Add a concentration f of 1 to about 0.014. Higher concentrations have the opposite effect in that even a slight excess of sulfur dioxide causes a severe retardation of the cure rate. #If the honey is thin, you will run into very low stability problems. Excess acid gas is removed under a high vertical atmosphere and the adhesive is left in the desired position. A similar explanation applies to nitric oxide or boron trifluoride. The prior art discloses the use of various other anionic inhibitors in the Lewis (L.
! i41 Permit No. 3,751.445, No. 2,467.9
No. 26 (City kjA), No. 2.763.677, No. 2,756,251, No. 2,514.387, No. 2,467.927 and No. 3,221.745. It will be done. These stabilizers are phosphoric acid, picric acid, hydrogen fluoride, string and various carboxylic acids. It is also known in the prior art to add the above-mentioned stabilizers to the finished monomers by distillation. Sulfur trioxide, nitric oxide, and aromatic sulfonic acids are a few other types of stimulants that have been used to stabilize monomer compositions. One of the difficulties encountered in incorporating these conventional stabilizers into cyanacrylate compositions as described above is that many of these stabilizers are highly volatile at room temperature; It escapes without being dissolved in the cyanoacrylate monomer. Thus, when alpha-cyanoacrylates incorporating inhibitors are stored for long periods of time, the inhibitors may spontaneously escape from the drug mass, which may give alpha-cyanoacrylates complete stability. making it difficult. (Page 1O) Now, to briefly summarize the present invention, the present invention includes: 2-cyanoacrylic acid. The concentration of acid gas (e.g., SO,) is typically
From about o,oos to about 0.01' by weight of the composition
1, while the same once range applies to acids. Adding these stabilizers to the cyanoacrylate composition in combination with each other results in a synergistic stabilizing effect;
It increases the shelf life and stability of cyanoacrylate adhesives far beyond what known stabilizers have been able to achieve on their own. The stability achieved does not negatively interfere with the cure rate, strength, or general performance of the adhesive composition, with an appropriate range of stabilizing component concentrations and pKa. Next, this invention will be described in detail. The esters of 2-cyanoacrylic acid used in the invention described herein can be prepared by the method described in US Pat. No. 2,467,927. This method involves formaldehyde and alkyl, y? o full kill, or
It involves the preparation of intermediate polymers through condensation reactions between phenyl esters of cyanoacetic acid. This condensation reaction can be accelerated by the presence of ammonium hydroxide, quinoline, piperidine, diethylamine, and a basic interlocking catalyst. Gentle warming, such as to about 0.9°C, is also desirable to initiate the reaction. Water and organic solvents are
Remove as much of it as possible, generally by distillation

[For example, the intermediate polymer is thermally decomposed to produce a monomeric ester of 2-cyanoacrylic acid. The monomeric ester has a wood tone absolute pressure of 1 to 1049
It is separated by fractional distillation at reduced pressures of a meter or less, generally in the presence of an acidic polymerization inhibitor such as phosphorous pentoxide. The monomer vapor is liquefied in a container containing the desired inhibitor for use in the final adhesive product disclosed above and described in detail below. Other similar processes include, for example, U.S. Pat.
It is disclosed in the specification of No. In the adhesive composition, esters of 2-cyanoacrylic acid can be used singly or in combination. C.I.
Preferably, a single ester is used, selected from the group consisting of I to C8 alkyl and cyclohexyl esters of 2-cyanoacrylic acid. The single most desirable ester is ethyl-2-cyanoacrylate. As mentioned above, the dual stabilizer system produces a synergistic effect,
Its effects have not been published to date. Such effects are a matter of computation, and it is likely that a reasonably skilled chemist will determine whether a synergistic or additive stabilizing effect is possible, based on the respective roles of the individual stabilizers. This is understandable if you consider the fact that it is predicted. There are likely many factors contributing to this stabilizer system in cyanoacrylate adhesives. I don't want to be bound by any theory. ^
Most Preferred Acids (Page 13) Gas 801 forms hydrates with the water present within the cyanoacrylate monomer, adding up to 7 water molecules per each So molecule. . The water is generally about 400 to 400 tons, o
It is generally present in the polymer as an impurity in the manufacturing process at concentrations of 0.00 ppm. This residual water alone, or in combination with ambient environmental moisture, can initiate anionic polymerization of the monomer. Such effects are undesirable and greatly reduce the shelf life of the adhesive composition. Forming hydrates with water molecules reduces the potential initiation of anionic polymerization. Additionally, it is hypothesized that the acid component of the stabilizer will form hydronium ions when residual water is present. The result of this reaction is to reduce free water and produce acidic hydronium ions, which are converted into SO
Both K and S serve as stabilizers. When any acid is present in extremely high concentrations in a cyanoacrylate adhesive composition, such acid has a negative impact on the stability of the adhesive. The reason for this is thought to be that the acid acts to form cyanoacrylic acid and alcohol when catalyzing the hydrolysis of the cyanoacrylic salt monomer. Once the alcohol reaches a sufficiently high level, it will serve as a catalyst for anionic polymerization. It is here that the joint role of the SO turtle and acid combination can be clearly demonstrated. Since the 80-unit functions to form hydrates and combine water molecules, there are very few water molecules involved in the acid hydrolysis process, and therefore the resulting alcohol, if any, is also There are very few. From these theoretical mechanisms, a reasonable person skilled in the art would expect a single additive effect, perhaps because the two inhibitors are present in the cyanoacrylate@adhesive composition. This is because each binds or reacts with the water present within the composition. It is then conceivable that the net result is simply a reduction in the total amount of residual water that could potentially and prematurely initiate polymerization and reduce the quality (page 15). It will probably decrease. Therefore, one skilled in the art would expect that the stability of the adhesive composition will be the sum of the effects of the individual stabilizers, provided the amounts of each stabilizer are balanced in an appropriate manner. It means that there will be. Thus, for example, if a particular concentration of SO, only yields a composition that is stable for y days, and a particular concentration is stable for X days, then the additive effect is
One would obtain a composition that is stable for a period of days plus days. However, this expected result does not negate the invention; rather, it provides an even more significant period of stability. It is clear that a synergistic effect is not evident if only a small amount of moisture is present in the stable cyanoacrylic acid composition, or if the container storing the composition is made of glass or aluminum. This may be the case if the tube is impervious to moisture or air. This is due to the following fact. That is, when there is no moisture present in the composition, the 80 components of the stabilizing system function well enough to attach to most, if not all, of the water molecules. Thus, the result in these cases is that K activates both the acid and 802.
Since there was too little d water present, there was no significant synergistic effect. Since SO2 can react with up to 7 molecules of water, there will be very little water with which the acid will react. However, in reality, plastic containers that are generally permeable to air and water, such as polyethylene, are used. In these types of containers, the synergistic effect is quite evident, as will be seen in the examples. Preferred acid gases in this invention are about 0 by weight of the composition.
．． 0005 to about 0.01 sulfur dioxide. A preferred range is about o, ooo by weight of the composition.
s to about 0.004, with the most preferred range being
It weighs about 0.002 cm by weight. The acid component of the stabilization system has a pKa of about -12 to about 7.
Preferably, it is present in a range. Most preferred (page 17) the range is from about -12 to about 2. Acids are generally selected from sulfonic, phosphorous, phosphorous and carboxylic acids. Among these, preferred acids are methanesulfonic acid, Henzendisulfonic acid, p-)luenesulfonic acid, hydroxypropanesulfinic acid, Banzenphosphorous acid, benzenephosphoric acid, Schereric acid, and pentafluorobenzoic acid. Acids which are also preferred by mosquitoes are acids of the sulfone group, especially methanesulfonic acid. The concentration range for the above acid may range from about 0.0005 to about 0.0 by weight of the composition.
1st place. The preferred concentration range is about 0.000 by weight
51% to about 0.004%, but the most preferred range is from about 0.00% to about 0.002% by weight. Mixtures with any suitable acids can also be mixed with acid gases. The composition of the present invention is prepared using a cyanoacrylate monopartite by a conventional mixing operation.The cyanoacrylate monopartite is distilled in a container containing a predetermined amount of acid, and the SO
, then add. It is often advantageous to add certain other ingredients to adhesive compositions to impart particular properties to the adhesive or cured adhesive product. Free radical polymerization inhibitors are generally included and desirable amounts include quinone, hydroquinone, p-tertbutylcatechol, p-methoxyphenol, 2:6-diterto! Chiruparacresol and 2,2-methylene-
It is a phenolic type such as bis-(4-methyl-6-tyldoptyl)phenol. These inhibitors can be used in concentrations of about 0.001 parts to about 1 part by weight of the adhesive composition. Most preferably, these inhibitors are used in an amount ranging from about 0.005% to about 0.11% by weight of the adhesive composition. Thickeners and potting agents can be added in proportions readily determined by those skilled in the art. Generally (C1 thickeners and plasticizers are used in the range of about 1% to 10% by weight of the adhesive composition,
The volatile solvent may range from 0 to about 251% by weight of the adhesive composition.
Use in the range of s or more. The most common thickening agents are acrylic acid salt resins such as polymethyl methacrylate and polyethyl methacrylate. Other suitable thickeners are polymerized alkylcyanoacrylate celluloses, such as cellulose acetate and cellulose butyrate, and polyvinyl ethers, such as polyvinyl methyl ether. The most common plasticizers are dibasic acids such as sebacic acid and malonic acid.
1 to CIO alkyl ester. Polyalkyl ethers and polyurethanes and other plasticizers can also be used. As mentioned above, the stability of cyanoacrylate adhesive compositions is affected by atmospheric moisture as well as residual manufacturing moisture. Therefore, the type and dimensions of the container chosen for storage of the adhesive will affect the stability of the root bark. The following examples are written to illustrate the synergistic stabilizing effect often found when acid gas and acid are dissolved in cyanoacrylate compositions. The cyanoacrylate monomer used in all examples was prepared using the method described above to produce 1 ml of IJ! It was ethyl-2-cyanacrylate. All Examples of Shinken Methanesulfonic Acid> and 0.0080% by weight of 802 were added to each cyanoacrylate composition (additionally 3
gram aluminum tubes and maintained at a temperature of 70°C. The adhesive composition was stable, did not spread, and maintained satisfactory performance for up to 61 days. The table below shows the survival rate of stability in days for each of the four selected combinations of stabilizer concentrations. As previously explained, MSA (methane sulfonic acid) or 80. The synergistic effect is not apparent when either is used only in an air-impermeable container such as aluminum or plastic tubes. This is demonstrated in both Tables 1 and n (Example ■). Table 1 shows 5 PI)
The composition is shown to be stable after 5 days with 802 and o ppm OMe of H. Therefore, when the composition does not absorb moisture from the surrounding environment, K
d, there is no notable change in stability.0 Table IT
h and 10 and 20 ppm of Table ■130. , op
The MSA data point of pm (page 21) has remained stable for more than 61 days to date, which further proves the above theoretical interpretation. table ! A. Stability (days) of CA stabilized with M8A/80m in a 3-gram aluminum tube at high temperature. 1. Concentration is expressed in PPm. 2. Stability is expressed in days. Example ■ Table ■ A. Stability (days) of CA stabilized with M8 μm/BO at 70°C in a test tube (Page I22) As observed in Table 1, the container used was In this case, results similar to those in Table I were obtained. The cyanoacrylate adhesive compositions were found to have excellent cure speed and adhesive strength after the respective periods indicated. EXAMPLE This example illustrates the stability effect when using an air permeable polyethylene bottle as a container. As shown in Table 1, which is the same as the above example, the optimum value of the concentration is 21 Jppwh for both 5OS4 Mj and the temperature range. At the same concentration (added ppm), the expected additive effect is a value of 13 days, but the synergistic effect results in an IK of 4. Table 11 [B is (page 23) MSA 480. Both MeM1S02 concentrations exhibit a stability of 20 ppm"e'ss days, which is twice the number of days expected if additive effects were present. Table ■ A, M8/80 in a 1 oz polyethylene bottle.
．． Stability of stabilized C (days) Spicy Container failure due to severe stress cracking. B, Ma at 70”C in an i oz. polyethylene bottle.
Stability (days) of Cum stabilized with A/SO, (2nd
(page 4) The examples below demonstrate 10 and 40 ppm concentrations of various acids in combination with o pyn and 101) Pm soQ. Example ■ Table y So, ethyl C stabilized at 70°C with acid
System stability (days) MSAIOPIIll 6 4 56
740PPli-4-- 101) pH11594 40PP Otori 1 1 5
9 4 (Page 25) Oxalic acid 101; 11) 11 1 1” 5
9 17401) 1) m 1 1 spicy 59 1゜PSA1 10ppm 12 7 59
110401111) 36 9
43 12 benzene Δedge 10pT) m 2 2 56
6401) pIn 13
16 56 17 Benzine salt 2 qppm 1 1
52 1640pI)! n 1
1 48 10 Benzine disulfonic acid 1101) p 22 14 36
13401>I)m 22 7
27 1710PI>m 6
7 56 1540ppm
22 12 48 15 Spicy container damaged 1, Hydroxy! Donkey/sulfonic acid 2, polyethylene bottle The table above shows 10-40 PI) 80.
(page 26) shows the dramatic effects obtained for various acids combined. As can be seen in the table, 10 Pm of methanesulfonic acid and 10 ppm of methanesulfonic acid added to the ethyl cyanoacrylate composition.
80.m. After heating at 70°C in a glass container for several days, a stable product with good performance (adhesion strength/curing speed) was produced. Similar results could be obtained with other sulfonic acids, phosphoric acid and phosphoric acid. Patent applicant Kutite, Coordination agent
Press 1) Long mourning - January 9, 1980 Mr. Haruki Shimada, Commissioner of the Japan Patent Office 1. Indication of the case 1982 Patent Application No. 158876 2. Name of the invention Composition of stable cyanoacrylate adhesive Things and their manufacturing methods, Mountain, Road, 705 4, agent correction number special request show! 16-1! i8@? 6 1 Specification No. zO true No. zθ line to 1st page 1st line r table!
...The data point is 80 of Loppm in Table 1 and ■.
The MSA data points for 1% B and lOppm are corrected as follows. Patent Applicant: ν Kutite, Fuboreshi's Agent: 1) Yoshihisa

Claims (1)

Claims: at least 1 monomeric ester of 1,2-cyanoacrylic acid and at least about o, ooo's* to 0.
001 'i is dissolved in a bath to form an acidic gas, sulfonic acid,
A stable nine-cyanoacrylate adhesive composition comprising phosphorous acid, phosphoric acid, and an acid selected from the carboxylic acid group of about 0,000 to about 0.01. 2. Esters of 2-cyanoacrylic acid have the formula NC = C-COOR, in which R represents Cl-16 alkyl, cycloargyl, alkenyl, cycloalkenyl, phenyl or a heterocyclic group. A composition according to claim 1, characterized in that: 3. Sulfonic acid has a weight of about o, oos (
2. A composition according to claim 2, characterized in that the methanesulfonic acid is present in a concentration of 0.002 mm. 4. Sulfonic acid is about 0.00051 to about 0.000 by weight.
002. A composition according to claim 2, characterized in that the hydroxypropanesulfonic acid is present in a low concentration. 5. Sulfonic acid is about 0.005% to about 0.0% by weight.
3. A composition according to claim 2, characterized in that the benzenedisulfonic acid is present in a concentration of 0.021. 6. Sulfonic acid has a heavy duty of about 0.0005% to about 0.00%.
3. A composition according to claim 2, characterized in that it is p-)luenesulfonic acid present in a concentration of 0.0021. 7. Phosphorous acid is about 0.0005 to about 0.0 by weight
2. The composition according to claim 4, characterized in that the benzene phosphorous acid is present in a concentration of 0.02 yen. 8. Phosphoric acid ranges from about o,oos to about 0.0 by weight.
3. A composition according to claim 2, characterized in that the benzene phosphoric acid is present in a concentration of 0.2 hours. 9. 3. The composition of claim 2, wherein the carb/acid is oxalic acid present in a concentration of about 0.0005 eIb to about 0.014 eIb by weight. 10. Carboxylic acid is approximately o, oooss F by weight
3. The composition of claim 2, wherein the composition is interfluorobenzoic acid present at a ski of F to about 0.011. 11. The composition of claim 2, wherein the acid gas is S02 present at a concentration of about 0.01 to about 0.01 parts by weight. 12. The composition according to claim 2, which additionally contains a free radical polymerization inhibitor. 13. At least about one monomeric ester of 2-cyanoacrylic acid and at least about 0,000 to about 0.011 by weight acid having a peIL of from about 12 to 7, and from about 0.0005 to about 0.0005 by weight. A stable cyanoacrylate adhesive composition comprising 0.01 g of dissolved acidic gas. 14. Esters of 2-cyanoacrylic acid have the formula N CHs=xC-COOR , where R is C1-1a alkyl,
11?Represents cycloalkyl, alkenyl, cycloalkenyl, phenyl or heterocyclic group? 913. The composition of claim 913. 15. The acid is about 0.0005 to about 0.0 by weight.
15. A composition according to claim 14, characterized in that it is methanesulfonic acid present in a concentration of 1.1. 16. The composition of claim 14, wherein the acid is p-)luenesulfonic acid present in a concentration of about 0.0005% to about 0.01% by weight.
15. The composition of claim 14, wherein . 18. The acid ranges from about 0.00% to about 0.01% by weight.
15. A composition according to claim 14, characterized in that it is pentafluorobenzoic acid present in a concentration of . 19. The acid ranges from about o,oos to about 0.0 by weight.
A special feature characterized by the presence of oxalic acid at a concentration of 1 t (page 5)
A composition according to claim 14. addition, the acid ranges from about 00OO05 qb to about 0.011 qb by weight.
15. The composition according to claim 14, characterized in that the hydroxypropanesulfonic acid is present in a concentration of 21. The composition of claim 14, wherein the acid is benzene phosphoric acid present in a predominant concentration of about 0.0005 to about 0.01. 22, @Sex Kasha, approximately 0.0005% by weight /
15. The composition of claim 14, wherein the composition is SO2 present at a concentration of about 0.01 F-fi. 15. The composition of claim 14, further comprising a free radical polymerization inhibitor. Finally, in the process of making a cyanoacrylate adhesive, the cyanoacrylate is combined with an acid having a pK of from about -12 to about 7 or more and from about 0.0005% to about 0.0% by weight of the monomer.
A process for making a stable cyanoacrylate adhesive by dissolving an acid gas at a concentration of 1. (Page 6)