JP6768551B2 - Anaerobic curable formulation for sealing and blocking bolts and nuts - Google Patents

Description

The present invention relates to anaerobic curable / crosslinkable formulations derived from acrylic resins in aqueous emulsions. Based on the composition of these formulations, reaction generation, especially to make it suitable for use as a sealant and / or breaker for the connection of screws, nuts, bolts and screw caps or sealing caps. It is possible to adjust the characteristics of the object.

Various formulations are commercially available that are suitable for use in sealing and blocking nuts and bolts. Some of these known patent publications are briefly described below.

International Patent Publication No. WO 00/01767 relates to a composition for sealing a nut against a screw and self-locking. This composition
(A) At least one polymerizable (meth) acrylic monomer present in an amount of 4% to 15% by weight of the total composition.
(B) A binder that is soluble or dispersible in water (reactive monomer),
(C) An emulsion or aqueous dispersion with an effective amount of free radical polymerization initiator (benzoyl peroxide) in the form of microcapsules.

A polymerization initiator (eg, hydroquinone) is added to impart stability to the polymer composition. A polymerization accelerator may be added to a composition containing a small amount of ferrocene (for example, an organometallic compound). The pH is controlled by adding a basic solution. This composition is highly resistant to heat-induced aging and is very stable on copper and bronze surfaces.

U.S. Pat. No. 4,417,028 describes an adhesive coating composition comprising a polymerizable monomer, a binding system and a polymerization initiator and accelerator (ferrocene). The polymerizable monomers used in this composition are described as a mixture of polyfunctional and monofunctional esters of acrylic acid (including urethane acrylate; hydroxypropyl methacrylate; hydroxyethyl methacrylate). The bonding system comprises a copolymer of anhydride and a compound selected from arylene, alkylene, alkoxylen, arylalkylene and the like. A preferred binder is ethylene / maleic anhydride. These binders form stable suspensions or dispersions and also contribute to the adhesion of pre-applied membranes to the substrate by hydrolysis of the anhydride ring. In order to obtain the optimum adhesion of the composition pre-applied to the substrate, a base (NH ₄ OH, NaOH) is used to control the pH of the composition. The composition has a long shelf life, is highly resistant to heat aging, and provides great self-locking between bolts and screws.

U.S. Pat. No. 4,546,125 describes an adhesive curable composition with excellent strength and adhesion rate. This composition is a monomer soluble in more than 0.5% by weight of water and polymerizable under at least 10% by weight of anaerobic; o-benzoic acid sulfonamide (polymerization accelerator); hetero to enhance heat resistance. Ring tertiary amines and / or aromatic amines; containing radical polymerization initiators and anaerobic polymerizable monomers containing water. Urethane poly (meth) acrylates are described as polymerizable monomers.

US 4,048,259 describes an adhesive sealing composition that cures under anaerobic conditions. The composition comprises a polymerizable acrylic ester, a peroxide polymerization initiator and an acrylic acid ester. The composition may contain stabilizers (hydroquinone), accelerators (aliphatic or aromatic quaternary amines), thickeners, dyes and fillers (CaCO ₃ , TiO ₂ and soluble dyes). .. Thickeners that can be used in the composition are poly (alkyl) acrylates and methacrylates. This composition is a non-corrosive adhesive mixture and provides a very strong fixation.

US 4,007,322 is anaerobic containing one or more unoxidized acrylic monomers, a polymerization initiator (organic peroxide), a polymerization initiator (hydroquinone) and a polymerization accelerator (benzoic acid sulfonamide). The sealing composition is described. The polymerization initiator provides a composition having a long shelf life when in contact with air. If none of the surfaces are metallic, then at least one of the contact surfaces must be pretreated with a primer.

US 3,855,040 is an anaerobic composition that polymerizes rapidly and contains a monomer of acrylic acid ester, a polymerization initiator (organic peroxide), a strong acid and an activator (containing a small amount of ferrocene). Regarding. Activators are selected to control the cure rate.

US 3,970,505 describes an anaerobic composition containing a polyfunctional monomer of an acrylic acid ester, a peroxide polymerization initiator, a substituted thiourea and an acid substituent. The composition cures quickly and at the same time maintains good mechanical properties (eg solidity, flexibility and sealability). The monomer used gives the adhesive characteristics and a long-lasting sealant. Examples of polyacrylic esters are diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, diglycerol diacrylate and the like.

US 4,410,644 is a polymerizable acrylic acid ester monomer, a polymerization initiator (hydrogen peroxide), a polymerization inhibitor (quinone), an organic sulfonamide type accelerator, a thickener (polyglycol), and a colorant. , Viscosity control agent (= rheology modifier), eg silica fume; anti-wear agent [(for metal wear caused by friction between parts in contact with metal), i.e. anti-wear agent, eg tetrafluoroethylene] and at least one. An anaerobic sealing composition comprising a type of plasticizer (glyceride) is described.

All these known formulations have been combined with different types of additives, polymerization initiators and accelerators to obtain cured reaction products with desirable physical, mechanical and chemical characteristics (meth). Derived from an acrylate compound. Nonetheless, applications that require a wide range of curing strengths without the use of primers and polymerization inhibitors can be satisfied and have better physical, mechanical and chemical features than those in the known art. An anaerobic curable / crosslinkable formulation with specific characteristics is required.

The present invention is an anaerobic and curable / crosslinkable formulation of an aqueous emulsion that cures / crosslinks in a relatively short period of time, has improved breaking power (represented by improved separation), and improved oil resistance. Provided is a reaction product exhibiting properties and high heat resistance.

The formulations of the present invention are in paste form and can be easily applied to the threads and bolts of screws, ensuring sealing and blocking effects, these formulations using primers and polymerization inhibitors. Does not need.

One aspect of the invention is polymerizable, curable under anaerobic conditions, and provides improved sealing power, especially for results that can be obtained using products of the known field. Includes new formulations useful for applying to threads of screws and bolts. The formulation comprises at least one acrylic resin and phenoxy-polyethoxysulfate in combination with other additives commonly used in the art. This formulation is hereinafter referred to as a "sealing formulation" in the present invention.

Another aspect of the invention is a screw to provide an improved blocking force to the results that are polymerizable, curable under anaerobic conditions and can be obtained using products in the known field. And contains new formulations that are particularly useful for applying to bolt threads. The formulation comprises at least one dimethacrylate, acrylic resin, polymerization and curing initiators, accelerators, and other additives commonly used in the art. Inhibitors and accelerators are used in microencapsulated form. This formulation is referred to in the present invention as a "self-locking formulation".

The reaction products of these formulations can perform the required bolt sealing and blocking action, which may be more or less strong and more or less rapid, depending on the intended type of application.

The above result is that the formulation is placed inside the threads of the screw by using a device known in the art, then dried in a dryer, during which the nut is tightened and polymerization begins. A reaction product is produced that gives.

The reaction products of these formulations are characterized by excellent resistance to vibration, heat and aggressive chemicals. These reaction products are specifically used to seal and block screw threads and mechanical devices to prevent loosening and leakage.

(Detailed Disclosure of Invention)
The encapsulating formulation contains 4-8% by weight acrylic resin and 40-70% by weight phenoxy-polyethoxysulfate. Preferably, the phenoxy-polyethoxysulfate used in the present invention is an aqueous mixture of nonylphenoxypolyethoxy branched-chain ammonium sulfate having a concentration of 40 to 45% and an aqueous ammonia solution of 0.1 to 0.2%. ..

The sealing formulation contains 20 to 35% by weight of water. Other additives such as plasticizers, dyes, fillers, corrosion inhibitors, etc. can be added to the encapsulation formulation.

The following is an example of the sealing formulation of the present invention.
Deionized water 20-35% by weight
Butyl glycol 4-7% by weight
Pigment 0.1-0.2% by weight
Titanium dioxide 2-3% by weight
Ammonia 28% 0.1-0.6% by weight
Acrylic resin 4-8% by weight
(Cured copolymer in aqueous emulsion)
Teflon® (powder) 9-16% by weight
Nonylphenoxy-polyethoxysulfate 40-70% by weight
(Aqueous emulsion state)
Ammonium benzoate 0.5-0.9% by weight
In the present invention, the amount expressed in% by weight refers to the total weight of the formulation.

The self-locking formulation contains dimethacrylate in an amount of 30-60% by weight. A portion of the dimethacrylate can be replaced with diurethane dimethacrylate, in which case the self-locking formulation preferably contains dimethacrylate in an amount of 15-30% by weight, while diurethane dimethacrylate is 15 Use in an amount of ~ 30% by weight.

The self-locking formulation further contains 5-9% by weight acrylic resin, 2-4% by weight inhibitor and 0.3-1.5% by weight accelerator. Both inhibitors and accelerators are used in microencapsulated form.

The following is an example of the self-locking formulation of the present invention.
Deionized water 40-60% by weight
Ammonium benzoate 0.5-2% by weight
Ammonium phosphate 0.05-0.2% by weight
Titanium dioxide 1-2% by weight
Ammonia 28% 0.3-0.7% by weight
Dimethacrylate 19-27% by weight
(Bisphenol A ethoxylate dimethacrylate)
Diurethane dimethacrylate 18-28% by weight
Acrylic resin 5-9% by weight
(Cured copolymer in aqueous emulsion)
Pigment 0.3-0.9% by weight
Talc 0.4 to 1% by weight
Benzoyl peroxide 2-4% by weight
Microencapsulated ferrocene 0.4-1.4% by weight
The amount expressed in% by weight refers to the total weight of the formulation.

According to a preferred embodiment of the invention, the pH of the encapsulating and self-blocking formulations is maintained in the range of 5-10, more preferably 6-8.

The pH can be adjusted by incorporating an effective amount of an organic or inorganic base into the formulation of the invention, which does not interfere with the polymerization of the acrylic resin and the dimethacrylate. Preferably, the pH is adjusted by adding NH ₄ OH or NaOH to obtain good curing characteristics of the sealing and self-blocking formulations.

Acrylic resins that can be used in the formulations of the present invention are water-based emulsions of cured copolymers selected from ASE SOL® ASE, 20, 60 and 75, preferably ACRYSOL® ASE 60.

The dimethacrylate that can be used in the self-locking formulation of the present invention is bisphenol A ethoxylate dimethacrylate.

Since the encapsulation formulation of the present invention does not contain a catalyst, the bolt fixing operation is not as strong as the self-locking formulation incorporating a polymerization initiator and accelerator.

The encapsulation formulation used an acrylic resin in combination with phenoxypolyethoxysulfate, the presence of which had a surprising effect on the performance of the reaction product. Incorporation of phenoxypolyethoxysulfate into the encapsulation formulation of the present invention gives the reaction product considerable resistance and stability to chemicals, while at the same time improving encapsulation.

Moreover, surprisingly, the sealants formulated in this way do not require pretreatment with a primer on the metal twill plastic surface prior to application. The pretreatment is essential for fixing other products in the known field to the part to be coated.

The self-locking formulation of the present invention contains a polymerization initiator and accelerator in microencapsulated form and is activated when the nut is tightened against a screw pre-treated with the self-locking formulation. Polymerization and curing begin under anaerobic conditions, and the chemical reaction immediately creates a blocking effect between the nut and the screw.

Unlike the known techniques, the self-locking formulations of the present invention initiate polymerization to produce short polymer chains to inactivate not only primary and secondary radicals, but also those responsible for polymer growth. Contains no agent. Short chains are produced due to the action of polymerization inhibitors and the resulting "glue" hardening is low and therefore the bolt's blocking power is weak. In addition, the absence of inhibitors means that the polymerization of the product placed on the screw occurs before the bolt is tightened. This phenomenon of "fast polymerization" adversely affects the blocking ability of reaction products. To avoid this drawback, the self-locking formulations of the present invention are characterized by the absence of a polymerization inhibitor on the one hand and the presence of microencapsulated polymerization accelerators on the other. Ferrocene is preferably used as the polymerization accelerator of the present invention.

Moreover, surprisingly, the blocking formulations constructed in this manner do not require a primer-based pretreatment on the surface prior to application, whereas the pretreatment is applicable to the part to be applied. Essential for fixing other products in known fields.

Ferrocene is coated by an innovative method with a film of protective material that prevents reaction with the polymerization initiator before the bolt is tightened. When the bolts are tightened, according to the present invention, the protective film breaks as a result of friction, thus providing ferrocene for polymerization.

The method used for coating the polymerization accelerator of the present invention includes a step of preparing a gelatin aqueous solution, a step of adjusting the pH of the aqueous solution to 4 to 7, a step of adding the accelerator to the gelatin aqueous solution, and a step of adding the accelerator. It includes a step of adding a curing agent and an anticoagulant material for the film to be coated, a step of separating the solid part from the aqueous part, a step of washing the solid part with water, and a step of drying the final product.

Advantageously, the polymerization accelerator is ferrocene, the curing agent is glutaraldehyde, and the anticoagulant material is silica (SiO ₂ ).

The use of microencapsulated polymerization accelerators in the formulations of the present invention eliminates the use of the adversely affecting polymerization stabilizers and inhibitors described above, resulting in long-term products without altering blocking characteristics. Can be protected.

Further features and advantages of the present invention will become apparent from the following description given as a non-limiting example with reference to the accompanying drawings.

FIG. 1 is an IR spectrum of a product Multi (engine lubricating oil as a medium). FIG. 2 shows two overlapping IR spectra of oil-immersed and non-oil-immersed screws treated with the encapsulation formulation of the present invention. FIG. 3 is an IR spectrum of the product Torma Prot (engine lubricating oil as a medium). FIG. 4 shows two overlapping IR spectra of oil-immersed and non-oil-immersed screws treated with the encapsulation formulation of the present invention.

The oil resistance of the sealing formulation was then tested by immersing the treated screws in two different media, engine lubricating oils: Multitor and TormaProt.

Methods for preparing the encapsulation formulation and test results for oil resistance and separating power are given in the following examples, which are simply described by non-limiting examples of the present invention.

(Example 1)
With stirring, add 30 g of deionized water, 4 g of butyl glycol, 0.1 g of pigment Unisperse® Blue ID 30466565 and 28% of 0.2 g aqueous ammonia solution to the turbomixer to obtain a mixture at pH 6.5. .. The compound is mixed at a rate of 1400 rpm, then 2 g titanium dioxide, 0.7 g ammonium benzoate and 4 g acrylic resin ACRYSOL® ASE 60 are added to the mixture with stirring. The resulting mixture is placed under reduced pressure of 0.6 bar and stirring is maintained for 5 minutes. The mixture is then brought to atmospheric pressure and 16 g of Teflon® is added with stirring while adding 60 g of phenoxy-polyethoxysulfate. The resulting mixture is kept agitated at 0.8 bar for 25 minutes.

The reaction time and reaction pressure must be maintained as in the examples in order to obtain the final product with optimum characteristics (eg, viscosity and sealing properties).

The product obtained in this example is subjected to an oil resistance test after immersing a screw having a surface treated with the product of Example 1. The IR spectrum of the Multitor product (engine lubricating oil as a medium) is recorded, and the IR spectrum shown in FIG. 1 is obtained. The outer surface of the screw is treated with the product obtained in Example 1 and the screw is immersed in the Multicil product. The recorded IR spectra are shown in comparison with FIG. 2 to emphasize the overlap of the two IR spectra on the surfaces of the oil-soaked screw 1 and the oil-impregnated screw 2. In conclusion, the two IR spectra in FIG. 2 show no relevant difference, simply that some absorption bands in the oiled sample are slightly increased, which is a sealing. It will be due to the transfer to the benzoate surface present in the product. No new absorption band was present and therefore no conversion occurred in the encapsulation product after the screws treated with the product of Example 1 were soaked in oil.

The same test was repeated using another type of medium, engine lubricating oil, sold under the name Torma Prot.

The IR spectrum of the Torma Prot oil is shown in FIG. 3, while FIG. 4 shows the IR spectrum of the outer surface of the oil-soaked screw 1 and the oil-soaked screw 2 treated with the encapsulation product of Example 1. Is shown. The IR spectra on the surface of the soaked and unsoaked screws show no relevant difference. It should be noted that the slight increase is due to the transfer of benzoate present in the sealant to the surface in some absorption bands of the oiled sample. No new absorption band was present and therefore no chemical conversion of the sealing product occurred in the sealant product after soaking in Torma Prot oil.

(Example 2)
55 g of deionized water was placed in a turbo mixer, and while stirring, 0.6 g of pigment UNISPERSE® RED ID 1996500, 0.4 g of ammonia aqueous solution 28%, 2 g of titanium dioxide, 0.8 g of talc, 1 g Ammonium benzoate, 0.1 g ammonium phosphate, 6 g acrylic resin ACRYSOL® ASE 60 and 18 g bisphenol A ethoxylate dimethacrylate were added. The pH of the mixture is 6.5. The temperature of the resulting mixture is set to ambient temperature, the mixture is placed under reduced pressure of 0.6 bar and stirring is maintained under reduced pressure for 5 minutes. The pressure of the mixture is then adjusted to ambient pressure and 21 g of bisphenol A ethoxylate dimethacrylate is added. The resulting mixture is placed under a reduced pressure of 0.8 bar and stirring is maintained for 20 minutes. To the product thus obtained, 3 g of microencapsulated benzoyl peroxide and 0.9 g of microencapsulated ferrocene are added and the mixture is stirred for 5 minutes.

The benzoyl peroxide initiator is microencapsulated according to conventionally known methods, while the ferrocene accelerator is encapsulated by the following method.

Add 80 g of deionized water to the mixer above and add 0.2 g of sodium hexametaphosphate and 4 g of gelatin with stirring. After adding the gelatin, keep stirring for a few minutes and let the mixture stand for 30 minutes. With stirring, bring the temperature of the mixture to 45-70 ° C, add sodium hydroxide, cool the mixture to 43 ° C, add 0.2 g of acetic acid, and finally add 15 g of ferrocene. Cool the temperature of the mixture to ambient temperature. The temperature of the resulting product is then immediately lowered to 10-18 ° C. and 2 g of glutaraldehyde and 1 g of silica (SiO ₂ ) are added.

The resulting product precipitates, then the aqueous solution is removed and the solid portion is washed with deionized water. This operation is repeated 3 times. The resulting product is then filtered and placed in a 40 ° C. dryer for 48 hours. The final product is microencapsulated ferrocene.

Surprisingly, the products thus formulated have a much higher separation value than the product in use, which values are very uniform. The separation values measured with M10 screws according to the DIN 267/27 standard are given in Table 1 below.

(Example 3)
55 g of deionized water was placed in a turbo mixer and then with stirring, 0.6 g of pigment UNISPERSE® GREEN ID 30267548, 0.4 g of aqueous ammonia solution 28%, 1 g of titanium dioxide, 1 g of ammonium benzoate. , 0.1 g of ammonium phosphate and 7 g of ACRYSOL® ASE 60 (used as acrylic resin). The temperature of the resulting mixture is brought to ambient temperature and the mixture is placed under reduced pressure of 0.6 bar. Stirring of the mixture is maintained under reduced pressure for 5 minutes. Bring the mixture to ambient pressure and add 25 g of bisphenol A ethoxylate dimethacrylate. Place under reduced pressure of 0.8 bar and maintain stirring for 20 minutes.

To the product thus obtained, 2 g of microencapsulated benzoyl peroxide and 0.4 g of microencapsulated ferrocene are added. The mixture is stirred for 5 minutes.

Surprisingly, the products thus formulated show very uniform separation values. The separation values measured with M10 screws according to the DIN 267/27 standard are given in Table 2 below.

(Additional note)
"Appendix 1"
(A) At least one type of acrylic resin and
(B) Containing an aqueous emulsion with phenoxy-polyethoxysulfate,
Anaerobic curable formulation.
"Appendix 2"
The acrylic resin is an aqueous emulsion of a cured copolymer.
The formulation according to "Appendix 1".
"Appendix 3"
Phenoxy-polyethoxysulfate is an aqueous mixture containing nonylphenoxypolyethoxy branched-chain ammonium sulfate and an aqueous ammonia solution.
The formulation according to "Appendix 1" or "Appendix 2".
"Appendix 4"
The acrylic resin is selected from ASE SOL® ASE, 20, 60 and 75.
The formulation according to any one of "Appendix 1" to "Appendix 3".
"Appendix 5"
(A) At least one type of dimethacrylate and
(B) At least one type of acrylic resin and
(C) Microencapsulated polymerization initiator and
(D) Containing an aqueous emulsion with a microencapsulated polymerization accelerator.
Anaerobic curable formulation.
"Appendix 6"
It is characterized by containing diurethane dimethacrylate,
The formulation according to "Appendix 5".
"Appendix 7"
The acrylic resin is an aqueous emulsion of a cured copolymer.
The formulation according to "Appendix 5" or "Appendix 6".
"Appendix 8"
Dimethacrylate is bisphenol A ethoxylate dimethacrylate,
The formulation according to "Appendix 5".
"Appendix 9"
The polymerization accelerator is a microencapsulated ferrocene.
The formulation according to "Appendix 5".
"Appendix 10"
It is characterized in that the pH is adjusted in the range of 5 to 10 using an inorganic base selected from NH ₄ OH and NaOH.
The formulation according to "Appendix 1" 1 or "Appendix 5".
"Appendix 11"
Use of the formulation described in "Appendix 1" as a sealant for threads, bolts and caps or sealing caps of screws.
"Appendix 12"
Use of the formulation according to "Appendix 5" as a self-locking agent for threads, bolts and caps or sealing caps of screws.
"Appendix 13"
Prepare an aqueous gelatin solution, adjust the pH of the aqueous solution to 4 to 7, add a polymerization accelerator to the aqueous gelatin solution, add a drug for curing gelatin and an anticoagulant material, separate the solid part from the aqueous part, and solidify. It is characterized by washing the parts with water and drying the final product.
A method for microencapsulating a polymerization accelerator.
"Appendix 14"
The polymerization accelerator is ferrocene, the curing agent is glutaraldehyde, and the anticoagulant material is silica.
The method described in "Appendix 13".
"Appendix 15"
The surface of the thread, bolt and screw cap or sealing cap of the screw is not pretreated with a primer.
Use of the formulations according to "Appendix 11" or "Appendix 12".

Claims (3)

Prepare an aqueous gelatin solution, adjust the pH of the aqueous solution to 4 to 7, add ferrocene as a polymerization accelerator to the aqueous gelatin solution, add a drug for curing gelatin and an anticoagulant material, and separate the solid part from the aqueous part. The solid part is washed with water and the final product is dried.
A method for microencapsulating polymerization accelerators , suitable for use in self-locking anaerobic hardeners . The curing agent is glutaraldehyde, and the anticoagulant material is silica.
The method according to claim 1. Use of a microencapsulated polymerization accelerator obtained by the method according to claim 1 or 2 for preparing a self-locking anaerobic curing agent.

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