JPH0320383A - Self-locking agent and locking tool - Google Patents

Abstract

PURPOSE:To obtain a self-locking agent with which a locking part of a locking tool is coated and which has excellent heat resistance and storage stability by microencapsulating an adhesive compsn. comprising each specified epoxy monomer and arom. diamine, thiosalicyclic acid and a binder. CONSTITUTION:An adhesive compsn. comprising an epoxy monomer with two or more epoxy groups (e.g. bisphenol A type epoxy resin), arom. diamines of formula I (wherein R1-4 are each a 1-3C alkyl, C4H9 or a halogen) and/or formula II (wherein R5-7 are each CH3, C2H5, C3H7 or a halogen), salicyclic acid and a binder (e.g. BR-95 manufactured by Mitsubishi Rayon Co., Ltd.) is microencapsulated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a self-locking agent that is applied to the fastening part of a fastener and fixes the fastened part by tightening the fastener, and the self-locking agent. [Prior art] Regarding applied fasteners, examples of adhesives for bonding and fixing the fastening parts of fasteners include, for example, the following.

■An anaerobic adhesive that mainly contains esters of acrylic acid and methacrylic acid and a polymerization initiator. A pre-coated adhesive made by microcapsulating the anaerobic adhesive from ■■, adding catalysts, fillers, binders, etc., and applying it to the joint area and drying it. ■Curing agent in microencapsulated epoxy monomer,
A pre-coated adhesive containing a filler and binder that is applied to the joint and allowed to dry. [Problems to be solved by the invention] However, the above-mentioned conventional technology has the following problems. That is, since the adhesive in (2) is in a liquid state, it is difficult to quantitatively apply the adhesive to the fastener during the application process, and it is difficult and costly to incorporate equipment into the line. In addition, since the presence of metal ions is essential for curing this anaerobic adhesive, for example, in the case of resin screws, curing may be insufficient, and the adhesive may protrude from the thread. Because it does not harden easily, it can adhere to other parts due to flowing down or volatilizing, which adversely affects the quality of the product.

The pre-coated adhesive described in (■) was designed to solve the problem in (■) above, and although it improved workability, ■
Since the same curing adhesive composition is used, if metal ions are not present on the coated surface, the quality of the product will deteriorate as in case (2). Although the Brecoat type adhesive described in (3) has improved workability and hardening of the protruding area, it has toxicity such as skin irritation and mutagenicity due to the use of aliphatic or alicyclic polyamines as a hardening agent, and is heat resistant. The stability and stability over time are insufficient. The present invention has been made in view of the above points, and aims to obtain a self-locking agent for fasteners having excellent heat resistance and storage stability, and a fastener coated with the self-locking agent.

[Means to solve the problem]

- In order to solve the problems mentioned above, the present invention provides (a) an epoxy monomer having two or more E epoxy groups, (b) an aromatic diamine of the following formula (a) and/or formula (2) (formula In (a), R and ~R4 are respectively 4, :
CH3, C2H,,C,H,,C:H(CH.). ．． C
Represents 4Hq or halogen. ) K7 (In the formula (portion), R and ~R7 each independently represent CH
、． C. Represents C, H, or halogen. ) (Q) A self-locking agent for fasteners in which an adhesive composition containing a thiosalicylic acid (d) binder is microencapsulated, and a fastener is constructed by applying this self-locking agent to the fastening part of the fastener. ．． In addition to the above-mentioned inventions (a) to (d), another aspect of the present invention provides (e) a self-locking agent for fasteners in which an adhesive composition containing a phosphate ester is microencapsulated, and this self-locking agent. The fastener was constructed by applying it to the tightening part of the fastener. The self-locking agent in the present invention is a microencapsulated adhesive composition. In this specification,
``Microencapsulating the adhesive composition'' means ``microencapsulating all or part of the substances that make up the adhesive,'' as explained below. The adhesive composition used in the self-locking agent for fasteners of the present invention contains at least the following epoxy resin, aromatic diamine, thiosalicylic acid, and binder,
Alternatively, it contains a phosphoric acid ester in addition to these, and further contains a filler and a solvent as necessary. The epoxy resin used in the present invention has at least two or more epoxy groups in one molecule, and includes, for example, bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, Talesol novolac-type epoxy resin, and phenol novolac-type epoxy resin. , cycloaliphatic type epoxy resin, glycidylamine type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novola, and yellow type epoxy resin. These epoxy resins can be used singly or in combination. It can be used as a mixture of more than one type. These epoxy resins may contain reactive diluents such as butyl glycidyl ether, epoxy monomers having at least one epoxy group in one molecule, and non-reactive diluents such as xylene resins, as necessary. Can be done. The aromatic diamine of the above formula (a) and/or formula (a) is used as a curing agent for the above epoxy resin.

As the aromatic diamine of the above formula (a), for example. 4.
4'-diamino-3.3',5.5'tetramethyldiphenylmethane. 4.4'-diamino-3.3',5.5
'-Tetraethyldiphenylmethane, 4.4'-diamino-3.3', 5.5'-tetraisopropyldiphenylmethane, 4.4'-diamino-3.3', 5.
5'-tetra n-propyldiphenylmethane. 4.
4'-diamino-3,3'-dimethyl-5,5'-jethyldiphenylmethane, 4,4'-diamino-3,3'
-dimethyl-5,5'-diisoprobyl diphinylmethane. 4.4'-diamino-3,3'dimethyl-5,5'
-D-n-probylisopropyldiphenylmethane, 4
．． 4'-diamino-3,3'-diethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-
3.3'5.5'-tetrachlorodiphenylmethane, 4
, 4'-diamino-3.3',5.5'-tetrabromodiphenylmethane, 4,4'-diamino-3.3'-dichloro-5,5'-dimethyldiphenylmethane, 4.4
'-Diamino-3,3'-dichloro-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'-dichloro-5,5'-diisopropyldiphenylmethane,
4,4'-diamino-3,3'-dibromo-5,5'-
dimethyldiphenylmethane, 4,4'-diamino-3,
3'-dibromo-5,5'-diethyldiphenylmethane. 4.4'-diamino-3,3'-dibromo-5,5'
-diisopropyldiphenylmethane. These aromatic diamines include 4,4'-diamino-3,3'-dichloro-5,5'-dibromodiphenylmethane, etc.
It can be used singly or as a mixture of two or more. Further, as the aromatic diamine of the above formula (2), for example, 2-methyl-4,6-diethyl-m-phenylenediamine, 2,4.6-trimethyl-m-phenylenediamine, 6-methyl-2,4- Diethyl-m-phenylenediamine, 2,6-dimethyl-4-ethyl-m-phenylenediamine, 4,6-dimethyl-2-ethyl-m-phenylenediamine, 2,4.6-triethyl-m-phenylenediamine ．． 2,4.6-Triprobyl-m-phenylenediamine, 4-probyl-2,6-diethyl-m-
Phenylene diamine, 2-chloro-4,6-dipromo m-phenylene diamine, 2,4,6-trichloro m
-phenylenediamine, 6-chloro-2,4-dibromo m-phenylenediamine, 2,6-dichloro-4-bromo m-phenylenediamine, 4,6-dichloro-2
-bromo m-phenylenediamine. Examples include 2,4,6-tribromo-m-phenylenediamine, and these aromatic diamines may be used singly or as a mixture of two or more. By blending the aromatic diamines of formula (a) and/or formula (a) above, a self-locking agent that is not mutagenic and can shorten gel time using a catalyst can be obtained. The above-mentioned aromatic diamine is blended in such a ratio that the ratio of the epoxy equivalent of the epoxy resin used to the amine equivalent of the aromatic diamine used is 0.5 to 1.5. In addition, in the present invention, thiosalicylic acid has the above formula (a)
and/or acts as a curing accelerator when the aromatic diamine of formula (2) is used as a curing agent for epoxy resin.
The benzene nucleus of this thiosalicylic acid may be substituted with chlorine or an alkyl group. In this case, curing accelerators generally include salicylic acid, benzoic anhydride, boron trifluoride or its alkylamine complex salts, acetic acid complex, etc. All of these curing agents can be cured at room temperature, but are heat resistant. Poor quality. However, by incorporating thiosalicylic acid as a curing agent, we were able to obtain a self-locking agent with particularly excellent strength under heat and storage stability. This thiosalicylic acid is blended in an amount of 5 to 80 parts by weight, preferably 10 to 30 parts by weight, per 100 parts by weight of the aromatic diamine of formula (a) and/or formula (a). in this case,
If the blending ratio of thiosalicylic acid is less than 5 parts by weight, the curing speed at room temperature will be slow. If it is more than 80 parts by weight, it may react with aromatic diamines and lose curability. Phosphate ester is used to improve the adhesion of the curing resin to the metal surface and to improve the adhesion of screws. In addition, especially in the present invention, the effect is remarkable when the nut is precoated. This phosphoric acid ester is
It is blended in a weight ratio of 0.5% to 50%, preferably 1% to 4%, based on the epoxy resin. In this case, if the blending ratio of phosphate ester is less than 0.5%.
If the amount is more than 50%, the formulation may become gelled or its shelf life may be significantly impaired. The binder is used to uniformly disperse a certain amount of the self-locking agent so that it can easily adhere to and hold onto the fastening parts of fasteners. The amount of this binder added is such that a certain amount of the above-mentioned self-locking agent is uniformly dispersed.
There is no particular limitation, as long as the amount can easily adhere to and hold the fastening part of the fastener. For example, it can be 3 to 20% by weight based on the weight of the solvent. This binder is solid and non-adhesive at room temperature! 5! Any material may be used as long as it has extractability, hydrophobicity, and solubility in the solvent used. Specific examples of the binder include polyvinyl butyral, vinyl acetate, methyl methacrylate, polyvinyl alcohol, styrene, and urea. One or more copolymers having melamine, polyurethane, or butyl rubber in the main chain can be used. Moreover, these binders can be used alone or as a mixture of two or more kinds.

As the filler, known fillers can be selected and used as appropriate, and for example, inorganic fillers such as alumina, talc, and silica, and organic fillers such as graphite and polyethylene powder can be used. In addition to using one type alone, it can also be used as a mixture of two or more types.

By incorporating these fillers, it is possible to improve heat resistance and reduce the frictional resistance of the tightening parts when tightening the fasteners. The self-locking agent of the present invention may contain a solvent in addition to the above-mentioned precepts. The solvent is one that does not dissolve the capsule wall membrane and is soluble in the constituent substances of the self-locking agent except for the filler, such as aromatic hydrocarbons such as toluene and xylene, trichloroethane, trichloroethylene, etc. Chlorinated hydrocarbons, etc. can be used. Further, these solvents can be used singly or as a mixture of two or more. In addition, for the purpose of improving the properties of the self-locking agent used in the present invention, other optional agents, such as hydrolysis inhibitors, stabilizers, and coupling agents, may be added. Additives such as ultraviolet deterioration inhibitors, colorants, and fragrances may also be added to the above adhesive composition. Furthermore, additives such as polymerization inhibitors, ultraviolet inhibitors, and antioxidants may be added for the purpose of maintaining the long-term storage stability of the adhesive composition.

The self-locking agent of the present invention is a product in which all or a part of the substances constituting the adhesive composition having the above composition is microencapsulated, and the above epoxy resin and aromatic It is blended in such a way that it does not react with the diamine. For example, it can be blended as shown in (1) to (2) below. (2) Aromatic diamine is powdered and mixed with epoxy resin microcapsules.

■ Aromatic diamine is microencapsulated separately from epoxy resin microcapsules and mixed.

(2) For example, an epoxy resin and an aromatic diamine are microencapsulated using the double microencapsulation method described in JP-A-58-189031. In addition, the method of blending phosphoric acid ester and epoxy resin is as follows.
For example, the following ■～■ can be used. ■ Mix phosphoric acid ester and epoxy resin to form microcapsules, and mix together binder, solvent, curing agent, etc. ■ Mix phosphoric acid ester, binder, solvent, curing agent, etc. into epoxy resin microcapsules.

■ Microcapsule phosphate ester and mix together with epoxy resin microcapsules, binder solvent, curing agent, etc. The microcapsules used in the present invention can be produced by, for example, coacervation, interfacial polymerization, in situ
It can be manufactured by a known microencapsulation method such as the in-situ method.

In addition, raw materials for the membrane material of the microcapsules include gelatin, gum arabic, sodium alginate, sodium polyacrylate, polyvinyl anolecole, polyacrylamide, sodium carboxymethyl cellulose, polyether, polyamide, polyurea, epoxy resin, Polyurethane, polystyrene, etc. can be used. The size of the microcapsules is not particularly limited as long as it can be effectively destroyed during tightening depending on the shape or size of the threads formed on the surface to which they are attached, but for example, about 0. 0.005mm to 3nn, preferably 0.005mm to 3nn.
01m+~0.3m.

If it is smaller than 0.005mm, it may be difficult to break.
If the length is greater than 3 m, uncured parts may occur after destruction, and handling may be inconvenient. In order to obtain the self-locking agent of the present invention, a portion of the above-mentioned composition is carefully stirred, for example, in a mixer. Further, the fastener of the present invention is constructed by applying the above-mentioned self-locking agent to the fastening part of the fastener, for example,
The adhesive composition obtained by carefully stirring each component of the self-locking agent in a mixer is applied to the entire or part of the joint by brushing, dipping, spraying, etc., and then leaving it at room temperature or with the adhesive composition. Air dry at a temperature that does not reduce performance.

The fastener coated with the self-locking agent of the present invention is suitable for fastening two or more members together, such as bolts, nuts, pipe joints, split pins, wood screws, and other threaded members. In addition, when joining and fixing parts, the capsule of the self-locking agent attached to a part or the entire surface of one or both of the parts to be joined is destroyed, and each composition of the adhesive is effectively stirred and mixed. Obtained, 111 qi, parts for machinery, architecture, etc.

For example, as shown in the figure, such a fastener consists of a bolt 1 and a nut 2. For example, a self-locking agent 4 is applied to the outer circumferential surface of the threaded portion 3 of the bolt 1, and the bolt 1 and the nut are tightened by hand or with a machine. By tightening the nut 2, the capsule 6 of the self-locking M4 is destroyed, each set or portion of the adhesive composition is mixed and stirred, and a curing reaction occurs even at room temperature or below the temperature condition, and the bolt 1 is The threaded part 3 and the threaded part 5 of the nut 2 are reliably identified, and the threaded part has a self-locking property that does not loosen or open unless a certain force is applied.

In addition, if necessary, after tightening the tightening parts,
By heating the tightened portion, the curing time of the graft composition can be further shortened.

By using the fastener coated with the self-locking agent of the present invention, the curing time of the adhesive composition is shortened, the fastening part is fixed by curing at a low temperature, and it has air drying properties and is especially self-locking. The reliability of the final product is improved because the agent has heat resistance and storage stability.
This eliminates health problems for workers caused by the toxicity of adhesives and improves the working environment.

〔Example〕

Examples of the present invention will be specifically described below. The self-locking agents of Example 1 and Example 2 were prepared by mixing in the proportions. The self-locking agents of Example 1 and Example 2 were tested with JIS 2nd grade M10XPI.
Apply it to No. 5 Fa bolt by dipping, then R
Test pieces of Example 1 and Example 2 were obtained by leaving them under TX50%RH for 24 hours. Comparative Examples 1 to 5 Self-locking agents of Comparative Examples 1 to 5 were prepared by mixing certain compositions shown in Tables 1 and 2 in the proportions shown in the same table. Using the self-locking agents of Comparative Examples 1 to 5, test pieces of Comparative Examples 1 to 5 were obtained in the same manner as in Example 1. Blank columns in Tables 1 and 2 indicate that they are not used. The epoxy resin, curing agent, curing accelerator, filler, solvent, and binder used in the examples and comparative examples of the present invention are as follows. (Microcapsules of eboxy resin) (In the columns of composition shown in Tables 1 and 2, it is simply indicated as capsules.) Ebicoat 828 (manufactured by IF Ciel Eboxy Co., Ltd.,
Product name: Bisphenol A type epoxy resin E E W
189) was microencapsulated using the coacervation method. (i! forming agent) A-1: 4t4'-diamino-3,3'5,5'-tetramethyldiphenylmethane A-2: 2,4.6-trimethyl-m-phe:, diamine a-1= Methyliminobisprobylamine a-2=4
．． 6-dimethyl-m-phenylenediamine (curing accelerator) B-1= Thiosalicylic acid b-1: Salicylic acid b-2: BF3 (CH, Cool {). (Filler) Mistron paper: Magnesium silicate fine powder manufactured by Nippon Mistron Co., Ltd., maximum grain size 6μ, specific gravity 2.75 (Solvent) C-1: Mixture C- of toluene and trichlene in a weight ratio of 4:9 2: Toluene (binder): BR-95: Manufactured by Mitsubishi Rayon Co., Ltd., a type of Dianal BR resin, Tg 80°C, MW 320 × 103 late stage (obtained in Examples 1 to 2 and Comparative Examples 1 to 5) The test pieces obtained were subjected to the torque test described below, and the test beads obtained in Examples 1 and 2 and Comparative Examples 4 and 5 were also subjected to the storage stability test described below.The measurement results of the torque test are shown in Table 3. The measurement results of the storage stability test are shown in Table 4. (Torque test) A Fe nut with a JIS grade 2 pitch of 1.5 was tightened to the specified torque on the test bead to destroy the microcapsules of the self-locking agent applied to the test piece. The hot torque (return torque) was measured after being left for 24 hours under curing conditions of RTX 50% Rh.The hot torque was measured at that temperature after being left in a drying oven at 150°C for 1 hour. ,
The measuring device used was a torque wrench manufactured by Tohnichi Seisakusho Co., Ltd. (Storage stability test) A part of the test piece was placed in a drying oven at 40℃ for 168℃.
After leaving it for a while, tighten a JIS2M pitch 1.5 nut on the test piece to the specified torque, and the curing condition is RTX50.
%Rh for 24 hours, and the return torque was measured. The measuring device used was a torque wrench manufactured by Tohnichi Seisakusho Co., Ltd. (Hereinafter, blank spaces) Table 1 Table 2 (Unit of compounding amount: 2 g) (Unit of compounding amount: g) Table 3 Table 4 Based on the torque test results shown in Table 3, Example 1 and implementation The bolt coated with the self-locking agent of Example 2, screwed together with a nut, and fixed with the self-locking agent is heated (150
It has been confirmed that it has excellent heat resistance as it has sufficient tightening strength even under temperature conditions of (°C) and securely fixes the nut. From the results of the storage stability test shown in Table 4, the self-locking agents of Examples 1 and 2 had a significantly higher RT torque value than the adhesive composition of the comparative example, and were difficult to screw together with nuts. It was confirmed that bolts fixed with self-locking agent have sufficient tightening strength and have excellent storage stability by securely fixing nuts. The self-locking agents of Examples 3 to 6 were prepared by mixing the compositions shown in Table 5 in the proportions shown in Table 5. Each of the self-locking agents of Examples 3 to 6 was
It was applied to Fe bolts of grade MIOXP1.5 by dipping, and then left under RTX 50% Rh for 24 hours.
Test pieces of Examples 3-1, 4-1, 5-1 and 6-1 were obtained. Further, each of the self-locking agents of Examples 3 to 6 was applied to a JI82 grade MIOXP1.5 Fe nut by dipping. after that. Examples 3-2.4-2, 5-2 and 6 were left under RTX 50% Rh for 24 hours.
-2 test beads were obtained. Raw calibration amount 6. 7. Self-locking agents of Comparative Examples 6 and 7 were prepared by mixing the components shown in Table 6 in the proportions shown in Table 6 (Comparative Examples 6 and 7 are also included in the present invention). Comparative Examples 6-1.7-1 (bolt), 6-2.7-2 (
Nut) test pieces were obtained. Blank columns in Tables 5 and 6 indicate that they are not used. The epoxy resin, curing agent, curing accelerator, filler, solvent, and binder used in the examples and comparative examples of the present invention are as follows. (Microcapsules of epoxy resin) (In the columns shown in Tables 5 and 6, it is simply indicated as capsule.) D-1: Epicoat 828 (manufactured by Shell Epoxy Co., Ltd., trade name, Bisphenol A type epoxy resin (EE W189) was microencapsulated by coacervation method. D-2: EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.,
(trade name, phenol novolak type epoxy resin, EEW190) and trimethylolpropane polyglycidyl ether were mixed at a weight ratio of 2:8, and microencapsulated using the coacervation method. (Curing agent) A-1 = Same as Example 1 (Curing accelerator) B-1: Same as Example 1 (Additive) E-1: JI'A514 (Johoku Kagaku Co., Ltd. > m. Product name, Lin acid ester) E-2: Kayamer PM-1 (manufactured by Nippon Kayaku Co., Ltd., trade name, phosphate ester) (filler) Mistronbaber: Same as Example 1 (solvent) C-1 = Example Same as 1 (binder): BR-95: Same as Example 1 Each test bead obtained in Examples 3 to 6 and Comparative Examples 6 to 7 was subjected to the following torque test.Measurement of torque test The results are shown in Tables 7 and 8. (Torque test) For each test bead of Examples 3-1.4-1, 5-1, and 6-1, Fe nuts with JIS Z class pitch P1.5 were used. Tighten to the specified torque, and Example 3-2, 4-2
, 5-2 and 6-2, JIS
Tighten Fe bolts with a second grade pitch P1.5 to the specified torque to destroy the self-locking agent microcapsules applied to each test bead, and the curing conditions are RTX50.
Leave it under %Rh for 48 hours, then heat torque (return torque)
was measured. The hot torque was measured after being left in a drying oven at 150°C for 1 hour. The measuring device used was a torque wrench manufactured by Tohnichi Seisakusho Co., Ltd. (Hereinafter, blank space) Table 5 (Unit of blending amount: Table 7 Table 8 Table B (Unit of blending amount: g) Example 3 From the torque test results shown in Tables 7 and 8 It was confirmed that the self-locking agents of ~6 had significantly higher return torque values than the adhesive compositions of comparative examples (also of the present invention), especially when applied to nuts.Other effects were found in Example 1. -2. [Effects of the Invention] As explained above, the self-locking agent for fasteners of the present invention has particularly excellent heat resistance and storage stability, and fasteners coated with this self-locking agent can be used. As a result, the reliability of the final product is improved, the health problems of workers caused by the toxicity of the adhesive are eliminated, and the working environment is improved. A larger return torque can be obtained.

[Brief explanation of drawings]

The figure is an explanatory drawing for explaining a fastener coated with a self-locking agent according to the present invention. In the drawings, 1 is a bolt, 2 is a nut, 3 and 5 are threaded parts, 4 is a self-locking agent, and 6 is a microcapsule.

Claims (1)

[Scope of Claims] 1. A self-locking agent to be applied to a fastening part of a fastener, characterized in that an adhesive composition containing the following (a) to (d) is microencapsulated. . (a) Epoxy monomer having two or more epoxy groups, (b) Aromatic diamine of the following formula (a) and/or formula (b)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) ( In formula (a), R_1 to R_4 are each independently CH_3, C_2H_5, C_3H_7, CH(CH_
3) Represents _2, C_4H_9 or halogen. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b) (In formula (b), R_5 to R_7 each independently represent CH_3, C_2H_5, C_3H_7 or halogen.) (c) Thiosalicylic acid (d) Binder 2 A fastener in which a self-locking agent containing microencapsulated adhesive compositions containing the following (a) to (d) is applied to the fastening part of the fastener. (a) Epoxy monomer having two or more epoxy groups, (b) Aromatic diamine of the following formula (a) and/or formula (b)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) ( In formula (a), R_1 to R_4 are each independently CH_3, C_2H_5, C_3H_7, CH(CH_
3) Represents_2C_4H_9 or halogen) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b) (In formula (b), R_5 to R_7 each independently represent CH_3, C_2H_5, C_3H_7 or halogen.) ( c) Thiosalicylic acid (d) Binder 3 A self-locking agent to be applied to the fastening part of a fastener, characterized in that an adhesive composition containing the following (a) to (e) is microencapsulated. Locking agent. (a) Epoxy monomer having two or more epoxy groups, (b) Aromatic diamine of the following formula (a) and/or formula (b)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) ( In formula (a), R_1 to R_4 are each independently CH_3, C_2H_5, C_3H_7, CH(CH_
3) Represents _2, C_4H_9 or halogen. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b) (In formula (b), R_5 to R_7 each independently represent CH_3, C_2H_5, C_3H_7 or halogen.) (c) Thiosalicylic acid (d) Binder (e) Phosphate Ester 4 A fastener in which a self-locking agent containing microencapsulated adhesive compositions containing the following (a) to (e) is applied to the fastening part of the fastener. (a) Epoxy monomer having two or more epoxy groups, (b) Aromatic diamine of the following formula (a) and/or formula (b)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) ( In formula (a), R_1 to R_4 are each independently CH_3, C_2H_5, C_3H_7, CH(CH_
3) Represents_2C_4H_9 or halogen) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b) (In formula (b), R_5 to R_7 each independently represent CH_3, C_2H_5, C_3H_7 or halogen.) ( c) Thiosalicylic acid (d) Binder (e) Phosphoric acid ester