JPH02208387A - Adhesive - Google Patents

Abstract

PURPOSE:To form an adhesive which undergoes instantaneous reaction, scarcely causes drug rash, is excellent in shelf stability, and has a high adhesive power to a wide range of materials by covering an epoxy compound, as a principal component, and/or a (meth)acryloyloxy acidic phosphoric ester, as a curing agent, with a film-forming substance. CONSTITUTION:This adhesive consists of a first component containing an epoxy compound and a second component containing an acidic phosphoric ester having acryloyloxy and/or methacryloyloxy groups, wherein at least one of said components is enclosed in a film-forming substance. The amount of the (meth) acryloyloxy acidic phosphoric ester in the second component is preferably 2-50 pts.wt. based on 100 pts.wt. epoxy compound of the first component. A desirable method for enclosing the first component and/or second component is encapsulation with a urea resin or melamine resin.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to an adhesive that has instantaneous adhesion ability to various materials. Therefore, it is suitable for use in fields where a film is formed and used, for example, as an adhesive for preventing loosening of screws.

(Prior Art) Anaerobic acrylic adhesives or epoxy adhesives are conventionally known as adhesives to be pre-coated onto objects to be treated.

[Problems to be Solved by the Invention] However, although the acrylic adhesive has a high instantaneous adhesion ability, it has a high selectivity to abrasive materials, whereas the epoxy adhesive has a low selectivity to 4A materials, but However, it had the disadvantage that it took a long time to bond.

Another problem was the toxicity of amine compounds commonly used as curing agents for epoxy adhesives.

On the other hand, phosphoric acid is known as a curing agent that has a high reaction rate and is less toxic than amine compounds.

However, the reaction rate of this curing agent is too high, and gelation occurs before it is mixed with the epoxy compound (New Epoxy Resin J, edited by Hiroshi Kakiuchi, published by Shokodo, p. 553).
It was impossible to mix the compound with the base compound, which is a chemical compound.

(B) Structure of the Invention [Means for Solving the Problems] The inventor of the present invention aims to avoid direct contact between the epoxy compound and the curing agent before use, and to cause the curing reaction under a uniform mixing state of both. As a result of studying a method to obtain an adhesive that can minimize the amount of unreacted curing agent remaining after the curing reaction, we created an adhesive in which either the epoxy compound or the curing agent, or both, are coated with a film-forming substance. did.

Furthermore, as a result of various studies on phosphoric acid curing agents that have instantaneous adhesion ability upon contact with epoxy compounds, good compatibility with epoxy compounds, low toxicity, and easy encapsulation, we found that acryloyloxy groups and/or or an acidic phosphate ester compound having a methacryloyloxy group (hereinafter referred to as “(
meth)acrylo4yloxy acidic phosphate ester. ) was found to satisfy the above conditions, and the present invention was completed.

That is, the present invention comprises: a first component containing a bogisi compound and a second component containing an acidic phosphoric acid ester compound having a (meth)acryloyloxy group, and at least one of the components is present in the film-forming substance. The present invention relates to an adhesive characterized in that it is contained in.

Specific examples of the compound in the first component include allyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycidyl ether. Aliphatic compounds such as glycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether or glycidyl (meth)acrylate; phenylglycidyl ether, p-talesylglycidyl ether, 0-phenylphenol glycidyl ether, 2,6-dibromo -4 ~ Aromatic compounds such as isopropylphenyl glycidyl ether, styrene oxide, resorcin diglycidyl ether, or bisphenol A-diglycidyl ether; Can be mentioned.

Among these, bisphenol A-diglycidyl ether is preferred because it has a high adhesion speed and is inexpensive.

Specific examples of the (meth)acryloyloxy acidic phosphate ester compound in the second component include 2-acryloyloxyethyl (meth)acrylate, 2-(meth)acryloxyethyl acid phosphate, and 2-(meth)acryloxy Propyl agitate phosphate, 3-
Examples include chloro-2-acid phosphoxypropyl (meth)acrylate, 2-(meth)acryloxyethyl acindobosphate monoethanolamine half ester, and the like.

Among these, 3-chloro-2-acid phosphoxypropyl (meth)acrylate is preferred because it can be easily encapsulated with a urea resin in the encapsulation described below.

Each of the above-mentioned substances can be added to each component of the adhesive of the present invention.

In addition to the above epoxy compound, the first component contains (
A redox catalyst or the like can be added in combination with a peroxide and a reducing agent that can radically cure the meth)acryloyloxy acidic phosphate ester compound.

An acid anhydride or the like which is another curing agent for the epoxy compound of the first component can be added to the second component.

In addition, the first component and/or the second component may include an acrylic ester monomer used in ordinary anaerobic acrylic adhesives in order to add oil resistance, which is a characteristic of anaerobic adhesives, to the adhesive of the present invention. and/or methacrylic acid ester monomers can be added. If a redox catalyst is used to cure this monomer, the catalyst is
component and therefore this monomer is the second
Add to ingredients.

When the content of the epoxy compound in the first component is 50% by weight or more, the characteristics of the epoxy adhesive, such as the difficulty in selecting the material of the adherend, are exhibited, which is preferable.

The content of the (meth)acryloyloxy acidic phosphate compound in the second component is preferably 50% by weight or more.

The preferred blending ratio of both components in the adhesive composition of the present invention is such that the epoxy compound in the first component is 100 parts by weight, and the (meth)acryloyloxy acidic phosphate ester in the second component is 2 to 50 parts by weight. be.

If the amount is less than 2 parts by weight, the curing reaction will be slow and it will be difficult for the reaction to proceed completely, and if it exceeds 50 parts by weight, the rigidity of the cured resin may decrease, which are both undesirable.

The adhesive of the present invention has a first component and/or a second component encapsulated in a film-forming substance.

As a method of encapsulation, encapsulation with urea resin or melamine resin is preferable.

In particular, in the second component, amine compounds, which are conventional curing agents for epoxy compounds, are often water-soluble and difficult to encapsulate, and even if they are poorly water-soluble, the amines themselves are basic, so it is difficult to encapsulate them. However, the curing agent of the present invention, the (meth)acryloyloxy acidic phosphate ester, is itself acidic. Therefore, encapsulation by the above method is easy without using an acid catalyst.

Furthermore, since both components are easily dispersed in the urea resin or melamine resin prepolymer, they can be encapsulated relatively easily.

After encapsulating at least one component in this way,
When mixed uniformly with other components, it becomes the adhesive of the present invention.

Another method is to use partially saponified polyvinyl alcohol, hydroxypropyl methyl cellulose, gelatin, etc. as a film-forming substance, emulsify one of the components in an aqueous solution, and apply this emulsion to the adherend. ,
Examples include a method in which a film of a film-forming substance is formed on the surface of the same component by drying the moisture, and then another component is applied on the film or on another adherend to be adhered to the adherend. .

In this case, it is preferable to form a film of the film-forming substance on the surface of the other component by forming an emulsion of the other component and then applying the emulsion, as this reduces the risk of chemical damage.

When butyral resin or water-soluble nylon is mixed with the adhesive of the present invention, it becomes easier to coat the capsule body on the adherend.
Moreover, a resin film is formed on the surface after coating, and a dry-touch coated surface can be obtained.

[Effect]

The adhesive of the present invention has high stability before use because the epoxy compound as the main ingredient and/or the (meth)acryloyloxy acid phosphate ester as the curing agent are coated with a film-forming substance. Because of their good compatibility, a curing reaction occurs instantly upon contact, and the reaction is uniform.

[Examples and comparative examples]

The present invention will be explained in more detail by giving Examples and Comparative Examples below.

As a method for evaluating the adhesive of the present invention, the adhesion performance to screws was tested using the following test method.

(Application of adhesive to screws) Screws made of stainless steel (SUS304), brass (copper:zinc - 65:35 weight ratio) and polyamide resin (nylon 6), 10mm diameter, 40mm long, yellow chrome-1. 0.2 g (in terms of solid content) of adhesive was uniformly applied to the groove portion over a width of 15 mm.

In the case of a water-based adhesive, it was dried at 80° C. for 20 minutes, and in the case of an oil-based adhesive, it was left as is, and the glue pre-coated with adhesive was used to obtain a screw type.

(Adhesive Performance Evaluation Test) The 10 coated screws were tightened to a nut with a torque of 300 kg/cm, and after being left at 23°C for 24 hours, the start-up return torque was measured and the average value was determined.

Example 1 (Production of first component) A capsule body made of urea resin of n-butyl glycidyl ether was produced by the following method.

■P, in a flask, 350 g of formalin aqueous solution with a concentration of 37% by weight, 131 g of urea, and 1.0 g of triethanolamine.
Pour 7g into the propeller sitting position 7 at 70°C! The mixture was stirred and reacted for 2 hours at 300 rpm using a l' apparatus to obtain a urea resin prepolymer.

Next is 2! Add the above prepolymer aqueous solution 348 to the beaker.
g and 609 g of pure water, and dilute p I-1 to 2 with 1N sulfuric acid.
．． After adjusting the temperature to
After reacting for 6 hours under stirring at rpm, the reaction was continued for 14 hours under stirring at 300 rpm using a propeller type stirring device.

The resulting slurry was neutralized with an aqueous solution of IN I'+1 sodium, purified with pure water and methanol, and dried on a tray at 40°C. As a result, n-butyl glycidyl ether was 85 g of capsules having a particle size of 20 to 501 tm and containing 115% of the urea resin by weight were obtained.

(Production of second component) 2-azinodophosphoxyethyl acrylate was used as it was.

(Preparation of enucleation) 83 g of capsules as the first component (containing 50 g as n-butyl glycidyl ether), 110 g of 2-acyntoposphoxyethyl acrylate, butyral resin B M-, S (Building Chemical Industry Co., Ltd.) as a binder. (Manufactured by 1 local government) 5g and 1.00g of luene] were added and mixed uniformly for 3 minutes using a lab mixer.

The resulting mixture remained stable without gelation for 3 months even when left at room temperature.

(Adhesive Performance Evaluation Test) Table 1 shows the results obtained for the adhesive according to the evaluation method described above.

Comparative Example 1 When an adhesive was produced using 50 g of unencapsulated r)-butyl glycidyl ether as it was in place of the first component in Example 1, gelation occurred during mixing with the second component. Ta.

Examples 2-4 Epoxy compound or (meth) used in Example 1
Table 1 shows the test results when the type and amount of acryloyloxy acidic phosphate ester were changed as shown in Table 1, and the other conditions were carried out in exactly the same manner as in Example 1.

Example 5 (Preparation a of the first component) 8 G of pure water in a 2β beaker Og'-Gohsenol GM
-1,4 (partially saponified polyvinyl alcohol with a degree of saponification of 86 mol% and an average degree of polymerization of 1400, Nippon Synthetic Chemical Industry Co., Ltd.
(Made by Kiku)], OOg was prepared and made into an aqueous solution. After that, 1000 g of bisphenol Δ-diglycidyl ether was separated into 1 liquid under stirring at 65 Orpm using a propeller type stirring device.
：i-l- for 10 minutes, and then added 1 g of cumene hydroperoxide and 1 g of dimethyl p-toluidine as sox-based catalysts, and continued stirring for 1 hour to obtain an aqueous emulsion. .

(Manufacture of second component) 2! A heater was charged with 348 g of the same urea resin prepolymer aqueous solution used in Example 1 and 609 g of pure water, heated to 30'C, and heated to 400°C using a homogenizer.
At pm stirring ■, 3-chloro-2-acynl
``Put 1 to 51 g of phosphoglycypropyl acrylate, raise the temperature to 40 ° C, react for 6 hours, and then continue to react for 14 hours under stirring at 3000 rpm using a propeller type stirring f' + 21ffi. Continuing iJ, 3-Rishi 10
-2-Acidophospho)-dipropyl acrylate-0
102 g of capsules with a particle size of 20 to 50 m/i are 43% by weight.

(Preparation of adhesive) 98 g of emulsion of the first component (50 g of Hisfurol △ diglycidyl ether, Kunon Hi l' Rober Oxai F0
．． 05g and Shimedilpara I/Luidine 0.05B) and 10g of capsules of the second component (3-ri-l Coro-2-acyl-pospoxypropylacryl □
(containing 5 g) were uniformly mixed for 3 minutes using Labo Mikily.

Even when the resulting mixed solution was left at room temperature, 3 did not gel for months and remained stable.

(Adhesive Performance Evaluation Test) Table 1 shows the results obtained for the adhesive according to the evaluation method described above.

Examples 6 to 7 Table 1 shows the test results when the test was carried out in exactly the same manner as in Example 5, except that the type and amount of the epoxy compound used in Example 5 were changed as shown in Table 1.

Comparative Example 2 In the production of the second component of Example 5, 3-chloro-2-
In place of phosphoxyprobyl acrylate, finely powdered I-phosphoric acid anhydride 51. Insert g,
The other conditions were the same as in Example 5, 60% by weight of 1-phosphoric anhydride was included, and the coating was made of urea resin) Diameter 2
4) Also, capsule bodies 85 LC of 0 to 50 mμ.

Next, in the preparation of the adhesive, 8.3 g of the capsules obtained in - in place of the second component capsules of Example 5.
(containing 1 g of anhydride to 5 g of limellic acid) and other conditions were the same as in Example 5 to obtain an adhesive.

The resulting mixture remained stable without gelation for 3 months even when left at room temperature.

When the adhesive was subjected to an adhesive performance test according to the evaluation method described above, the adhesive speed was slow, and as shown in Table 1, the adhesive performance was also poor.

Example 8 (Preparation of first component) Hisphenol A- used as the first component in Example 5
An aqueous emulsion containing diglycidyl ether was applied to the grooves of screws made of various materials and dried at 80° C. for 20 minutes to form a precoat film.

(Preparation of second component) In a 22-heater, 860 g of pure water and Gohsenol GM-
14,100 g was charged, made into an aqueous solution, and stirred at 650 rpm using a propeller type stirring blade.
1. Add 1000 g of 1-2-acet phosphoxypropyl acrylate at the separation port = 1 for 10 minutes, and then continue stirring to obtain aqueous emulsion 11. Ta.

Apply this emulsion to the groove of pear 1- and heat it at 80°C for 2
A precoat film was formed by drying for 0 minutes.

(Adhesive Performance Evaluation Test) When an adhesive performance test was conducted using the pre-coated screws and nuts according to the evaluation method described above, yellowing was observed.
The mate screw had a weight of 450 kg/cm, and the stainless steel screw had a weight of 390 kg/cm.

In addition, when an adhesive performance test was conducted on the screws and Nano 1 which had been pre-rolled at room temperature for 3 months, no deterioration in performance was observed.

(C) Effects of the Invention The adhesive of the present invention is of an instantaneous reaction type, has little fear of chemical damage, has excellent storage stability, and has high adhesive strength to a wide range of materials.

The adhesive of the present invention is used in fields where it is precoated with a metallic phase to form a coating film with the adhesive;
For example, it is suitable as an adhesive for screw loosening.

Claims (1)

[Claims] 1. Consisting of a first component containing an epoxy compound and a second component containing an acidic phosphoric acid ester compound having an acryloyloxy group and/or a methacryloyloxy group, at least one of the components being included in the film-forming substance. An adhesive characterized by: