JPS6178884A - Anticorrosive adhesive - Google Patents

Abstract

PURPOSE:To improve the inhibitory effect on corrosion, by incorporating baked mountain leather into a resin for an adhesive. CONSTITUTION:0.5-30pts.wt. baked mountain leather prepared by heat-treating (baking) the powders of a fibrous hydrated magnesium silicate clay mineral, such as sepiolite, attapulgite or palygorskite, at 400-1,100 deg.C, is added to 100pts. wt. resin for an adhesive to give the titled adhesive. This adhesive can be made to have suitable viscosity to make it easy to apply, due to the state wherein the clay mineral is properly dispersed in the resin or by suitably adding a sol vent. In addition, a filter for giving suitable viscosity, adhesive strength, etc., a curing agent for setting up the resin, an antiseptic for a resin, a plasticizer, a curing accelerator, etc. may suitably be added to this adhesive.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] More specifically, the present invention relates to an adhesive having excellent anti-corrosion properties in environments where corrosion is likely to occur.

Doctor! j71. 2. Description of the Related Art Equipment, household goods, etc., or joined products of their parts are required not only to have adhesive strength and durability, but also to have corrosion resistance.

Adhesives can be used not only to bond metal materials together, but also to bond plastic films and metals, asbestos slate plates, aluminum, rubber materials and metals, and ceramics and gold.

Adhesion of wood materials and metals, as well as non-metallic materials, and its uses are wide-ranging. What are the adhesives made using these adhesives?

They are sometimes used in environments where corrosion is likely to occur, such as being exposed to wind and rain containing seawater or being placed in a high-temperature, humid environment.

However, in recent years, as the demand for resource conservation has increased, there has been a desire to develop adhesives that do not deteriorate in performance over a long period of time due to causes such as corrosion. In addition, the environment in which adhesives are used has become more diverse as their applications have expanded, and the number of cases in which they are used in harsh environments where corrosion is likely to progress has increased.In this sense, there is also a demand for adhesives with excellent corrosion resistance. has become even stronger.

When placed in an environment where corrosion is likely to occur.

Various ions, water, oxygen, etc. that cause corrosion infiltrate from the end portions of the joint, and corrosion eventually progresses at the joint, resulting in a phenomenon in which the adhesive performance of the armpit region deteriorates.

Since the adhesives used for bonding these adhesives are mainly composed of polymeric materials, they are expected to improve the corrosion resistance of the adhesive layer itself.

In reality, many corrosion problems occur, and at present we have not yet developed an adhesive that is highly effective in preventing and suppressing corrosion.

In order to prevent this corrosion of adhesives, several solutions have been provided through the efforts of many researchers. These methods basically maintain a balance between the adhesion and cohesive force of the adhesive, while reducing moisture permeability and water absorption without containing any material components with excellent anti-corrosion effects in the adhesive itself. The idea is to increase the adhesive strength.

Specifically, we focused on improving the adhesive strength between the adherend material and the adhesive, and published Japanese Patent Application Laid-Open No. 50-139129.
A method of introducing a compound that forms a chelate bond at the interface between an adherend and an adhesive as disclosed in No. 151523,
Alternatively, a method has been considered in which a coupling agent is interposed at the interface between the adherend and the adhesive, as disclosed in JP-A-53-113835. However, resins that can be chelated or coupled have selectivity, which has the drawback of restricting the selection of resin materials for adhesives.

In addition, there is a method of incorporating rust-inhibiting additives into adhesives to prevent corrosion. Among them.

Chromate additives such as synchromates are often used. When these additives come into contact with moisture, they elute chromate ions, and their strong oxidizing action damages metal surfaces.
It has a corrosion-preventing effect. However, compounds containing such heavy metals are toxic and
It had the disadvantage of lack of safety.

Therefore, the inventors of the present invention have conducted intensive research to solve these conventional problems, and have conducted various systematic experiments.

This has led to the present invention.

[Problem of the present invention]

The present invention can be exposed to wind and rain containing sodium chloride,
The purpose of the present invention is to provide an adhesive that has the effect of suppressing @corrosion even in environments where corrosion is likely to occur, such as under high temperature and high humidity.

Furthermore, the present invention provides an adhesive with low pollution potential without using additives that have safety problems such as toxicity.

[Structure of the invention]

That is, 1. The food protection adhesive for women of the present invention is an adhesive mainly composed of an adhesive resin, and contains 0.5 to 30 parts by weight of calcined mountain skin per 100 parts by weight of the adhesive resin. It is characterized by:

The adhesive resin used in the present invention is a resin used in conventional adhesives, and is easily formed into a film, mixes well with the calcined mountain bark, and can be dispersed appropriately. An appropriate one should be selected in consideration of the purpose of use, conditions, etc.

Specific examples include pheno-11/resin, melamine resin, and isobutyne-maleic anhydride copolymer.

Thermosetting resins such as urea resin, resorcinol resin, furan resin, saturated or unsaturated polyester resin, acrylic copolymer resin, epoxy resin, polyurethane resin, silicone resin, alkydo resin, amino alkyd resin, polyvinyl acetate, polyvinyl Alco-/I/(Pobel 1PVA)
, nylon resin, polyvinyl chloride, polyvinyl butylene, thermoplasticized polyacrylic acid ester/vl nitrocellulose, etc., and in the case of inbutene-maleic acid copolymer, made water-soluble by adding alkali. and use it. In addition, suitable curing agents, etc. 9 For example, triethylamine and triethylenetetramine for epoxy resins.

By adding appropriate fkFA such as diamine diamide, the contact force against the adherend can be changed.

The fired mountain bark is made by heat-treating (calcining) powder of a female hydrated magnesium silicate clay mineral in a temperature range of 400 to 1100°C.

Here, the R male hydrous magnesium silicate clay mineral (hereinafter referred to as the clay mineral) is commonly known as mountain cork (M
mountain cork), mountain wood (M
It is a mineral called mountain wood, mountain leather, etc. It is a mineral whose main component is hydrated magnesium silicate and has highly reactive hydroxyl groups on its surface. Incidentally, a part of magnesium may be replaced with aluminum, iron, sodium, nickel, etc.

Specifically, sepiolite whose main component is hydrated magnesium silicate + attabulgite whose main component is hydrated magnesium aluminum silicate, palygorskite, loglinite + sepiolite (Meers-chaum), etc., and one or a mixture of two or more of these are used.

These clays E%7 are aggregates of long fibers having a rectangular cross section with sides of 0.01 to 0.1 μm culmability, and the aggregates have many holes in the length direction of the fibers. are doing. Also,
The clay mineral itself has the property of absorbing and adsorbing a large amount of water.

The fired mountain skin of the present invention is obtained by heat-treating these clay minerals, and this heat treatment is performed at a predetermined temperature for at least 15
It is preferable to hold it for about a minute.

The longer the holding time is, the more stable the performance can be obtained.

Structural changes caused by this heat treatment are not necessarily clear, but compared to the clay mineral before firing, the fiber shape of the fired mountain bark remains the same, but the attached water and groove water contained in the crystal structure It is thought that it has the property of taking in a larger amount of Na ions because it has been modified into a structure with less amount of what is called bound water or water of crystallization. (Thus, due to this property, it exhibits a more excellent inhibitory effect against corrosion caused by sodium chloride, etc., than the clay mineral.

Most preferably, the fired mountain bark used in the present invention is one obtained by heat-treating the clay mineral at a temperature of about 900°C.

If the material is heat treated in a temperature range of 400° C. or higher and 1100° C. or lower, a corrosion inhibiting effect is recognized.

Further, the calcined mountain bark may be used in the form of a single powder or a plate, but a powder-like one is preferable, and the particle size of the powder is preferably about 01 to 100/7 m.

The amount of the calcined mountain bark to be mixed is 05 to 30 parts by weight per 100 parts by weight of the adhesive resin. When the mixing amount is within this range, the advantages of the adhesive are not impaired and the corrosion inhibiting effect is produced. Among these, it is preferable to use 5 to 15 parts by weight, and the above-mentioned effects can be more effectively achieved. If the amount of calcined mountain bark mixed is less than 0.5 parts by weight, the corrosion inhibiting effect will not be sufficient, and if it exceeds 30 parts by weight, the viscosity of the adhesive will be too high and the coating will be difficult. Workability is reduced and the flexibility of the adhesive after bonding.

This is not preferable because the tackiness decreases.

The anti-corrosion adhesive according to the present invention is in a state in which the clay mineral is appropriately dispersed in the above-mentioned resin for adhesive.

Alternatively, it may be made easy to apply by adding a suitable solvent to give it a suitable viscosity.

In this case, the solvent used is one that stabilizes the adhesive, specifically water as well as xylene.

Ethylene glyco-mu motubutyl ether, ≠ sopropymu
There are organic solvents such as alcohol and methyl ethyl ketone.

In addition, a filler to impart appropriate viscosity and adhesive strength, a curing agent to solidify the resin, a resin pot preventer, a plasticizer, a curing accelerator, etc. can be added as appropriate to this contact agent. .

For example, fillers that are commonly used in adhesives can be used. Specifically, inorganic fillers such as carbon black, silica powder, calcium carbonate, clay aluminum stain, short fiber nylon (about 5H in length) can be used. ), organic fillers such as polypropylene powder, and even vegetable fibers such as pulp. By mixing these fillers, the smoothness, viscosity, workability, reinforcing properties, etc. of the adhesive composition can be improved. The amount of the filler to be mixed may be as long as it achieves the above-mentioned effects and does not inhibit the intended function of the adhesive.
Usually, 01 to 100 parts by weight per 100 parts by weight of adhesive resin.
Parts by weight.

Further, as the curing agent, those commonly used in adhesives can be used, and the curing agent is appropriately selected depending on the functional groups possessed by the adhesive resin. For example, for epoxy resin, add an appropriate amount of a curing agent such as triethylamine, triethylenetethumine, or dicyandiamide.

The hardness of the resin after curing, the adhesive strength to the adherend, etc. can be changed.

A typical method for preparing the uninvented anti-corrosion adhesive is as follows.

First, a commonly used adhesive resin is prepared. Next, the powdered clay mineral is placed in an adhesive resin and thoroughly mixed to obtain a preservative adhesive. When mixing, Bo! Remille, sand grinder, automatic mortar,
It is preferable to mix the clay mineral using a roller mill or the like until the clay mineral is sufficiently dispersed in the adhesive resin. Furthermore, fillers, solvent 1 reinforcing agents, and other additives are added to this adhesive as appropriate.
Mix by the same mixing method as above. In addition, when adding these additives, especially solvents, as mentioned above, they can be added and mixed with the entire preservative adhesive, or they can be mixed with the adhesive resin in advance and then the clay mineral can be added to the mixture. The additives may be mixed and dispersed, or the additives may be further added thereafter.

The preservative total adhesive of the present invention can be applied to or between two objects to be adhered.
The coating is applied by a well-known coating method, such as manual methods such as brush coating, transfer method using a roller, tactile pressure method using a ball point, spray method using a nozzle type, and gravity drip method.

Then, if necessary, heat or dry to adhere and join.

[Operation and effects of the invention]

The antiseptic adhesive of the present invention is an excellent adhesive that suppresses corrosion even in environments where corrosion is likely to occur, such as in environments where corrosion is likely to occur, such as in environments where sodium chloride is exposed to the wind and rain. be.

Furthermore, since the fiber-shaped calcined skin is uniformly dispersed in the adhesive, the adhesive exhibits appropriate thixotropy and has excellent application workability.

Although the mechanism by which the adhesive of the present invention exerts this effect is not necessarily clear yet, it is thought to be of the following order.

Therefore, when various types of ions, such as Na+, that cause or accelerate corrosion, enter the interior from the joint terminal, the calcined bark in the adhesive takes in various ions such as Na+, and the ions This seems to be because the particles do not reach the surface of the adherend. Also, if there is a scratch on the joint end, the i part of the solvent is the anode.

Then, the suffix 1 interface around the eccentric part becomes the cathode.

When Na ions, etc. are present in this cathode part, the OH- ions generated in this cathode part are successively neutralized by Na+ ions, etc., and corrosion of the adherend progresses. Due to the presence of fired mountain bark.

It is thought that Na + ions and the like are incorporated into the fired mountain bark, thereby suppressing corrosion.

〔Example〕

Two examples of the present invention will be fully explained below.Example 1゜As adhesive resins, commercially available Ebisu type epoxy resin, urethane modified resin and Nl3R modified resin were used as a5:aO:
A mixture of 15 parts was prepared.

In addition, a fired mountain skin was prepared by firing sepiophyte powder having a particle size of 200 mesh or less in a Luch type nichrome furnace in a dioxidizing atmosphere at the temperature shown in Table 1 for 2 hours.

Next, 10 parts by weight of the calcined skin was added to 100 parts by weight of the adhesive resin, and dispersed using a three-roll mill until the particle size of the calcined skin was no more than Q,'l pm on a grain gauge. To the Takako mixture, 161 parts by weight of dianediamide, 70 parts by weight of aluminum powder, 5 parts by weight of kaolin, and 3 parts by weight of soft p-carbonate were added to 100 parts by weight of the adhesive resin. The mixture was mixed for 1 hour at normal pressure using a pickler, and then ground and mixed for 3 hours under reduced pressure to obtain a preservative complete adhesive according to the present invention.

Adhesive performance evaluation test of the obtained anti-corrosion adhesive.

A tensile shear test and a corrosion resistance test were conducted.

First, a tensile shear test was conducted. First, the obtained anti-corrosion adhesive was applied to a 5POC mild steel plate (25 x 100
7) The adhesive was spread to a position 10fi from one end in the longitudinal direction so that the adhesive thickness was 0.5ff. Next, all of the BPOC soft steel plates of the same shape are glued on top of each other in a staggered manner so that they overlap in the longitudinal direction and the parts that are not coated with adhesive do not face each other, and are heated to 180°C. The sample was cured for 20 minutes to prepare a test specimen. These test pieces 20℃
A tensile shear test was conducted in an atmosphere of The results are shown in Table 1.

Next, a corrosion resistance test was conducted using a salt spray test. 5PCC pre-degreased with thinner and petroleum benzene
The obtained adhesive was placed on a mild steel plate (70 x 130 x C1, 8, m) in a length of 1J30ff and 120 m in length.

A test specimen was coated to a thickness of 0.3 runs.

These test pieces were left in a salt spray tester based on JIS K-5400 for 60 days, 45 days, and 60 days, and after washing with water, the adhesive was peeled off and the state of black rust on the surface of the mild steel plate was observed. The results obtained are shown in Table 1. Note 1
Since the size of black rust that occurred in each sample was almost the same, the evaluation of spot rust was determined by focusing on the amount of black rust that occurred. The amount generated is calculated by calculating the ratio of the total area of black rust in the test specimen, and the evaluation value in Table 1 is 1:0% or more and less than 0.5%.

2: 0.5% or more and less than 2%, 3: 2% or more and less than 6%.

4:65 or more and less than 10%, 5110% or more and less than 14%, 6114% or more and less than 18%, 7+18% or more and less than 22%, 8122% or more and less than 26%, and 9:26% or more (hereinafter the same) .

For comparison, evaluation tests were conducted without firing the mountain bark or at a firing temperature of 200°C and 1200°C. The results are also shown in Table 1.

In addition, the number of tests in each test is three points for each adhesive, and the number in one table is the average of the three test points (the same applies below).

As is clear from Table 1, the adhesive according to the present invention has superior corrosion resistance compared to the comparative adhesive.

Example 2 In this example, various adhesives were prepared by changing the amount of mountain skin calcined at 900°C.

To 100 parts by weight of the adhesive resin prepared in Example 1, the amount of calcined mountain bark powder prepared in Example 1 at a firing temperature of 900°C was added in the amount shown in Table 2, and the calcined mountain bark powder was prepared in a three-roll mill. The particles were dispersed until the particle size became 0.2 μm or less using a particle gauge.

Add the additives used in Example 1 to this mixture.

By mixing in the same manner as in Example 1, 9 anticorrosive adhesives according to the present invention were obtained.

A test piece similar to that in Example 1 was prepared using the obtained No. 9 anti-corrosion adhesive, and the same adhesive performance evaluation test as in Example 1 was conducted. The results are shown in Table 2.

For comparison, we prepared a comparative adhesive with the same composition as above, except that it did not contain fired mountain bark or had an excessive amount of fired mountain bark mixed in, and conducted the same adhesive 1 performance evaluation test. (Sample numbers 04 to 06).

The results are also shown in Table 2. In the table, P)IR
is + Per &ndrad Re5in, which means the ratio of additive to 100 resin (the same applies hereinafter).

As is clear from Table 2, the adhesive according to the present invention has superior corrosion resistance compared to the comparative adhesive.

Example 3 In this example, two adhesives having different compositions were prepared, and an adhesive evaluation test was conducted using these adhesives.

In advance, a piece of calcined mountain skin was prepared by calcining Spanish sepiolite powder having a particle size of 200 METSI or less in a crucible-type nichrome furnace in an oxidizing atmosphere at the temperature shown in Table 3 for 2 hours.

Next, as an adhesive resin, methyl methacrylate/L'3
00 parts by weight and methacrylic acid-2-hydroxy 34ethyl/
L/130i [Oki part, methacrylic acid 40 parts to 1 part.

A mixture of 80 parts by weight of acrylonitrile-butadiene copolymer was prepared by stirring and dissolving it at 60°C.

To 100 parts by weight of this resin, 10 parts by weight of the above-mentioned calcined mountain bark powder was added and uniformly dispersed and mixed in a heated loaf at 60° C. until the particle size of the calcined mountain bark powder became 0.2 μm or less. After cooling, 5 parts by weight of ethylene thiourea was added to the mixture based on 100 parts by weight of the resin.

An adhesive according to the present invention was obtained by stirring and mixing with L crush.

In addition, as adhesive resin, methacrylic acid methyl yv40
0 parts by weight and 2-hydroxyethyl methacrylate/I/7
0 parts by weight, acrylonitri-butadiene copolymer 90
parts by weight are stirred and dissolved at 60°C,
To 100 parts by weight of this resin, 10 parts by weight of the above-mentioned calcined mountain bark was added and dispersed and mixed in the same manner as above. After cooling, 35 parts by weight of cumene hydrobaquine was added to the mixture based on 100 parts by weight of the resin, and the mixture was stirred and mixed by swelling.

Adhesive B according to the present invention was obtained.

Adhesive performance evaluation tests were conducted using the obtained adhesives A and B. First, a tensile shear test was conducted. Si'cc mild steel plate (25X100) previously degreased with thinner and petroleum benzene
X0.8. 'fi) is prepared, and the thickness of the adhesive layer is 0.2 from the longitudinal end of the steel plate to about 10 fins.
Adhesives A and B were each applied so as to give 5 fi. Next, these steel plates were alternately stacked and adhered so that the adhesive-coated parts overlapped in the longitudinal direction and the non-adhesive-coated parts did not face each other, and a test specimen was obtained. These sample pieces were subjected to a tensile shear test in a 20°C atmosphere. The results obtained are shown in Table 5.

Next, a corrosion resistance test was conducted using a salt spray test. A mixture of adhesives A and B was applied to the surface of a 5PCO mild steel plate (70x130x0.8 fi) that had been previously degreased with thinner and petroleum benzene.

The adhesive layer was coated to have a width of 30 m x length of 120 m and a thickness of 0.3 fi to form a test sample piece. These sample pieces were subjected to the same salt spray test as in Example 1.

The results are shown in Table 5.

For comparison, the mountain bark was not fired.

Alternatively, comparative adhesives having the same compositions as the above-mentioned adhesives M and B were prepared, except that the firing temperature of the mountain bark was 200°C and 1200°C, respectively, and the same adhesive performance evaluation test as above was conducted. The results are also shown in Table 3.

As is clear from Table 3, the adhesive according to the present invention has superior corrosion resistance compared to comparative adhesives even when mixed with different compositions. Recognize.

Example 4 In this example, various adhesives were prepared by changing the amount of mountain bark fired at 900° C. added to the two types of adhesive compositions prepared in Example 5.

To 100 parts by weight of the adhesive resin prepared in Example 3, fired mountain skin 4 prepared in Example 3 at a firing temperature of 900° C.: Each of the amounts shown in Table 4 was added and mixed once. The additives used in Example 3 were added to these mixtures and mixed in the same manner as in Example 5 to obtain adhesives C and D according to the present invention. .

Sample pieces similar to those in Example 3 were prepared using the obtained adhesives C and D, and the same adhesive performance evaluation test as in Example 3 was conducted. The results are shown in Table 4.

For comparison, the adhesives C and D described above were used, except that they did not contain fired mountain skin or had an excessive amount of fired mountain skin mixed in.
Prepare a similar adhesive for comparison.

A similar adhesive performance evaluation test was conducted. (Sample number 01
0~Cl2).

The results are also shown in Table 4.

As is clear from Table 4, the adhesive according to the present invention has superior layer corrosion resistance compared to the comparative adhesive even if the amount of calcined mountain bark added changes. r To have - is understood.

Example 5 First, 60 parts by weight of urea and 200 parts by weight of 30% Ho/1 Thumarin were mixed, the mixture was neutralized to pH 7 with sodium hydroxide, the mixture was heated and boiled, and the mixture was allowed to flow for 10 minutes. 0.5 parts by weight of formic acid was added to this reaction mixture.

The mixture was heated and boiled again for 2 hours to obtain an adhesive resin.

In addition, as the burned mountain skin, attabulgite powder having a particle size of 100 mesh or less was heated in Example 1 at the temperature shown in Table 5.
A similar firing process was prepared.

Next, 10 parts by weight of the calcined mountain bark was added to the adhesive resin based on 100 parts by weight of urea, and the calcined mountain bark powder was uniformly heated with a heated roller at 30°C until the particle size became 0.2 um or less. ′ was dispersed and mixed.

Further, to this mixture, 1.5 parts by weight of ammonium sulfate and furfuryl alcohol/v3 were added to 100 parts by weight of urea.
0 parts by weight of walnut shell powder and 10 parts by weight of walnut shell powder were added thereto, and mixed and crushed for 3 hours to avoid crushing damage, to obtain an adhesive according to the present invention.

A test piece similar to that in Example 1 was prepared using the obtained adhesive, and an adhesive performance evaluation test was conducted in the same manner as in Example 1. The results are shown in Table 5.

For comparison, unburned mountain bark was used. Alternatively, comparative adhesives having the same compositions as those described above except that the firing temperatures were 200° C. and 1200° C. were prepared, and similar adhesive performance evaluation tests were conducted. The results are also shown in Table 5.

As is clear from Table 5 of Shinoko, the adhesive according to the present invention has superior corrosion resistance compared to the comparative adhesive.

Example 6゜The adhesive resin prepared in Example 5 was added with 1 urea in the resin.
The firing temperature prepared in Example 5 was 900 parts by weight.
Add the calcined mountain bark powder at the temperature shown in Table 6 to the temperature shown in Table 6, and heat it with a heated roller at 30°C until the grain size of the calcined mountain bark is Q, 21i on the grain gauge.
The mixture was dispersed and mixed until it became less than m.

Next, add the additives used in Example 5 to this mixture,
By mixing in the same manner as in Example 5, an adhesive according to the present invention was obtained.

A test piece similar to that in Example 5 was prepared using the obtained adhesive, and the same adhesive performance evaluation test as in Example 5 was conducted. The results are shown in Table 6.

For comparison, we prepared comparative adhesives with the same composition as above, except that they did not contain fired mountain bark or had an excessive amount of fired mountain bark mixed in, and conducted similar adhesive performance evaluation tests. (Sample numbers 016-018).

The results are also shown in Table 6.

As is clear from Table 6, it can be seen that the adhesive according to the present invention has superior corrosion resistance compared to the comparative adhesive even if the amount of calcined mountain bark added changes. .

Claims (2)

[Claims] (1) 0 parts of baked mountain bark per 100 parts by weight of adhesive resin
．． An anticorrosion adhesive characterized by containing 5 to 30 parts by weight. (2) Calcined mountain bark includes sepiolite, attabulgite,
The anticorrosive adhesive according to claim (1), which is a material obtained by heat-treating a powder of a fibrous hydrated magnesium silicate clay mineral such as palygorskite in a temperature range of 400 to 1100°C.