JPS6116915A - Composition curable in water - Google Patents

Abstract

PURPOSE:To obtain the titled composition having controllable viscosity and curability and excellent handleability, and capable of accepting a large amount of cement, by using a (meth)acrylic acid ester in combination with an unsaturated isocyanate. CONSTITUTION:The objective composition can be produced by compounding (A) an unsaturated isocyanate [preferably a compound synthesized by the addition reaction of a polyvalent isocyanate compound with an unsaturated monoalcohol containing (meth)acryloyl group] and (B) a (meth)acrylic acid ester [preferably mono-(meth)acrylate] at a weight ratio of preferably (50-80):(20-50), mixing (C) preferably 50-350pts. of cement to 100pts. of A+B, and compounding (D) 0.5-5pts., based on 100pts. of the component A, of an organic peroxide (e.g. cumene hydroperoxide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-curable composition that cures in water and that adheres extremely strongly to a desired substrate surface, even in water or under wet conditions.

Work in civil engineering, architecture, and waterproofing, such as tunnel construction, floor lining, wall protection, etc., generally involves work that is wet or, in extreme cases, requires painting or gluing underwater. Since there are many conditions, an underwater curable composition that can be used even under such conditions is desired.

Conventionally, this type of underwater curable composition has mainly been cured with a polyamide resin synthesized by condensation of an aliphatic diamine having an aromatic structure (for example, xylylene diamine) and dimer acid, which is called an underwater curable type. Epoxy resins used as agents are commonly used.

However, this epoxy resin does not necessarily have sufficient adhesion to the substrate, depending on the usage conditions, and cannot be said to be reliable. In addition, this epoxy resin is suitable for civil engineering,
When used in fields such as architecture, it has the disadvantage of being relatively expensive.

The present inventors have conducted various studies on compositions that can be cured in water, are inexpensive, can be cured not only on wet surfaces, but also in water, and can adhere extremely well to substrates. A composition consisting of 1) an unsaturated isocyanate, (2) a cement, and (3) an organic peroxide has been found to be effective and has already been proposed.

However, the unsaturated isocyanate used in this composition has a relatively high viscosity of several tens to hundreds of f.
Not only does it have some difficulties in handling, but there is a limit to the amount of cement that can be mixed in (up to 200 parts by weight per 100 parts by weight of unsaturated isocyanate), and the form of the composition is
There is also a risk that it will be limited to a te-like shape. Additionally, this composition has the disadvantage of short shelf life.

From this point of view, the present inventors further investigated and found that the above-mentioned drawbacks can be overcome by using an unsaturated isocyanate and (meth)acrylic acid ester in combination, and have completed the present invention.

(4) The effect of using a water-curable composition composed of an organic peroxide is extremely remarkable. That is, (a) the viscosity and curing properties of the composition can be freely controlled, and it is easy to handle; ←) the amount of cement mixed in increases, and the cement
It has the advantages of being able to mix up to 0 parts by weight, and being able to do the following.

The unsaturated isocyanate used in the present invention is
One molecule contains (meth)acryloyl groups in an amount of 0.1 equivalent or more, preferably 0.5 equivalent or more and 1.8 equivalents or less, and an isocyanate group in an amount of 0.1 equivalent or more, preferably 0.5 equivalent or more.
8 foil amount or less.

When oligoacrylates containing isocyanate groups are used, the curability and adhesion are insufficient and are not suitable.

Various types of unsaturated isocyanates are known, but from a practical standpoint, those synthesized by addition reaction between an unsaturated monoalcohol containing a (meth)acryloyl group and a polyvalent isocyanate compound are used. It is preferable to do so.

As the polyvalent isocyanate compound, for example, 2.4-
) lylene diisocyanate, 2.6-) lylene diisocyanate), 2.4-) lylene diisocyanate and 2.
6-) mixture with lylene diisocyanate, diphenylmethane diisocyanate), 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate,
Examples include hexamethylene diisocyanate and polyisocyanate synthesized from novolak.

Examples of the unsaturated monoalcohol containing a (meth)acryloyl group include 2-hydroxyethyl acrylate, 2
-hydroxyzorobyl acrylate, trimethylolzoropane acrylate), 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, trimethylolzoroi4 dimethacrylate, and the like. The reaction ratio of the polyvalent isocyanate compound and the unsaturated monoalcohol containing a (meth)acryloyl group is 0.1 to 1 mol of the unsaturated monoalcohol containing a (meth)acryloyl group to 1 mole of the polyvalent isocyanate compound. .9 mol, preferably within the range of 0.5 to 1.5 mol.

Synthesis of unsaturated isocyanates is carried out by adding dropwise an unsaturated monoalcohol containing a (meth)acryloyl group to a monomer [(meth)acrylic acid ester] or a polyvalent isocyanate compound dissolved in a solvent. The reaction method is convenient, and in this case, it is advantageous to use a urethanization catalyst such as a tertiary amine or an organic compound of tin.

The (meth)acrylates used in the present invention include mono-, di-, and tri-methacrylates, but from a practical standpoint including cost, mono(
Meta)acrylates are useful. However, it is extremely useful to use di- and tri-(meth)acrylates in combination when the number of (meth)acryloyl groups in the unsaturated isocyanate is small.

Specific examples of (meth)acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate) , 1.6-hexanediol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, glycerin triacrylate, methyl methacrylate, ethyl methacrylate, isozorobyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-
Ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, phenoxydiethyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate , 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, and the like. These (meth)acrylic esters are vinyl ester resins, oligopolyesters (
It is also possible to use it in combination with meth)acrylate and the like.

The (meth)acrylic esters may be added in advance during the synthesis of the unsaturated isocyanate, or may be blended after the unsaturated isocyanate is synthesized.

The mixing ratio of unsaturated isocyanate and (meth)acrylic ester varies depending on the required viscosity and physical properties of the cured resin, but it is usually 20 to 95% by weight of unsaturated isocyanate and 5% by weight of (meth)acrylic ester. 80 parts by weight, preferably 50 to 80 parts by weight of unsaturated isocyanates and 20 to 50 parts by weight of (meth)acrylic esters.

If the mixing ratio of (meth)acrylic esters is less than 5% by weight, there is little point in adding it; if it is more than 80% by weight, the concentration of isocyanate groups decreases, resulting in poor adhesion and slow curing. That's it.

The cement used in the present invention is necessary for accelerating hardening in water or under wet conditions, especially in water, and for developing hardness of the cured product, and cement is used in combination with unsaturated isocyanates and (meth)acrylic esters. Only then can reliable adhesion be achieved in water or under wet conditions.

As the cement, a commonly available commercially available type called Portland cement or alumina cement is sufficient, although white cement can also be used.

Cement may be used in combination with fillers that are known to react with cement, such as fly ash, fine silica powder, and the like.

The blending ratio of unsaturated isocyanate, (meth)acrylic ester, and cement varies depending on the purpose of use, so it cannot be determined unconditionally, but in general, a mixture of unsaturated isocyanate and (meth)acrylic ester is 100%.
It is appropriate to use 10 to 500 parts by weight, preferably 50 to 350 parts by weight, based on the weight of cement. If the blending amount of cement is less than 10 parts by weight, it will take a long time to remove water and the physical properties will not develop quickly. On the other hand, if the blending amount of cement is more than 500 parts by weight, it will be difficult to form a uniform putty (9) depending on the type of unsaturated isocyanate, which will cause problems in workability.

In the present invention, an organic peroxide is used to harden the unsaturated isocyanate, but if the hardness is insufficient, it takes a long time to develop the final hardness, which considerably impairs practicality.

The organic peroxides used in the present invention include cumene hydroperoxide, t-butylhydro i4-
Hydroperoxides such as oxide, acyl peroxides such as benzoyl peroxide, lauroyl peroxide, 2,5-dichlorobenzoyl gloss oxide, methyl ethyl ketone, etc. - oxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, and other ketone peroxides.

These organic peroxides exhibit sufficient curing action even when used alone, but in order to further accelerate curing, organic peroxides, especially ketone peroxides and hydroperoxides, are recommended. When using these, it is preferable to use these together with a curing accelerator such as an organic acid salt of cobalt or acetylacetonate of vanadium. The amount of curing accelerator used is about 0.1 to 5 parts by weight per 100 parts by weight of unsaturated isocyanate.

The amount of organic peroxide blended is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the unsaturated isocyanate. If the amount of organic peroxide is less than 0.1 part by weight, curing will not be sufficient and only a soft product will be obtained.

On the other hand, if the amount of organic peroxide added is more than 10 parts by weight, no effect can be observed by increasing the amount, but rather disadvantages arise such as shortened storage life and increased cost.

The water-curable composition of the present invention is prepared by uniformly mixing an unsaturated isocyanate, (meth)acrylates, cement and an organic peroxide;
There is no particular restriction on the order of addition of each component. When an organic peroxide is used together with a curing accelerator, the curing accelerator may be blended with the unsaturated isocyanate in advance.

The underwater curable composition of the present invention may contain reinforcing materials, colorants, and other additives as necessary.

The compositions of the present invention can be applied to substrates in water or under wet conditions by means such as lining, spraying or roll coating, casting, and glazing, but it will be understood that the compositions can be applied in water or under wet conditions. It is also possible to apply the coating to a wet substrate, ie, a dry substrate, by the same means as described above, and then cure it while immersed in water.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Synthesis of unsaturated isocyananite (A) 21 separable flasks K equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser, a lJL/diisocyanate mixture (2,4 bodies, 80 parts by weight).

2.6 bodies (20 weight ratio), 348 g (2 mol), methyl methacrylate 220 g, dibutyltin dilaurate 0.
8g of rose benzoquinone and 0.1g of rosebenzoquinone were added and stirred. li
' (3 mol) was added dropwise.

Immediately after the dropwise addition was started, the temperature started to rise, and when it reached 60°C, it was cooled, and the temperature was maintained at 60°C until the dropping was completed.

When the reaction was continued for 1 hour after the completion of the dropwise addition, as a result of infrared analysis,
It was determined that free hydroxyl groups had disappeared. In addition, it is recognized that the amount of isocyanate groups has decreased to about 174, which is the original amount, and the following (a).

Unsaturated isocyanate (4) considered to be a mixture of (b)
) methyl methacrylate solution (methyl methacrylate content: 22:1) was obtained. The product was light yellowish brown in color and had a viscosity of 2.9 poise.

(a) (b) Add 300 parts by weight of Portland cement and 1 part by weight of cobalt naphthenate to 10 parts by weight of a solution of unsaturated isocyanate (A) (methyl methacrylate), and mix well to form a paste. , 3 parts by weight of cumene hydroperoxide were added, and the mixture was further kneaded.

The resulting composition was immersed in 3 liters of saline solution, 150 x 25
■ A steel plate with a thickness of 3 to 5++ m was glued to a thickness of 3 to 5++ m on the 12 m+ edge of a somewhat rusted steel plate.

This was similarly immersed in 3-chloride salt water and 7'C150 yang x
Glue to polished steel plate e12■ of 25 fights x 311 II,
A test piece was created by pressing, and was left to harden in water.

The pot life of the composition in air was about 24 hours, and the pot life in water was about 3 hours.

The test piece in water was hardened after 5 hours, hardened after standing overnight, and could not be peeled off from the steel plate without damaging the hardened product.

In addition, the tensile shear strength of steel plate to steel plate is 91 to 14, 7
kg/cm2, the composition of the present invention exhibited sufficient performance as an adhesive.

Example 2 Synthesis of unsaturated isocyanate (B) 333 g (1.5 mol) of isophorone diisocyanate, 155 g of phenoxyethyl acrylate, and dibutyl were placed in 11 separable flasks equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser. Tin dilaurate 0.6 j
j, weigh out 0.1 g of rose benzoquinone, and add 2-
312 g (2.4 moles) of hydroxyethyl methacrylate was added dropwise.

After the dropwise addition, the temperature gradually rose, and when it reached 60°C, it was cooled. When heated and stirred at 60° C. for 3 hours, infrared analysis revealed that free hydroxyl groups disappeared and isocyanate groups remained.

The obtained unsaturated isocyaner) (B) phenoxyethyl acrylate solution (phenoxyethyl acrylate content: about 20% by weight) was pale yellow in color and had a viscosity of 4.7.
i? It was Is.

Unsaturated Isocyaner) To 100 parts by weight of the phenoxyethyl acrylate solution of (B), 150 parts by weight of white cement, 3 parts by weight of nozocymentane hydroperoxide, and 10% acidic butyl phosphate solution of vanadium acetylacetonate (2,4 parts by weight) % vanadium) was mixed therein.

150 x 25 tubes soaked in water with the resulting composition
After attaching it to the end 12wn of the slate board of 1+II++×6 tone, another slate board of the same size is crimped and tightened.
It was left in water for 4 hours. After taking it out and drying it at room temperature for a day and a night, we measured the adhesive strength, and found that the slate plate broke at around 30 kg/crn2, and further measurements could not be made.
The strength of the adhesive part exceeded that of slate.

Example 3 Synthesis of unsaturated isocyaner (C) In 11 separable flasks equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser, 250 g (1 mol) of diphenylmethane diisocyaner and 15° of triethylene glycol dimethacrylate were added. 11 dibutyltin dilaure) 0.6 g, benzoquino y 0.069 e, t) limethylolzolo i 47 diacrylate (containing a small amount of mono- and triacrylate) '220.9 (equivalent to 0.8 mol) were added dropwise.

Since the temperature rose with the dropping, it was cooled when the temperature reached 60°C, and thereafter maintained at 60°C until the dropping was completed.

After reacting at 60°C for 3 hours, it was determined that free hydroxyl groups had disappeared as a result of infrared analysis, and a triethylene glycol dimethacrylate solution of unsaturated isocyanate (C) (triethylene glycol dimethacrylate content: approx. 24
% by weight) was obtained with a light reddish brown color and a viscosity of 9.5 poise.

250 parts by weight of alumina cement and 2 parts by weight of benzoyl peroxide (base) (50% benzoyl peroxide) were mixed and kneaded with 100 parts by weight of a triethylene glycol dimethacrylate solution of unsaturated isocyanate (c). , a putty-like composition was obtained.

The resulting composition was puttyed over the entire surface of a bent steel plate (mouth-shaped, height 5 crns, width 10 crns) wet with water, and then immediately poured into a factory drainage outlet (water flow rate approximately 10 m/min).
I placed it inside.

When the putty on the bent steel plate was observed after being left in a factory drainage outlet overnight, no matrix had flowed out, and the putty had become extremely hard. In addition, the adhesion between the steel plate and the gutte was also good.

In addition, the surface was polished to a smooth surface, and it weighed more than 50 kg and 7 cm when tested with an Elcometer.

Claims (4)

[Claims] (1) unsaturated isocyanate, (2) (meth)acrylic esters, (3) cement, and (4) Organic peroxide A water-curable composition consisting of: