JPS6117459A - Underwater curable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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.

In fields such as civil engineering, architecture, and waterproofing, such as tunnel construction, floor lining, and wall protection, work conditions generally involve being wet with water or, in extreme cases, having to be painted or glued underwater. Therefore, there is a desire for an underwater curable composition that can be used even under such conditions. .

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 always have sufficient adhesion to the substrate, depending on the usage conditions, and cannot be said to be reliable. Furthermore, this epoxy resin has the disadvantage that it is relatively expensive to use in fields such as civil engineering and architecture.

The present inventors have developed various compositions for the purpose of obtaining a composition that is low in cost, can be cured not only on a wet surface, but also in water, and can be cured in water, and which adheres extremely well to a substrate. As a result of the investigation, (1) unsaturated isocyanate
We have discovered that a composition consisting of 1 to (2) cement and (3) organic peroxide can achieve the above objects very effectively, and have completed the present invention.

The unsaturated isocyanate used in the present invention is -
The molecule contains one or more acryloyl or methacryloyl groups (hereinafter abbreviated as (meth)cri[1-yl group]) and 0.1 to 1.8 isocyanate groups.

When oligoacrylates containing no isocyanate groups are used, the curability and adhesion are not sufficient and it is not suitable.

Various types of unsaturated isocyanate-1 are known, but from a practical standpoint, those synthesized by an addition reaction between an unsaturated monoalcohol containing a (meth)acryloyl group and a polyvalent isocyanate compound are preferred. It is preferable to use

Examples of polyvalent isocyanate compounds include 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2.6-tolylene diisocyanate.
Synthesized from a mixture with 1-lylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, novolak Examples include polyisocyanates.

Examples of the unsaturated monoalcohol containing a (meth)acryloyl group include 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, trimedylolpropane diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, trimethylolpropane dimethacrylate, and the like.

The reaction ratio of the polyvalent isocyanate compound and the unsaturated monoalcohol containing the (meth)acryloyl group is 0.1 to 1 mol of the polyvalent isocyanate compound and the unsaturated monoalcohol containing the (meth)acryloyl group. .9 mol, preferably within the range of 0.5 to 1.5 mol.

For the synthesis of unsaturated isocyanates, it is convenient to add an unsaturated monoalcohol containing a (meth)acryloyl group dropwise to a polyvalent isocyanate compound dissolved in a solvent as needed, and carry out the addition reaction. In this case, it is advantageous to use urethanization catalysts such as tertiary amines and organic compounds of tin.

The cement used in the present invention is necessary for accelerating curing in water or under wet conditions, especially in water, and for expressing Ifi of the cured product, and reliability can only be achieved by using cement and unsaturated isocyanate together. Adhesion in water or under wet conditions F is achieved.

As the cement, a commercially available type commonly called Portland cement or alumina cement is sufficient, but 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 and cement varies depending on the purpose of use, so it cannot be determined unconditionally, but in general, it is preferably 10 to 200 parts by weight of cement to 100 parts by weight of unsaturated isocyanate. 50 to 150 parts by weight is suitable. If the blending amount of cement is less than 10 parts by weight, the effect of the present invention cannot be obtained. On the other hand, if the blending amount of cement is more than 200 parts by weight, a uniform putty-like shape may not be obtained, although it depends on the type of unsaturated isocyanate. It becomes difficult to form, causing problems in workability.

In the present invention, an organic peroxide is used for curing the unsaturated isocyanate, but if this is lacking, it will take a long time to develop the final hardness, and the practicality will be considerably impaired.

Examples of the organic peroxides used in the present invention include hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, and 2,5-dichlorobenzoyl peroxide. Examples thereof include acyl peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and ketone peroxides such as methyl inbutyl ketone peroxide.

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 Q used is unsaturated Sardine-1-101-1
The amount is approximately 0.1 to 5 parts per 0 parts.

The amount of the organic peroxide to be blended is usually 0.1 to 10 parts by weight, preferably 0.5 to 1 part by weight, per 100 parts by weight of the unsaturated isocyanate.

If the amount of organic peroxide blended is less than 0.1 parts by weight, curing will not be performed sufficiently;
If the amount is more than 0 parts by weight, curing will not be promoted, but rather the cured product will show deterioration in physical properties such as becoming brittle.

The water-curable composition of the present invention is prepared by uniformly mixing the unsaturated isocyanate, cement, and organic peroxide, and there is no particular restriction on the order of addition of each component. When using an organic peroxide in combination with a curing accelerator,
A 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 composition of the present invention can be applied to a substrate in water or under wet conditions by means such as lining the substrate, coating by spray or roll, casting, puttying, etc., but it is understood that the composition should not be wetted with water. It is also possible to apply the coating to a substrate, ie, a dry substrate, by the same means as 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 isocyanate (A) Tolylene diisocyanate mixture (80% by weight of 2,4, 2 .6 bodies 20% by weight) 3489 (2 mol) was added, and while stirring, 2-
A solution of 0.7 g of dibutyltin dilaurate and 0.1 g of rosebenzoquinone in 432 g (3 moles) of hydroxypropyl methacrylate was added dropwise.

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

When the reaction continued for 1 hour after the completion of the dropwise addition, as a result of infrared analysis,
Although it was somewhat difficult to determine, residual hydroxyl groups were confirmed, and unsaturated isocyaner 1 (△), which is thought to be a mixture of (a) and (E)) below, was obtained as a light yellowish brown, viscous liquid. Ta.

1-I II 10 CH3 hl Unsaturated isocyanate (Δ>ioo) 100 ffiffi parts of portland cement and 1 part by weight of cobalt naphthenate were blended into a paste. 3 parts by weight of oxide was added and the mixture was further kneaded well.

The resulting composition was immersed in 3% saline solution in a 150m×25
Edge 12I of mX3InM steel plate with some rust
IllII was puttyed to a thickness of 3''-5mm.

To this, 150ma soaked in 3% saline solution like 10j
+X25sX3m polished steel plate was glued to 12m, pressed together to create a test piece, and then hardened in water.
Ta.

The pot life of the composition in air was about 8 hours, and the pot life in water was about 1 hour.

The test piece in water was hardened after 2 hours, hardened after standing overnight, and could not be peeled off from the steel plate without damaging the hardened product.

In addition, the tensile g:J breaking strength of steel plate to steel plate is 73 to 144
was 9/cM, indicating that the composition of the present invention exhibited sufficient performance as an adhesive.

Example 2 Synthesis of unsaturated isocyanate (B) Isophorone diisocyanate 333y (1.5 mol) was charged into an 11-liter separable flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser. ℃
After raising the temperature to , a solution of 0.69 g of dibutyltin dilaurate and 0.1 g of rosebenzoquinone in 312 g (2.4 mol) of 2-hydroxyethyl methacrylate was added dropwise while stirring 1↑.

After the dropwise addition was completed, the reaction was carried out at 60°C for 3 hours, and as a result of infrared analysis, it was confirmed that the free hydroxyl groups had completely disappeared.
Unsaturated isocyanoboo h(B) was obtained in a pale yellow liquid form.

For every 100 parts by weight of unsaturated isocyanate (B), 80 parts by weight of white cement, 3 parts by weight of paramethane hydroperoxide, 0.43 parts by weight of a 10% acidic Nisder butyl butyl phosphate solution (2.4% vanadium) of vanadium acetylacetonate. were mixed.

The obtained composition was immersed in water, 150 mm x 2.
After adhering to the end 12 m of a slate plate of 5 mm and thickness, another slate plate of the same size was pressed and clamped and left in water for 24 hours.

After taking it out of the water and drying it indoors for a day and night, we measured the adhesive strength, and found that the slate broke at around 30 kg/cA, making further measurements impossible, and the strength of the adhesive portion exceeded that of the slate. .

Example 3 Synthesis of unsaturated isocyanate (C) Equipped with a stirrer, dropping funnel, thermometer, and reflux condenser7. -11 separable flask, 250 g (1 mol) of diphenylmethane diisocyanate, 50 g of dioxane
g, and additionally 0.5 g of dibutyltin dilaurate,
0.05 g of benzoquinone was added, and 220 g (equivalent to 0.8 mol) of trimethylolpropane diacrylate-1. (including mono- and triacrylates) was added dropwise.

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

After holding at 60° C. for 3 hours, as a result of infrared analysis, it was determined that free hydroxyl groups had disappeared, and unsaturated isocyanate (C) with remaining isocyanate groups was obtained in the form of a pale reddish brown liquid.

To 100 parts by weight of unsaturated isocyanate (C), 120 parts by weight of alumina cement, benzoyl peroxide paste (5 parts by weight)
2 parts of 0% benzoyl peroxide) were blended and kneaded to obtain a putty-like composition.

This composition was filled with putty in water over the entire surface of a bent steel plate (mouth shape, height 5 cm, width 10 cm) submerged in water. When left in water overnight, the composition hardened and hardened.

When the bent steel plate was taken out of the water, the surface was polished and a tensile adhesion test was performed using an Elcometer, the strength exceeded the strength of the epoxy resin adhesive used and was 50K9.
/c++i or higher.

Claims (3)

[Claims] (1) Unsaturated isocyanate (2) Cement and (3) Organic peroxide A water-curable composition consisting of: