JPS6164717A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition having a long pot life, excellent workability and improved adhesive strength, by mixing a synthetic resin emulsion with an unsaturated isocyanate and a peroxide. CONSTITUTION:A curable composition comprising a synthetic resin emulsion, an unsaturated isocyanate having 1 equivalent or below of isocyanato groups and 1 equivalent or above of acryloyl or methacryloyl groups in the molecule and a perioxide. A preferable synthetic resin emulsion is an emulsion of a polymer having functional groups reactive with the isocyanato groups of the unsaturated isocyanate or an emulsion containing PVA or the like as a protective colloid. Said unsaturated isocyanate serves to enhance the adhesive strength of the composition and improve the water and heat resistances of a film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a synthetic resin emulsion that can be cured at room temperature and has a long pot life.
The present invention relates to a curable composition that has excellent workability and improved adhesive strength.

Currently, known methods for forming a film from a synthetic resin emulsion and curing it include a method in which a polyvalent isocyanate compound is added to a synthetic resin emulsion, a method in which a polyvalent aziridine compound is added to a synthetic resin emulsion, and the like. However, the method of adding a polyvalent isocyanate compound to a synthetic resin emulsion has the disadvantage that the pot life of the synthetic resin emulsion is short, while the method of adding a polyvalent aziridine compound to a synthetic resin emulsion has the disadvantage that
It has the disadvantage of being relatively expensive.

The ability to cure adhesives and the like made of synthetic resin emulsions at room temperature and improve their physical properties without significantly increasing costs would be extremely useful for expanding the uses of synthetic resin emulsions.

As a result of intensive studies in view of the above-mentioned circumstances, the present inventors have found that a composition containing unsaturated isocyanate and peroxide in a synthetic resin emulsion cures the film of the synthetic resin emulsion at room temperature. The present inventors have discovered that the adhesive material can be used at a low cost, has a long shelf life, is easy to work with, has improved adhesive strength, and has completed the present invention.

That is, the present invention provides (1) a synthetic resin emulsion, (2) an unsaturated isocyanate containing 1 equivalent or less of an isocyanate group and 1 equivalent or more of an acryloyl group or a methacryloyl group in one molecule, and (3) a synthetic resin emulsion. The present invention relates to a curable composition comprising an oxide.

As the synthetic resin emulsion used in the present invention, various synthetic resin emulsions can be used, and there are no particular restrictions on the heptamers that constitute the polymer component, such as ethylene, vinyl acetate, vinyl glopionate, Methacrylic acid esters such as methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid 2
- Acrylic acid esters such as ethylhexyl, acrylonitrile, styrene, chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, acrylamide, methylolacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxyethyl acrylate, 2-hydroxymethacrylate, acrylic acid, methacrylic acid, itaconic acid, etc. 75;

In the present invention, among the synthetic tree emulsions containing the above-mentioned monomers as 4 remer components, functional groups reactive with the isocyanate group of unsaturated oleisocyanate,
For example, emulsions of polymers having functional groups such as hydroxyl groups, cardexyl groups, acid amide groups, etc., emulsions using polyhydric alcohols, water-soluble cellulose esters, etc. as protective colloids are preferred.

The unsaturated isocyanate used in the present invention is 1
It contains 1 equivalent or less of isocyanate group and 1 equivalent or more of acryloyl group or methacryloyl group [hereinafter abbreviated as (meth)acryloyl group] in the molecule, and one example is the one shown by the following formula. be able to.

In the present invention, the unsaturated isocyanate has the role of increasing the adhesive strength of the composition and improving the water resistance and heat resistance of the film.

When using an unsaturated isocyanate containing more than 1 equivalent of isocyanate groups in one molecule, or
When using an unsaturated isocyanate containing less than the equivalent amount of (meth)acryloyl groups, r
This is undesirable because it tends to become distorted.

Various types of unsaturated isocyanates 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 the unsaturated monoalcohol containing a (meth)acryloyl group include 2-hydroxyethyl acrylate, 2
-Hydroxyprogyl acrylate, trimethylolzoronognoacrylate, 2-hydroxyethylmethac! J shih, 2-hi)'.

Examples include xyzolol methacrylate and trimethylolglopannomethacrylate.

As the polyvalent isocyanate compound, for example, 2.4-
) lylene diisocyanate, 2.6-lylene diisocyanate), 2.4-) lylene diisocyanate and 2.6
- mixtures with trile/noisocyanate, diphenylmethane noisocyanate, 1,5-naphthylene diisocyanate, nograf phenylene diisocyanate, xylylene diinoisocyanate, inholone noisocyanate),
Examples include 1,6-hexamethylene diisocyanate and hydrogenated xylylene diisocyanate.

The unsaturated isocyanate used in the present invention contains 1 to 1.8 mol, preferably 1 to 1.4 mol, of an unsaturated monoalcohol containing a (meth)acryloyl group per 1 mol of the polyvalent isocyanate compound. It is produced by reacting within the range of

Unsaturated innoanates can be synthesized in monomers such as acrylic esters and methacrylic esters, in solvents such as ethyl acetate, methyl ethyl ketone, or dioxane, or in dibutyl phthalate 1. A method of adding dropwise an unsaturated monoalcohol containing an acryloyl group to a polyvalent isocyanate compound in a plasticizer such as nooctyl phthalate or diethyl acrylate phthalate can be used as it is in a monomer solution, a solvent solution, or Although it is convenient because it can be used as a plasticizer solution, a polyvalent isocyanate compound and an unsaturated monoalcohol having a (meth)acryloyl group may be reacted without using a monomer, a solvent, or a plasticizer.

In this case, it is preferable to use a urethanization catalyst such as a tertiary amine or an organic compound of tin.

In the unsaturated isocyanate used in the present invention, the isocyanate group and the (meth)acryloyl group do not necessarily have to be equimolar. For example, polyvalent isocyanate 1
1 obtained by the reaction of 1 to 1.8 mol of an unsaturated monoalcohol having a (meth)acryloyl group.
Any compound containing 1 equivalent or less of isocyanate group and 1 equivalent or more of (meth)acryloyl group in the molecule may be used. For example, using 2-hydroxyethyl methacrylate as an unsaturated monoalcohol having a (meth)acryloyl group,
For example, when a reaction is carried out using 2,4-tolylene diinocyanate as a multi-sided isocyanate compound, a mixture of monoacrylate and diacrylate with defects is produced. Mixtures may also be used.

(a) Monoacrylate■-C-0-CH2-CH2-0-CneyC-CH2←
) Diacrylate Unsaturated isocyanate mixtures containing diacrylates as described above have the advantage of increasing the curing speed of the film formed from synthetic resin emulsion and improving the physical properties of the cured film. Instead, the free isocyanate groups are protected and the isocyanate groups and synthetic resin emulsion ()! This has the advantage of increasing the reaction with the polymers that make up the polymer.

The amount of unsaturated isocyanate to be added varies depending on the purpose of use of the composition, so it cannot be determined unconditionally, but it is generally 5 to 200 parts by weight per 100 parts by weight of the solid content (resin content) of the synthetic resin emulsion exchanger. , preferably within the range of 20 to 150 parts by weight. If the amount of unsaturated isocyanate blended is less than 5 parts by weight, the effect of addition is small, and if the blended amount of unsaturated isocyanate is more than 200 parts by weight, the effect of increasing the amount is no longer observed.

Peroxides used in the present invention include, apart from hydrogen peroxide, methyl ethyl ketone and monooxide, cyclohexanone noso oxide, ketone nog-oxyPs such as methyl isobutyl ketone/IP-oquindo, and cumene hydrochloride. No J? -hydrono-P-oxides such as t-butylhydrono and monooxide, 74-hydrono-P-oxides such as L-butylhydrono-oxy-2-ethylhexoate,
Examples include organic peroxides such as oxyesters, acyl groups such as benzoyl peroxide, lauroyl/4'-oxide, and 2,5-nochloropenzoyl peroxide.

These peroxides exhibit a sufficient curing effect even when used alone; for example, acyl peroxides (benzoyl peroxide) are used as polyvalent isocyanates to form aromatic isocyanates during the synthesis of unsaturated isocyanates. When using a curing accelerator, the curing is relatively quick even without using a curing accelerator, but in order to further accelerate curing, it is preferable to use an organic peroxide and a curing accelerator together. For example, when using an organic peroxide, especially a hydroperoxide (Kiemen hydro A-oxide) as the organic peroxide, if it is used in combination with a curing accelerator of cobalt naphthenate, curing will be accelerated. It has a long pot life and is convenient to use.

The amount of peroxide to be blended is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total solid content (resin content) of the synthetic resin emulsion and unsaturated isocyanate. Within this range is appropriate. The amount of peroxide added is 0.1
If the amount is less than 10 parts by weight, the curing properties at room temperature will be insufficient. On the other hand, if the amount of peroxide is more than 10 parts by weight, there will be no effect of increasing the amount, and the cost will be high. This has the disadvantage of causing a decrease in the physical properties of the cured product.

When a curing accelerator is used in combination with a peroxide, the amount of curing accelerator used is 0.00 parts by weight per 100 parts by weight of the total solid content (resin content) of the synthetic resin emulsion and unsaturated isocyanate.
It is desirable that the amount is 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight.

The curable composition of the present invention is prepared by uniformly mixing a synthetic resin emulsion, an unsaturated isocyanate, and a peroxide, and there is no particular restriction on the order of addition of each component. When a peroxide is used in combination with a curing accelerator, the curing accelerator may be blended with the unsaturated isocyanate in advance.

The composition of the present invention hardly cures while moisture is present, and cures only after moisture is removed by dehydration or evaporation.

It has a long triso and has good workability.It also increases the hardness of the film formed from the synthetic resin emulsion, improves solvent resistance and creep resistance, and has extremely excellent adhesion to the substrate. Therefore, it is useful as paints and adhesives.

The composition of the present invention is cured by grafting the unsaturated isocyanate to the 4-limer constituting the synthetic resin emulsion using the isocyanate group in the unsaturated isocyanate, and crosslinking the polymers with each other using the (meth)acryloyl group. .

The curable composition of the present invention optionally includes polymers,
Fillers, colorants, and other additives may be added.

The curable composition of the present invention can be applied by means such as lining the substrate, spraying, and coating with a roll, but in actual use, it is preferably coated with a lining on the substrate.

Naturally, peroxide is added to the synthetic resin emulsion, a curing accelerator is added to the unsaturated isocyanate as required, and each of these components is painted using a double-headed spray gun. good.

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

Example 1 Synthesis of unsaturated isocyanate prisoner A 11-liter chamber equipped with a stirrer, a thermometer with a gas inlet tube, a dropping funnel, and a reflux condenser. In the rubble flask, 2.4
-) Lylene isocyanate 174y- (1 mol) was charged, and at 60°C in dry air, 2-hydroxyglobil methacrylate 173? (1.2 mol, 0.3? of diptyltinnolaurate, containing 0.071 of penzoquinone) was added dropwise.

Since the temperature rose with the dropping, it was cooled and kept at around 60°C.

When the temperature was kept at 60°C for 2 hours after the dropping, infrared analysis showed that
It was determined that free hydroxyl groups had disappeared. Next, ethyl acetate was added to give a light yellowish brown color and a viscosity of about 10.
A solution of Poise's unsaturated isocyanate (6) in ethyl acetate was obtained.

The obtained unsaturated isocyanate prison contained 0.8 equivalents of isocyanate groups and 1.2 equivalents of methacryloyl groups.

Polyacetic acid containing polyester, = 79 air yone (manufactured by Showa Kobunshi Co., Ltd., Polysol + 1200)
, viscosity (50% by weight DOP paste) was added, and the mixture was uniformly stirred and mixed to obtain a polyvinyl acetate emulsion (a).

To 200 parts by weight of polyvinyl acetate emulsion/(a), 1100 parts by weight of an ethyl acetate solution of the unsaturated isocyanate (4) was mixed with stirring. No foaming was observed, and after one night, the ends and surface of the mixture, where water had evaporated and turned into solid matter, were glued, but the internal water-containing portion remained fluid. In the adhesion test using oak wood, the normal compressive shearing force was 250 kg/art2, and the compressive shearing force after the water resistance test was 177 kg/crn2.

-10,000, if unsaturated isocyanate (4) is not used,
The normal compressive shear force was 230 kg/crIL2, and the compressive shear force after the water resistance test was 144 kg/cIrL2.

Example 2 Synthesis of unsaturated inholone isocyanate (B) 22:l (1 mol) of inholone isocyanate (B) was added to 11 seven-piece crabble flasks equipped with a stirrer, a thermometer with a gas inlet tube, a dropping funnel, and a reflux condenser. Preparation,
0.4 y- diptyltin dilaurate at 60°C, 0.
04? 2-Hydroxyethyl acrylate 152i containing Nono and Rapenzoquinone! -(1.4 mol) was added dropwise.

The temperature was maintained at 60° C., and after the completion of the dropwise addition, the reaction was allowed to continue at the same temperature for 3 hours. As a result of infrared analysis, it was determined that free hydroxyl groups had disappeared.

It was light yellowish brown in color, had a viscosity of about 180 poise, and contained 1.4 equivalents of unsaturated insilyloyl groups.

Ethylene-vinyl acetate copolymer resin emulsion containing I-vinyl alcohol (manufactured by Showa Kobunshi Co., Ltd., EVA
AD-3, viscosity 30 poi, e, pH 3.0, Fill
FT 0°C, solid content 50% by weight) and 100 parts by weight of Cumen Hydrono J? -3 parts by weight of oxide and 3 parts by weight of water were added and mixed uniformly with stirring to obtain ethylene-vinyl acetate copolymer resin Emulnoyon (b).

Ethylene-hinyl acetate copolymerization fat emulsion (b)
103 parts by weight of unsaturated isocyanate (
B) 50 parts by weight and 1 part by weight of cobalt naphthenate (6 Ticobalt) were added and stirred until a homogeneous solution was obtained.

The obtained composition was applied to the end portion of a slate board measuring 150+m x 25m x 6m, and the slate boards of the same size were overlapped only at the 13th part and crimped with a load of 170mm.

After standing overnight, the adhesive strength by tensile shearing was measured, and the slate body broke at 43 kg/CWL2, and the strength of the adhesive portion exceeded the strength of the slate board. In addition, after immersed in water for 24 hours, 43 kli/ctn
2 or more, the slate broke.

On the other hand, in the case of using ethyl-vinyl acetate copolymer resin (B) alone without using unsaturated isocyanate (B), slate fracture did not occur at 20 kg/12 or less after being immersed in water for 24 hours. Ta.

Patent applicant: Showa Kobunshi Co., Ltd. Representative Patent Attorney Kiku Ji Sei - Procedural Amendment 70th a3, 1982

Claims (3)

[Claims] (1) Synthetic resin emulsion, (2) unsaturated isocyanate containing 1 equivalent or less of isocyanate group and 1 equivalent or more of acryloyl group or methacryloyl group in one molecule, and (3) Peroxide A curable composition consisting of: