JPS6218464A - Curable composition - Google Patents

Abstract

PURPOSE:To provide a curable compsn. having excellent adhesion to the surface of a substrate wetted with water and suitable for use as paints, putty, etc., by mixing a synthetic resin emulsion, a radical-curable resin compsn, cement and a peroxide. CONSTITUTION:An unsaturated alkyd (A) obtd. by reacting a phenolic resin with an epoxy resin contg. 2-4 epoxy groups per molecule in a ratio of 0.5-1 equivalent of the hydroxyl group per equivalent of the epoxy group and adding an alpha,beta-unsaturated polybasic acid (anhydride) (e.g. maleic anhydride) to carry out an esterification reaction, is mixed with a polymerizable monomer (B) (e.g. styrene) to prepare a radical-curable resin compsn. The resin compsn., a synthetic resin emulsion (e.g. acrylic resin emulsion), cement and a peoxide (e.g. benzoyl peroxide) are mixed together to obtain the desired curable compsn.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides coatings and adhesives that have excellent adhesion and adhesion to the surface of a substrate wet with water or under a wet condition;
In particular, the present invention relates to a curable composition useful for lining, filling, sealing, etc.

[Conventional technology]

Currently, there are epoxy resins, vinyl ester resins, polyurethane resins, etc. as resins used for linings, gutters, sealings, etc., and each of these resins is widely used by taking advantage of its characteristics.

[Problem that the invention seeks to solve]

However, these existing resins do not have good adhesion or adhesion to the base material, such as when painting on a wet base material (for example, concrete) to ensure good adhesion, or when the paint is placed on a beach and then soaked in seawater. The reality is that the performance of these devices is not satisfactory and improvements are required.

As an underwater curable resin, for example, an epoxy resin that uses I-lyamide resin obtained by condensation of xylylene diamine and dimer acid as a curing agent is also known, but this resin actually has no water adhesion. There is a great deal of variation;
It has the disadvantage of poor reliability.

Generally, when applying protective lining to steel structures at work sites, it is often difficult to completely remove rust before painting. Therefore, there are many cases where it is necessary to paint just enough to remove loose rust, and there are cases where sufficient adhesion and rust prevention are required even under such adverse conditions.

[Means for solving problems]

As a result of extensive studies in view of the above-mentioned circumstances, the present inventors have found that (1) a synthetic resin emulsion, (2) a radically polymerizable composition obtained by the following reaction, namely: [ID (4) 1 (B) Reacting an epoxy resin having 2 or more than 2 but not more than 4 epoxy groups in the molecule with phenols such that the amount of hydroxyl groups is 1 to 0.5 equivalents per 1 equivalent of epoxy groups; Next, an unsaturated alkyd obtained by adding and esterifying a (0α-β unsaturated polybasic acid or its acid anhydride) and a radical-curable monomer (hereinafter abbreviated as “monomer”) obtained in combination resin composition (hereinafter referred to as epoxy (EP)
OXY) ~ Phenol ~ Ester (
A curable composition consisting of (3) cement, and (4) peroxide can be coated even under adverse conditions such as the above, and We discovered that it has excellent adhesion and adhesion to the surface of a substrate wet with water or under a wet condition.
The present invention has now been completed.

[Effect]

A method of mixing a synthetic resin emulsion and cement has been known for a long time, but this method takes a long time to cure, and the paint diameter film may come into contact with water in an uncured state, or it may be exposed to high humidity. If placed in an environment of However, it has drawbacks such as slow curing, insufficient adhesion, hair cracks depending on the thickness of the film, and the film no longer serves its purpose.

This drawback is completely solved by the composition of the invention.

Various synthetic resin emulsions can be used as the synthetic resin emulsion used in the present invention.
The monomers constituting the polymer component are not particularly limited, and examples include ethylene, vinyl acetate, vinyl zolopionate, vinyl versatate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate,
Examples include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, octyl methacrylate, nonyl methacrylate, lauryl methacrylate, acrylonitrile, styrene, vinyltoluene, and vinylitadiene chloride.

Emulsification is carried out using conventionally commonly used anionic, nonionic, or cationic surfactants, and there is no need to place any particular restrictions on the emulsification.

The raw materials constituting the EPE resin used in the present invention include:
(a) Epoxy resin, (b) phenols, (c) α-
β-unsaturated polybasic acids or their acid anhydrides include monomers, and commercially available products are available for each.

Epoxy resins include bisphenol A diglycidyl ether type, Nodelac? Examples include the liglycidyl ether type and the so-called peracetic acid type in which the intramolecular double bond is oxidized.
There are commercially available products that are equivalent to each.

Phenols are monovalent phenolic compounds such as phenol, cresols, xylenol, A? Examples include substituted alkylphenols, phenylphenol, nografylphenol, α-naphthol, and β-naphthol.

When reacting an epoxy resin with a phenol, it is necessary to use a reaction catalyst such as a tertiary amine or a quaternary ammonium salt.

The reaction ratio of the epoxy group and the phenolic hydroxyl group is substantially 0.5 or more and 1 equivalent or less of hydroxyl group per equivalent of epoxy group.

Further, as the α-β unsaturated polybasic acid or its acid anhydride,
Mention may be made of maleic anhydride, maleic acid, fumaric acid, itaconic acid, which are sufficient for the purposes of the present invention.

Esterification is generally carried out in accordance with the production of unsaturated polyester resins.

To aid in understanding, the production of EPg resin is shown by the formula 1
Give an example.

This unsaturated alkyd is copolymerizably dissolved in a monomer to obtain an EPE resin.

The hexamers can be selected from the various types mentioned above, but the most common ones are styrene and vinyltoluene.

The ratio of unsaturated alkyd to monomer is 80:20-30
The most suitable range is a monomer amount of 40.
~601st place.

The appropriate amount of EPE resin to be blended is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight of the solid content of the synthetic resin emulsion. EP
If the amount of E-resin is less than 20 parts by weight, the physical properties of the cured coating film will be insufficient, no increase in hardness will be observed, and the solvent resistance will be poor, so it is not preferable. If the amount is higher, the properties of the EPE resin will become stronger,
Not only does it take a long time to harden the coating, but the thixotropy becomes poor and the coating tends to sag.

The cement used in the present invention is necessary for accelerating hardening in water or under wet conditions, particularly in water, and for developing hardness of the cured product. As the cement, a commonly available commercially available type called Portland cement or alumina cement is sufficient, although white cement can also be used.

The amount of cement mixed is 1 solid content of the synthetic resin emulsion.
30 to 300 parts by weight, preferably 5 parts by weight
It is 0 to 200 parts by weight. If the amount of cement added is less than 30 parts by weight, it will not be sufficient to absorb the moisture of the synthetic resin emulsion, and therefore sufficient physical properties of the coating film will not be obtained.
If the amount of cement added is 300 parts by weight or more, either the physical properties will not improve due to the increased amount, or the viscosity will increase, making workability difficult.

In the present invention, peroxide is used to harden the EPE resin, but if peroxide is lacking, it takes a long time to develop final hardness, which considerably impairs practicality.

Examples of peroxides include ketones/4'-oxides such as methyl ethyl ketone oxide, cyclohexanone monooxide, acetylacetone peroxide, ethyl acetoacetate/IP-oxide, and acyl oxides such as lauroyl, monooxide, and benzoyl peroxide. Peroxides, cumene hydroperoxide, t-bufk hydroperoxide, etc. -Organic peroxides such as oxides.

The amount of peroxide added is 1 solid content of the synthetic resin emulsion.
0.5 to 10 parts by weight, preferably 1
~5 parts by weight. If the amount of peroxide is less than 0.5 parts by weight, curing properties at room temperature will be insufficient, while if the amount of peroxide is more than 10 parts by weight, no effect will be observed by increasing the amount. In addition, it has the drawbacks of high cost and deterioration of the physical properties of the cured product.

Peroxide exhibits a sufficient curing effect even when used alone, but in order to further accelerate curing, it is preferable to use peroxide and a curing accelerator together.

Examples of the curing accelerator include cobalt organic acid salts, vanadium acetylacetonate, and dimethylaniline.

The appropriate amount of the curing accelerator is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the EPE resin.

The curable composition of the present invention is a synthetic resin emulsion, EP
It is prepared by uniformly mixing E-resin, cement, peroxide, and a hardening accelerator if necessary, but if all components are mixed at once, the composition will vary depending on the blending ratio of each component. The viscosity may increase within a short period of time.

Such curable compositions are suitable for rapid curing. Although it is useful as a liquid, it is often difficult to spray the liquid.

Therefore, in such a case, (a) (Liquid A), which is a synthetic resin emulsion mixed with cement, is separately added to the EPE resin with a peroxide that has the ability to harden the resin, and if necessary, accelerates hardening. (b) Contrary to the method (a) above, the EPE resin is coated with cement (liquid B) as needed. Mixed with curing accelerator (Liquid A)
and synthetic resin emulsion mixed with peroxide (
It is preferable to adopt a method of simultaneously spraying and painting liquid B) using a double-headed spray gun in the same manner as in (a) above.

The curable composition of the present invention forms a uniform coating film and can provide a non-stick coating and curability within a short period of time, which could not be obtained with a simple mixture of synthetic resin emulsion and cement. It was also found that the physical properties of the coating film were improved compared to the synthetic resin emulsion with cement added.

The curable composition of the present invention may optionally contain other fillers,
Reinforcing materials, coloring agents, radical curing resins such as unsaturated polyester resins and vinyl ester resins, and other additives may be blended.

〔Effect of the invention〕

The curable composition of the present invention cures in water, has excellent adhesion and adhesion to the surface of a desired substrate even in water or in a wet state, and has excellent water resistance and chemical resistance. This makes it a great advantage for paints and adhesives.

〔Example〕

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

Example 1 In an IJ separable flask equipped with a stirrer, a fractionating condenser, a thermometer, and a gas inlet tube, 350 g of DER-330 from Asahi Dow Co., Ltd. as an epoxy resin and 232 g of 3.5-xylenol were added. ! 9 (0 hydroxyl groups per equivalent of epoxy group)
．． 95 equivalents), benzyldimethylamine, and 1.8% F are charged and heated. When the temperature exceeds 110'C, heat generation begins rapidly. Therefore, the temperature should be cooled to prevent the temperature from exceeding 160°C.

After the reaction was then carried out at 150 to 160° C. for 5 hours, it was confirmed by infrared spectroscopy that the free epoxy groups had completely disappeared.

Next, 110 g of fumaric acid was added and esterified at 200 to 210° C. in a nitrogen gas stream, resulting in an acid value of 14.1, so 0.12 ge of hydroquinone was added, and the mixture was poured into a metal vat and solidified.

A dark brown unsaturated alkyd with a melting point of approximately 110-115°C (
4) was obtained.

The average molecular weight was 4,600.

Grind 100 parts of unsaturated alkyd (4) and add 1 part of styrene.
00 parts by heating and dissolving at 60 to 70°C.

An EPE resin (B) with a viscosity of 9.7 poise was obtained.

A system in which 100 parts of EPE resin (B), 2 parts of methyl ethyl ketone peroxide, 1 part of cobalt naphthenate, and 0.2 parts of dimethylaniline were added, glued at room temperature in 49 minutes, generated a gentle heat, and reached a maximum temperature of 133. ℃ reached.

The heat distortion temperature of the cast product was 108°C.

As a cationic acrylic emulsion, 0LX-6185-2 manufactured by Showa Kobunshi Co., Ltd. (solid content 40 cm, viscosity approximately 2.
5 poise, PH4-6, MFT: 6°C) and 170 parts of cement were mixed to form a liquid.

Separately, add methyl ethyl ketone iE to 100 parts of EPE resin.
- 2 parts of oxide, 1 part of cobalt naphthenate added, (b)
It was made into a liquid.

7 kg/c using a double-headed spray gun whose discharge volume was adjusted so that equal volumes of both liquids a and b could be sprayed.
30 cm x 30 cm x 30 cm x 30 cm
A 2 mm steel plate was spray-painted to a thickness of about 0.5 tran.

The coating film became non-adhesive about 5 minutes after spraying and was cured 60 minutes later.

The physical properties of the coating film left for 24 hours were as shown below, and its practicality as a lining was recognized.

Surface hardness 3~4H Paint film adhesion Goban test 100/100 Dolly
Tensile strength due to use When dropping 30 kg or more of acetone, whitening occurs but no stickiness occurs.

Spot Test When the acetone evaporates, the surface returns to its original state.

Example 2 As a bisphenol F type epoxy resin, Epicoat 807 manufactured by Yuka Shell Co., Ltd. was used at 350! i, phenol 179I
(Ratio of epoxy group to phenolic OH 1:0.95)
were weighed into the same apparatus as in Example 1, mixed uniformly at 50°C, and trimethylbenzylammonium chloride 0
．． When 5g is added and the temperature is raised, it rapidly generates heat at 110°C to 130°C and reaches around 160°C, so it is cooled during this time.
Keep below 60℃.

After reacting at 155 to 160° C. for 3 hours, infrared spectroscopic analysis showed that the absorption of epoxy groups completely disappeared.

Next, 90J of maleic anhydride was added and heated to 200-210°C.
When esterified in an inert gas stream, the acid value becomes 2 after 5 hours.
It became 1.4.

Add 0.1 g of hydroquinone, pour into a metal vat, and cool. An unsaturated alkyd (C') having a melting point of about 100° C. and an average molecular weight of about 2,600 was obtained.

100 parts of unsaturated alkyd (C) was crushed, dissolved in 100 parts of para-methylstyrene by heating at 60°C, and cooled to room temperature to form an EPE-resin (D) with a Gardner color number of 2 to 3 and a viscosity of 3.9 poise. Obtained.

A system in which 100 parts of EPE-resin, 2 parts of methyl ethyl ketone peroxy P, 1 part of cobalt naphthenate, and 0.1 part of trimethylaniline were added, calcified in 33 minutes at room temperature, slowly exothermed, and reached a maximum temperature of 144. ℃ reached.

The heat distortion temperature of this casting resin was 98°C.

EVA AD-3 manufactured by Showa Kobunshi Co., Ltd. as an ethylene-vinyl acetate copolymer emulsion (solid content 50% by weight, viscosity approximately 30 poise, pH 2.5-3.5, MFT O'°C)
100 parts by weight (hereinafter referred to as "parts by weight"), 5 parts of water, and 5 parts of cumenohydroboroxide were uniformly mixed to obtain liquid (d).

Separately, 100 parts of EPE-resin 0), 1 part of cobalt naphthenate, and 200 parts of Portland cement were mixed (
,) as a liquid.

When 100 parts of liquid (d) and 250 parts of liquid (,) were mixed and stirred, it immediately became soft and sticky, and after remaining in that state for about 15 minutes, it gradually became hard and hardened after about 2 hours. .

A slate board about 4 inches thick was coated with a bar coater to a thickness of 100 microns, and a tensile test using a dolly of the hardened coating resulted in the surface of the base material being destroyed and a weight of 30 kg.
/ cm or more.

Example 3 1! Equipped with a stirrer, a fractionating condenser, a gas inlet tube, and a thermometer! In a four-bottle flask, 827t-370g of Ebiko (produced by Yuka Shell Co., Ltd.), 195g of para-cresol (ratio of dipoquine group to phenolic hydroxyl group: 1:09), and 1.59g of benzyldimethylamine were added as the resin. When heating the mixture, it rapidly generates heat when the temperature exceeds 110°C, so it is necessary to cool it to prevent it from rising above 160°C.

After the reaction was then carried out at 150 to 160° C. for 5 hours, it was confirmed by infrared spectroscopy that the free epoxy groups had completely disappeared.

Next, add 110 g of fumaric acid and add 200 to 200 g of fumaric acid in an inert atmosphere.
When heated at 10℃ for 6 hours, the acid value is 19.6! : Therefore, 0.13!1 of hydroquinone was added, poured into a metal vat, and solidified.

An unsaturated alkyd with a tan color and a melting point of about 110°C to 115°C was obtained. Average molecular weight was 3200.

Add 100 parts of styrene to 100 parts by weight (hereinafter referred to as "parts") of unsaturated alkyd, and heat and stir at 60 to 70°C to obtain EPE-resin (Gardner color number 2).
~3, with a viscosity of 9.6 poise.

A system in which 100 parts of EPE-resin (F'), 2 parts of methyl ethyl ketone peroxide, and 2 parts of cobalt naphthenate were added was glued in 49 minutes, and the maximum temperature reached 139° C. with gradual heating.

The heat distortion temperature of the cast product was 108°C.

As a nonionic acrylic ester emulsion,
Add 200 parts of alumina cement to 100 parts by weight (the same applies hereinafter) of Polysol AP-612 manufactured by Showa Kobunshi Co., Ltd. (solid content 58% by weight, viscosity approximately 10 poise, MFT 0°C) and mix uniformly to form (f) liquid. And so.

Separately, 3 parts of 328E manufactured by Kayaku Nouri Co., Ltd. and 1 part of cobalt naphthenate were added to 100 parts of EPE-resin (T) to prepare an omega solution.

100 parts of solution (g) were mixed with 200 parts of solution (f) with vigorous stirring.

Immediately after mixing, the mixture was formed into a putty and kept in that state for about 30 to 40 minutes.

Next, the mixed composition was applied to a thickness of about 1 wrL onto the slate board that had just been immersed in water and pulled up.

- After being left in the sun, the surface had hardened into a non-adhesive, reedy, and elastic coating. Moreover, even when the slate board was bent and torn, the coating film did not break and remained attached to the slate board.

Separately, a slate board measuring 150 gourds x 25 mm thick and 4 inches thick is immersed in water, and immediately after being pulled up, the mixture is applied to a length of 25 meters at the end, and then slate boards of the same size are stacked. I glued it together. After leaving it for 3 days, I fixed one end of the test piece and applied a load to the other end to try to pull it off, but the slate broke at about 10 kg, and the adhesive strength exceeded the strength of the slate itself. .

Claims (4)

[Claims] (1) Synthetic resin emulsion, (2) [I] (A) an epoxy resin having 2 or 2 to 4 epoxy groups in one molecule, and (B) 1 equivalent or less of hydroxyl group per 1 equivalent of epoxy group, and 0.
React the phenols so that the amount is 5 equivalents or more, then (C) add an α-β unsaturated polybasic acid or its acid anhydride,
A radically curable resin composition obtained by using an unsaturated alkyd obtained by esterification in combination with [II] a polymerizable monomer, (3) Cement and (4) Peroxide A curable composition comprising: