JPH03109977A - Improvement of coated film surface - Google Patents

Abstract

PURPOSE:To enhance wear resistance and black heel mark resistance by applying an unsatd. polyester resin on the surface of a base material and thinly applying an aq. resin thereon in the initial period of curing of this resin, thereby removing the tackiness of the surface. CONSTITUTION:The aq. resin is thinly applied on the surface of the base material to remove the tackiness of the surface and to improve the surface in the case of the application of the unsatd. polyester resin on the surface of the base material and the application of this material to a coating floor. The cured matter having the uniformly cured surface is obtd. in this way and stains are prevented. The unsatd. polyester resin obtd. from an unsatd. polyester compd. and 20 to 80wt.% unsatd. monomer copolymerizable with this compd. is adequate. The aq. resin which contains an acrylic copolymer emulsion and an aq. urethane resin is adequate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for improving the coating surface of a liquid coating material useful as a flooring material for buildings.

[Conventional technology and its issues]

BACKGROUND ART Synthetic resins such as epoxy resins and urethane resins are commonly applied as coating materials for floors and hallways of buildings to achieve a uniform and smooth finish.

However, these resins require curing time after being applied and curing before walking becomes possible, which means that people are not allowed to enter or exit the building during this time, allowing other work to be carried out, significantly prolonging the completion period. There is a demand for materials that harden more quickly.

Unsaturated polyester resins and acrylic resins are expected to meet these demands because they can be polymerized by radical reactions, become polymerized in a short time, and can quickly develop practical strength.

In particular, unsaturated polyester resin is
As described in 7, the constituent components, the crosslink density in the molecule,
By appropriately selecting the position of the functional group, etc., it is possible to design a resin suitable for waterproofing materials and flooring materials.

However, when unsaturated polyester resin is used to form a coating film, the surface of the coating material is susceptible to curing interference due to oxygen in the air, and in extreme cases, even after the unsaturated polyester resin has been cured, it remains "sticky." When used as a building floor coating material, it leaves stains and the surface becomes easily damaged, and the film strength of the cured product decreases significantly, which can cause practical problems such as cracks and breakage.

In order to solve these problems, conventional methods have been used to improve the surface hardening of unsaturated polyester resins, but there are many problems when painting on building floors, hallways, etc.

One method is to use raw materials that prevent oxygen interference, such as cyclopentadiene and head acid, in the resin skeleton, but the proportion of these raw materials used is relatively large and expensive, so the resin price is low. becomes high.

Another method is to coat an unsaturated polyester resin and then overlay a slow-closing film of polyethylene, polyester, or the like thereon to prevent air pockets from forming.

Since the surface of the cured product does not come into contact with air, this method quickly determines the hardness, and is suitable for use in places such as factories where the location and method of use are limited, and is used when manufacturing polyester decorative laminates. However, when used as a curing method for painted surfaces such as building floors and hallways, it is extremely troublesome.
It is unrealistic because uniform products cannot be obtained.

Yet another method is to add paraffin to the unsaturated polyester resin, which has a melting point higher than the operating temperature, so that after application and before the resin begins to harden, the paraffin is liberated on the surface and air lag occurs. This method is commonly used because of its ease of operation.

However, in on-site painting work, such as the construction of building floors and hallways, variations in coating thickness and temperature changes during construction can cause paraffin to float unevenly on the surface, and the drying properties of the paint film surface are still poor. Not enough.

[Means for Solving the Problems] In order to solve these problems, the inventors of the woodworks have conducted various studies, and as a result, they applied a water-based resin to the unsaturated polyester resin in the early stage of curing, thereby improving the surface of the coating film. "We discovered a method to remove sticky J and arrived at the present invention.

That is, according to the present invention, when applying an unsaturated polyester resin to the surface of a base material and applying it to a painted floor, a thin layer of water-based resin is applied after the "initial stage of curing" to prevent "stickiness" on the surface. By removing and improving the surface, a cured product with a uniform hardened surface can be obtained and stains can be prevented.

The unsaturated polyester resin used in the present invention is composed of an unsaturated polyester compound and an unsaturated monomer copolymerizable with the compound, and has good workability, flexibility, hardness, weather resistance, solvent resistance, drying properties, etc. Depending on the intended use, the content of unsaturated monomers may range from 20 to 80% by weight, preferably from 30 to 70% by weight.
is within the range of

The unsaturated polyester compound used in the present invention can be obtained by condensation and addition reactions of alcohol compounds and carboxylic acid compounds (including acid anhydrides and carboxylic acid alkyl ester compounds). Those derived from dicarboxylic acid components are preferred.

More preferably, based on the total amount of dicarboxylic acid, 1 to
It has 25 mol% of unsaturated acid, and the chain of the unsaturated polyester compound does not contain an unsaturated bond, or even if it does contain an unsaturated bond, the ratio of unsaturated carboxylic acid to the total dicarboxylic acid is 8.0 mol. % or less is preferable.

If the amount of saturated acid at the terminal is more than 25 mol %, the elongation of the cured product will be significantly reduced, the rubber elasticity will be impaired, and the product will become hard and unable to follow cracks in the base.

If the amount of terminal unsaturated acid is less than 1 mol %, the number of crosslinking points in the unsaturated polyester compound will decrease, resulting in poor gelation and reduced curability.

Also, if the amount of unsaturated bonds in the chain is more than 8.0 mol%,
At low temperatures, the performance of the paint film becomes hard, loses its elasticity, and falls to its knees.

The diol component mainly consists of dihydroxy compounds, but
It may partially contain, for example, up to 20 mol % of polyhydroxy compounds, such as triol compounds, in which case the average number of functional groups is adjusted to dihydroxy compounds, for example by incorporating monohydroxy compounds. is appropriate.

Examples of dihydroxy compounds include aliphatic dialcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3 butanediol, 1,4 butanediol, and neopentyl glycol, and alicyclic dihydroxy compounds such as 4,4-dihydroxydicyclohexylpropane. Examples include aromatic dihydroxy compounds such as alkylene oxide adducts of bisphenol A such as ethylene oxide or propylene oxide.

Examples of polyhydroxy compounds include trimethylolpropane, chrycerin, and pentaerythritol.

Examples of monohydroxy compounds include aliphatic monoalcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 1so7'' alcohol, and nonyl alcohol, alicyclic monoalcohols such as hexanol, and aromatic monoalcohols such as benzyl alcohol. Can be mentioned.

Carboxylic acid compounds include adipic acid, cepatic acid,
Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 3,6-nindomethylenetetrahydrophthalic anhydride,
Saturated acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrachlorophthalic anhydride; maleic anhydride, maleic acid, phthalic acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, acrylic acid, and methacrylic acid. One or more unsaturated acids such as, etc. are used.

Examples of unsaturated monomers used in the present invention include styrene, vinyltoluene, methyl (meth)acrylate,
Ethyl (meth)acrylate, n-butyl (meth)acrylate, 1so-butyl methacrylate, tert-
Butyl (meth)acrylate, n-octyl (meth)acrylate 2-ethylhexyl (meth)acrylate,
There are lauryl (meth)acrylate, stearyl (meth)acrylate, (methyl)glycidyl (meth)acrylate, dimethylamine ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc., which can be used singly or in combination of two or more. It will be done.

Such unsaturated polyester resins contain polymer compounds, plasticizers, curing catalysts (crosslinking initiators, crosslinking initiation aids, etc.) in order to adjust the viscosity, modify the physical properties of the cured product, and improve the curing speed.
, fillers can be added if necessary.

Polymers that can be used include reducing manufacturing costs,
It is mixed to improve coating performance or coating performance when used as a coating material, such as acrylic resin, polyester resin, polyurethane resin, styrene-allyl alcohol copolymer, polyethylene, or paraffin wax. I can list them.

Examples of the plasticizer include dioctyl tucrate, dibutyl phthalate, butylphthalyl butyl glycolate, tricresyl phosphate, and chlorinated paraffin.

The curing catalyst added as necessary can be appropriately selected depending on the curing method.

When using high energy such as an electron beam, no particular polymerization initiator is required, but when using light or ultraviolet rays, a well-known photosensitizer is required as a polymerization initiator.

In addition, if thermal energy or far infrared rays are used, peroxides such as hendyl peroxide, methyl ethyl ketone peroxide, ditertiary butyl peroxide, lauroyl peroxide, and cumene hydroperoxide are suitable as polymerization initiators, and polymerization can be started. Suitable starting aids include metal soaps such as cobalt naphthenate, tertiary amines such as dimethylaniline, alcoholades such as sodium methylate, lauryl mercaptan, and N-ethyl metatoluish.

In addition to these components, various substances can be added for the purpose of improving the performance of the cured product.

These additives include pigments such as titanium white, Kao pump rack, and hengara, solvents such as xylene, toluene, methyl ethyl ketone, and mineral tobilit.
Fillers such as polyethylene, polypropylene, nylon, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, alumina, sauce, kaolin, talc, diatomaceous earth, silica gel, mica powder, glass fiber powder, ashest powder, silica powder, hentonite , colloidal silicic acid, castor oil derivatives, and the like can be added.

The method for applying the unsaturated polyester resin used in the present invention is to apply the coating using a conventional coating method such as a construction tool such as a spatula, a brush, or a roller, or a mechanical coating such as a spray.
Just let it harden.

The amount of coating per time is usually 0.1 to 5.0 mm.

Preferably it is 0.3 to 3.0 mm. If the coating film is thinner than 0.1 mm, bottle balls are likely to occur in the coating film, and if the coating film is thicker than 5.0 mm, the cured product will shrink, and when used for flooring, the edges will Peeling may occur.

1. If you want to apply a thick coating, it is desirable to increase the number of coatings to ensure the desired coating thickness.

In that case, the interval between coatings is preferably within 2 to 24 hours at room temperature; if a long period of time passes, the adhesion between the eyebrows may decrease due to paraffin, etc. contained in the unsaturated polyester resin, and peeling may occur.

As the aqueous resin in the present invention, synthetic resin aqueous liquids such as acrylic copolymer emulsions, water-based urethane resins, water-soluble polyester resins, and water-soluble ebogishi resins are used, but among them, acrylic copolymer emulsions and aqueous It is preferable to use a combination of urethane resins.

When these polymeric coating materials are contained, a thin, tough coating is formed on the surface of the unsaturated polyester resin,
Drying properties are improved, and as a result, not only surface stickiness is eliminated, but also durability such as black heel mark resistance and abrasion resistance is improved.

The acrylic copolymer emulsion is a copolymer of at least one vinyl monomer such as acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, styrene, α-methylstyrene vinyl chloride, vinyl acetate, ethylene, propylene, etc. Examples include synthetic resin emulsions obtained by.

Furthermore, a metal cross-linked type material in which a polyvalent metal chelating agent is added as known in JP-A-49-1548 can also be used.

As water-based urethane resin, for example, Japanese Patent Publication No. 532254
Examples include an alkaline salt aqueous emulsion of polyurethaneurea polyamide polycarboxylic acid disclosed in Publication No. 8, an aqueous emulsion in which a polymeric polyurethane is dispersed in water with an anionic or nonionic surfactant, etc. I can do it.

In addition to these known water-based urethane resins, water-based urethane resins having carboxylic acid and/or carboxylate salts in the polyurethane resin chain may also be used.

In addition, 3 polyurethane produced by a crosslinking reaction with an addition reaction product of a polyol and a diisocyanate, or a prepolymer having an isocyanate group at the terminal position and a chain extender is dispersed in water, and emulsified with a polymerizable ethylenically unsaturated compound. JP-A-59- obtained by polymerization
Polymers of polymerizable ethylenically unsaturated compounds and polyurethanes, which are described in detail in JP-A No. 138210, JP-A-59-1.38212, and JP-A-59-157101, can be used.

In the aqueous resin used in the present invention, the weight ratio of the solid content of the aqueous urethane resin to the solid content of the acrylic copolymer emulsion is preferably 3 (1 nia) to 70:30.

If the ratio of the aqueous urethane resin is less than 30%, the abrasion resistance of the aqueous resin will be poor, and if it exceeds 70%, the removability when the aqueous resin is removed with an alkaline detergent will be poor.

When the aqueous resin used in the present invention is applied to a flooring material, wax can be emulsified and used in combination to improve gloss, water resistance, stain resistance, and firmness.

The wax used in the wax emulsion may be any commonly used wax, including natural wax and synthetic wax.

Natural waxes include animal wax, vegetable wax, and mineral wax. Animal waxes include beef tallow, hydrogenated lard wax, lanolin, beeswax, spermaceti wax, etc., and vegetable waxes include soybean oil. Wax obtained by hydrogenating castor oil, wax obtained by hydrogenating castor oil, carnauba wax, candelilla wax, wood wax, wax wax, etc. Mineral waxes include monk wax, ceresin wax, paraffin wax, microcrystalline one An example of this is

Also, as a synthetic wax, the molecular weight is between 500 and 5.00.
There are polyethylene wax, polypropylene wax, wax produced by the Fischer-Tropsch process, and oxides and modified products of these synthetic waxes.

Preferred is polyethylene wax. These are already widely known.

A wax emulsion can be produced by a known method by adding an emulsifier to the above wax and emulsifying it using various emulsifiers.

In addition, the weight ratio of the total weight of the solid content of the aqueous urethane resin and 1 part of the acrylic copolymer emulsion of the aqueous resin used in the present invention to the solid content of the wax emulsion is to
:o, preferably 5 to 1.0:2.0.

If the proportion of wax emulsion is smaller than this, the black heel mark resistance of the floor coated with water-based resin will be poor, and if the proportion of wax emulsion is larger than this, the abrasion resistance will be reduced.

In addition to the above ingredients, the water-based resin may contain ethylcarpitol, methylcarpitol, butylcarpitol, Plasticizers such as toll, dibutyl phthalate, tributoxyethyl phosphate, ε-caprolacta, etc., styrene-maleic acid copolymers, rosin-maleic acid copolymers, high acid value low molecular weight acrylic-styrene copolymers, or Conventional polishing agents include functional group resins such as alkali-soluble resins such as high acid value, low molecular weight acrylic ammonium 6 salts, or alkali metal salts, leveling agents, surfactants, wetting agents, antifoaming agents, and preservatives. It can contain auxiliary ingredients used in formulations.

In addition, water-soluble resins such as water-soluble polyester resins and water-soluble epoxy resins may be added.

The method of applying the aqueous resin used in the present invention is as follows:
Painting can be done using ordinary painting methods such as construction tools such as rollers and motsupu, or mechanical painting such as spraying, and the amount of application per coat should be as thin and uniform as possible, and usually the solid content is 1. , 0 to 20.0 g/m2, preferably 5.0 to 10.0 g/m2.

If the coating film is thinner than 1.0 g/m 2 , uniform coating cannot be achieved, leaving uncoated areas and the effects of the present invention cannot be fully exhibited.

On the other hand, if the coating thickness is greater than 20.0 g/m2, cracks will occur on the surface of the water-based resin.

In the present invention, the "initial stage of curing" of an unsaturated polyester resin means that the unsaturated polyester and the polymerizable monomer 7 are polymerized (gelled) by a radical reaction, the fluidity of the liquid resin is lost, and mechanical This refers to the time when the strength has reached approximately 80% compared to when fully cured, and the method of displaying it differs depending on the purpose of use, but in the case of flooring materials, it is expressed by the surface hardness of the cured coating film. Common.

In the case of the unsaturated polyester resin of the present invention, the "initial stage of curing" is normally reached in 2 to 5 hours at room temperature, although it is also related to the environmental temperature, and the surface hardness by the Shore hardness tester is 50.
~80 (Shore A).

If a water-based resin is applied with a roller, brush, mop, etc. before the "initial stage of curing," the surface of the coating film will be damaged because the reactivity of the surface of the unsaturated polyester resin is still low.

The base materials used in the present invention include cement mortar,
Examples include inorganic base materials such as concrete, polymer base materials such as urethane resin, epoxy resin, and vinyl chloride resin.

These substrates can be coated directly with unsaturated polyester resin, or, to further improve adhesion to the substrate8, an undercoat may be applied as necessary, followed by unsaturated polyester resin. It's okay.

Desirable primers include urethane resin-based primers that contain active isocyanate groups and react with moisture.

In this way, when the surface improvement method of the present invention is applied to flooring materials coated with unsaturated polyester resin, the tack-like uncured state on the surface of the cured product is significantly improved, resulting in excellent film strength and durability. A product with excellent black heel mark properties and abrasion resistance can be obtained.

Furthermore, when used to improve the surface of roof coating waterproofing materials, it can improve stain resistance and durability.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the invention is not limited thereto.

Further, in the following, parts are based on weight unless otherwise specified.

In addition, the test results of Examples and Comparative Examples are listed together in Table 1.

9 In addition, the performance test method and comparative performance evaluation used in this test are described below.

Surface embedding and surface curing properties were measured according to the following surface tack measuring method. The smaller the adhesion force obtained by the surface tank measurement method, the better the drying properties of the surface.
If the adhesive strength is less than 200 gf/cm2, there will be no sticky feeling when you touch the surface of the coating with your fingers, but if the adhesive strength is greater than this, you will feel sticky when you touch it with your fingers. It may stick to your fingers, indicating that the surface has not yet hardened.

A polyethylene jig with a disk with a contact area of 5.7 cm2 and a rod with a diameter of 0.8 cm in the center was placed on the surface of the test specimen, and a 100 g weight was placed on the jig for 10 seconds. Place it on the jig, remove the weight, and slowly pull the tip of the rod-shaped part of the jig using a spring gauge. Pull the jig until it comes off, read the maximum load, and calculate the load per unit area.

0 Sword and Soil Japan Floor Polish Industry Association JFPA standard test standard tile (vinyl asbestos tile) - Apply the sample at a rate of 10±2 m per square meter. After drying at room temperature for 30 minutes, the test piece was coated four more times and left to dry at room temperature for 68 hours, and then evaluated by measuring the degree of wear using a taper tester.

A test piece coated on a standard white tile (vinyl asbestos tile) for Boo-Kheal Mark JFPA standard testing at a thickness of 10±2m per square meter was dried at room temperature for 24 hours.
Snel (Snel) containing 6 x 30mm square rubber pieces
l) Attach the mold stain capsule by screwing the specimen onto the surface and rotating in both directions at a speed of 50 rpm for 2.5 minutes each. Visually observe and evaluate the amount of black heel marks attached to the tile.

A test piece coated on a standard tile (vinyl asbestos tile) for slow release JFPA standard testing according to the method for measuring black heel mark resistance is left overnight at room temperature with a relative humidity of 80% or less. Place the test piece in a thermostat at 38 ± 2°C for 6
After leaving it for an hour and immersing it in fundamental sound water at room temperature for 1 hour, the test piece was taken out and left in a constant temperature room at 38±2°C for 18 hours.

The stripping solution is 3.97g of potassium hydroxide (KOH85%)
and 17.7 g of oleic acid were mixed with 5 m of ammonia water (M
Using soapy water dissolved in 1000 m of distilled water containing H40H28%), soak the boar bristle brush of the Gardnas Tradeline Washability Tester in the stripping solution for 2 minutes, then pour 10 ± 2 m of soap onto the test piece and immediately test. Start.

After 25 reciprocations, the specimen is rinsed with clean water and then determined whether it has been completely removed.

ASTM-D- for washability tester
1792-66.

Reference example 1 Water parallel to stand up ll U [l production 2 Average molecular weight 1 consisting of adipic acid and ethylene glycol
000 polyester polyol and hexamethylene diisocyanate to produce a prepolymer having an isocyanate group at the end, then add dimethylpropionic acid and 1,4-butanediol as a chain extender to cause a polymerization reaction, Ammonia as a neutralizing agent and water as a solvent are added and stirred uniformly.

This product (referred to as WU) had a solid content of 33% and a viscosity of 500 centiboise at 25°C.Reference Example 2 Acrylic Out: In 48.8 parts of pure water in the emulsion, 0.5 parts of sodium lauryl sulfate as an emulsifier.
and 1.0 part of 30 mole adduct of ethylene oxide of nonylphenol, 0.1 part of ammonium persulfate as a polymerization initiator, and while stirring at 70°C, 6 parts of butyl acrylate, 10 parts of methyl methacrylate, 10 parts of styrene,
A mixture of 4.6 parts of methacrylic acid was added dropwise over 3 hours,
Further, stirring was continued for 30 minutes at the same temperature to complete the polymerization, and 19 parts of a metal crosslinking agent consisting of 7% zinc oxide, 12% ammonium carbonate, 14% aqueous ammonia, and 67% water was added to 3.
Acrylic copolymer emulsion (WA) with a solid content of 33%
) was obtained.

Example 1 In a fourth flask equipped with a stirrer, a thermometer, a fractionator with a condenser, and a nitrogen inlet tube, 1104 g (10.6 mol) of neopentyl glycol and 1418 g of adipic acid were added.
(9.7 mol) and 35 g (0.3 mol) of fumaric acid were charged, and an esterification reaction was carried out at 215°C in a nitrogen stream, and water was distilled off until the acid value reached 6.0 mg KOII / g. did.

Next, cool this to 150°C and 78g of maleic anhydride.
(0.8 mol) was added and after reacting for 2 hours at 150'C, the reaction was cooled to 100'C.

After reaching to o'c, 1300 g of styrene and 150 mg of hydroquinone were added. The mixture thus obtained had a solids content of 57%.

To 100 parts of this unsaturated polyester resin, 0.2 parts of paraffin with a melting point of 456-58°C, 0.5 parts of Modaflow as a dispersant, and Disparon 193 as an antifoaming agent were added.
Immediately before use, 0.1 part of 11 (manufactured by Hashimoto Kasei Kogyo Co., Ltd.) and 10.0 parts of titanium oxide (Teikoku Kako Department) as a pigment were uniformly mixed and dispersed under high speed stirring at room temperature. 1.5 parts, 0 aniline as starting aid
．． Using a formulation containing 5 parts, it was applied to a slate board with a brush to a thickness of 2.0 mm under a 20''C environment.

1 hour, 3 hours and 5 hours after application, the aqueous urethane resin and acrylic copolymer emulsion produced in Reference Example 2 was applied to a part of the surface of the cured product at a weight ratio of 5.0:5.0. A cloth was impregnated with the mixed aqueous resin liquid (referred to as Wl), applied thinly and uniformly, and after drying at room temperature for 1 hour, surface hardening properties were tested. In addition, abrasion resistance, black heel mark resistance, and removability were also tested.

Example 2 The same procedure as Example 1 was used except that an aqueous resin liquid (referred to as W-2) in which the ratio of the aqueous urethane resin and acrylic copolymer emulsion was 1.01.0 was used. Similarly, surface hardening abrasion resistance, black heel mark resistance, and removability were tested.

Example 3 Aqueous resin in which the ratio of aqueous urethane resin and acrylic copolymer emulsion was 9.0:1.0 in Example 1? Surface hardening abrasion resistance, black heel mark resistance, and removability were tested in exactly the same manner as in Example 1, except that ffj (referred to as W-3) was used.

Comparative Example 1 Surface curing abrasion resistance and black heel mark resistance were obtained in exactly the same manner as in Example 1, except that the aqueous resin liquid was not applied to the surface of the cured unsaturated polyester resin product. , tested for removability.

The results of these tests are shown in Table 1.

6 [Effects of the Invention] It can be seen that the method of the present invention eliminates tackiness on the coating film surface and further improves abrasion resistance and black heel mark resistance compared to the conventional method (comparative example). It is clear from 1.

Claims (1)

[Claims] 1. A method for improving the surface of a coating film, in which unsaturated polyester resin is applied to the surface of a base material, and a water-based resin is applied thinly during the "initial stage of curing" of the resin to remove stickiness from the surface. , the unsaturated polyester resin consists of an unsaturated polyester compound and an unsaturated monomer copolymerizable with the compound,
2. The method for improving the surface of a coating film according to claim 1, wherein the content of the unsaturated monomer is in the range of 20 to 80% by weight. 3. The method for improving the surface of a coating film according to claim 1, wherein the aqueous resin contains an acrylic copolymer emulsion and an aqueous urethane resin.