JPS5820909B2 - Method for improving surface properties of substrates using spiroacetal resin paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION In general, materials with porous and water-absorbing surfaces tend to have foreign substances attached to the substrate surface due to the movement of water, and soluble substances can penetrate into the substrate together with solvents, causing cleaning is often impossible as it contaminates the

In particular, water-curable materials deposit efflorescence and mirabilite on their surfaces due to the movement of moisture, resulting in severe staining.

Furthermore, mold grows on surfaces that absorb moisture, resulting in contamination.

As described above, the surface properties of porous substrates have many drawbacks, such as the fact that in cold weather, the permeated moisture freezes and expands, damaging the surface.

The present invention is a photocuring type that can be applied to the surface of a porous inorganic base material such as a hydrated cured product, an unglazed pottery, a brick, a water-absorbing stone, or a cured product of slag, which has permeability into the porous base material in a natural environment atmosphere. Aku IJ A base material characterized by applying and penetrating a spiroacecool resin paint having more than one loyl group or methacryloyl group, and irradiating ultraviolet rays when the paint has penetrated into the base material to a depth of 5 to 5000 μ. This invention relates to a method for improving the surface properties of materials.

The present invention aims to improve the surface properties of architectural finishing materials that are porous and have weak points on their surfaces by using spiroacecool resin (hereinafter referred to as spiroacecool resin) paints having more than one acryloyl group or methacryloyl group. Through photopolymerization, which allows the polymer to penetrate into the skin and to freely adjust the curing time, polymerization starts when the penetration conditions are most appropriate.
By performing the treatment while freely controlling the hardening state, the properties of the surface layer of the base material are completely modified, making it water-impermeable, preventing the precipitation of efflorescence and Glauber's salt, eliminating mold growth, and heat-resistant. A porous and water-absorbing paint made of spiroacecool resin, which has a strong surface hardness and significantly improves stain resistance, chemical resistance, solvent resistance, durability, cold resistance, appearance properties, etc. The present invention relates to a method for improving the surface properties of a substrate having a rough surface.

Conventionally, methods such as painting and resin impregnation have been attempted to improve this surface quality, but they are not durable or are technically difficult to improve only the surface, so the entire base material must be treated. However, there was no suitable method, as it was extremely expensive and could not be used by the general public.

In other words, it is common practice to apply ricin paint, emulsion paint, fiber wall paint, or air-drying alkyd paint to a porous, water-absorbing inorganic substrate to beautify its appearance; Improvements are focused on beautifying the surface of the substrate, and the aforementioned improvements in the properties of the surface layer of the substrate are not achieved.

Another useful method is to impregnate a porous, water-absorbing inorganic base material with a monomer or prepolymer containing a radical generator, and then cure it at room temperature or by heating to improve the physical properties and appearance of the base material. However, since it takes time for polymerization and requires polishing, there are problems with productivity. It is not easy to select the shape and size of the object because there are contradictory circumstances in that it is desirable that the object be of good quality, while on the other hand it is desirable that it be small from the point of view of easy impregnation.

Furthermore, since the surface that comes in contact with the air prevents the polymerization of the seven polymers, it is extremely difficult to impregnate and cure only a portion of the surface with monomer; rather, we focus on impregnating and curing deep within the base material. is generally placed.

Another problem in this case is that since the entire surface is impregnated with resin, it has poor durability and fire resistance, and its use as an interior building material is restricted.

The curing mechanism in this case is a normal room temperature curing method using a radical generating source such as an organic peroxide, or a medium temperature heating curing method.

These full-surface impregnations have the following disadvantages: (1)
In the case of impregnated acrylic monomers such as methyl methacrylate, the surface portion becomes paperized and must be polished after polymerization; (2) the production method is batch-type, for example, 2 hours for impregnation and 4 hours for polymerization; , It takes 1 hour to wash with water, the amount of energy consumed is too large, and mass production is not possible. (3) There is a residual amount of unreacted monomer of 0.5 to 1.0%.
(4) When the monomer polymerizes, the volume shrinks by about 20 times, which causes water to enter and exit, making it impossible to form a completely continuous film. (5) If the acrylic monomer is introduced into the entire base material, the base material itself will undergo thermal cracking due to the heat generated during polymerization, and product cracks will occur at a rate of 20%. (6) Manufacture of counter parts that cannot ensure cigarette proof. Sometimes it was necessary to separately top coat acrylic urethane on the upper surface, and in addition, acryloyl or methacryloyl groups were added to the molecule, such as epoxy-acrylate type (vinyl ester type), polyester-acrylate type, and polyurethane-acrylate type. A method has also been proposed in which the surface is coated with a photocurable resin containing bisphenol, polyester, or polyurethane skeletons and photocured, and this method is extremely effective.

However, when these existing photocurable resins are used, they may cause significant problems depending on the application.

That is, if the purpose is simply to improve the moisture absorption prevention properties of the surface, satisfactory results can be obtained using the various photocurable resin paints described above, but if the appearance is important,
In particular, existing photocurable resins cannot provide satisfactory properties in terms of so-called visual product sensations, such as weather resistance, yellowing, surface hardness and crack resistance, and appearance and sensation.

For example, when looking at yellowing, even if the product is left indoors under diffused light after painting, it will undergo considerable discoloration after about six months, resulting in a significant loss of commercial value.

Furthermore, if the surface hardness is set to a pencil hardness of 4H or higher, which is considered to be difficult to scratch easily under normal usage conditions, cracks will inevitably occur in molded products with relatively large areas, such as building materials.

The present inventors have conducted intensive studies on methods for improving the properties of the surface layer of a porous, water-absorbing inorganic base material, and have found that the method of the present invention, which cures a photocurable spiroacecool resin paint using ultraviolet irradiation, is satisfactory. succeeded in obtaining the desired product.

That is, the following advantages were obtained by using spiroacecool resin.

(1×a) Since the viscosity of the spiroacecool resin itself is low and the hardness of the cured product of the resin itself is high, the degree of freedom in coating is large and a cured product with high surface hardness can be obtained.

(b) On the other hand, conventional resins have a high viscosity. Therefore, when painting, it is necessary to dilute with a 7-mer to adjust the viscosity to the desired level, but when diluted with a monomer, it hardens. Hardening of objects decreases.

If a hardness is selected that does not reduce the hardness, cracks will appear in the cured product.

(2) High weather resistance, especially yellowing resistance.

(3) High stain resistance.

That is, for example, cigarette proofing is high and magic ink resistance is high.

(4) Non-combustible building materials with low smoke generation can be obtained.

(5) The treatment can be performed even when the base material is wet with moisture, and a strong anchor can be obtained.

(6) None of the photocurable resins according to the prior art is superior to Spiroacecool in terms of (2) to (5).

That is, the present invention applies light that can penetrate the porous substrate in an environmental atmosphere to the surface of a porous inorganic substrate such as a water-cured material, unglazed pottery, brick, water-absorbing stone, or cured slag. This method of improving the surface properties of a substrate is characterized in that a hardening type spiroacetal resin paint is applied and penetrated, and when the paint has penetrated into the base material to a depth of 5 microns to 5000 microns, ultraviolet rays are irradiated.

Therefore, according to the method of the present invention, an ultraviolet irradiation device that can instantaneously gel a photocurable paint is used, with the paint penetrating from 5 microns to 5,000 microns of the surface layer of the base material. In combination, the permeation state of the paint can be adjusted at will, and it can be gelled on the spot, so it is very suitable for improving the surface layer of the base material.

In a normal system using a room-temperature curing catalyst, even if a curing accelerator is used, gelation is far from instantaneous, and gelation takes several minutes at most, during which time the paint penetrates deeply into the base material. It is not suitable for improving the properties of the surface layer.

On the other hand, in the UV curing method, the paint gels only during UV irradiation.
Alternatively, as curing progresses and gelation or curing stops immediately when irradiation is stopped, a very detailed coating schedule can be established and it is easy to deal with changes in penetration properties that vary depending on the substrate.

Furthermore, the advantage of using a method of gelling and curing paint using ultraviolet irradiation is that it has poor thermal conductivity and does not easily follow elevated environmental temperatures. This is more noticeable compared to the curing method.

In the case of a base material using a hydraulic material such as cement or plaster as a binder, heating itself to raise the temperature is undesirable, so in this case, a curing method using ultraviolet irradiation is most suitable.

As the ultraviolet irradiation device, a commercially available device equipped with a high-pressure mercury lamp and a metal halide lamp can be used.

Due to the nature of the light, those using high-pressure mercury lamps have difficulty reaching deep inside the substrate, but on the other hand, they have the property of shortening the curing time.On the other hand, those using metal halide lamps can easily reach deep inside the substrate and can be delivered quickly. Because it has excellent properties, it can be used appropriately to take advantage of these properties.

Appropriate penetration of the paint is from 5 microns to 5,000 microns on the surface of the base material.

If the permeation layer is too thin, for example, if the permeation is less than 5 microns, the anchoring effect of the paint will be small, and the adhesion of the paint and the sufficient reinforcing effect of the surface layer of the base material will not be obtained.

The conditions for imparting the above-mentioned penetration layer to the paint and causing it to gel are the type and viscosity of the paint, the quality of the irradiated ultraviolet rays, the output, the irradiation distance, the irradiation time, the type and amount of the photosensitizer, the dyes and pigments to be added, and the filling. Conditions are set based on various combinations such as the type and amount of material, the degree and type of porosity of the base material, etc., but by selecting other conditions, the irradiation time of ultraviolet rays can be set to 0.5 seconds. to 5 minutes, preferably 1 second to 1 minute, and the viscosity of the paint is set to 0.5 poise to 300 poise, preferably 2 poise to 100 poise.

If the viscosity of the paint is lower than 0.5 poise, the penetration is too thick and is inappropriate, and if it is higher than 300 poise, it is difficult to modify the surface layer of the base material by providing sufficient anchoring and reinforcing effects.

If the penetration of the paint is greater than 5,000 microns, it is difficult for ultraviolet rays to reach the area, resulting in areas that are insufficiently cured by ultraviolet irradiation.

5 to improve the properties of the surface layer of the base material even when the thickness of the base material is large.
000 microns of paint penetration is almost sufficient, but
In some cases, it may be necessary to reinforce deeper.

At that time, keep it at room temperature. It is preferable to use a curing type curing system together.

With this method, the paint that has penetrated into the deep layers where ultraviolet rays do not reach will require a little extra time to harden, but it will eventually harden and will be useful for reforming the deep layers, such as reinforcing them, and uncured paint will remain. It will emit a long-lasting odor.

You can prevent this from happening.

There is no particular reason why the UV irradiation time is set to 0.5 seconds to 5 minutes, preferably 1 second to 1 minute, but UV irradiation allows for such instantaneous and wide-ranging gelling or curing time control. This is a characteristic of the curing method, and considering the production speed and the penetration of the paint into the porous substrate, it is natural that it should be set on the short-time irradiation side.

The paint may be applied in one coat or in two coats.

One-time coating is generally desirable from the viewpoint of productivity and economy, and is sufficient for the purposes of reinforcing the surface layer of the base material, improving brittleness, preventing suction, preventing contamination, and preventing efflorescence.

If the purpose is to improve the appearance and weather resistance of the surface of the substrate, it is more desirable to apply two coats.

That is, in the case of the first coating, a metal halide lamp with fast delivery is used, and in the case of the second coating, a high pressure mercury lamp with poor delivery but high curing speed can be used as appropriate.

In principle, curing of paint by UV irradiation is carried out at each painting stage, and it is not only necessary to gel the paint film, but also to cure the paint film at each painting stage, and then to cure the paint film at each painting stage. It is something to do.

This may be sufficient if the porosity of the surface base material is not large.

If the surface of the substrate is very porous and the penetration of paint is slow, the two coats that are commonly applied will not adhere well between the undercoat and topcoat, and delamination is likely to occur due to impact. This can be a fatal flaw.

In such a case, by introducing the method described below, it is possible to perform coating with extremely good adhesion between the undercoat and the topcoat without causing delamination even when subjected to impact.

The method described below applies a single coat of paint, and before the applied paint has completely penetrated into the base material, it is irradiated with ultraviolet rays while it remains on the surface of the base material to gel it. This is to stop the flow and penetration of the paint, and to stop the IL at the gelation stage.

In this case, gelation by ultraviolet irradiation is a method in which the gelation occurs almost instantaneously, and when the UV irradiation is stopped, the progress of gelation of the paint stops instantaneously. This is a perfect way to stop it.

The second coat is applied after the first coat has been brought into the above-described state, and may be applied immediately or at an appropriate time.

The undercoat and topcoat are then completely cured by UV irradiation.

According to this method, the cured film of the top coat applied a second time exhibits very good adhesion to the cured film of the undercoat applied once.

This is surprising and unexpected.

The reason for this is not because of the difference between the first coat and the second coat. Since the adhesion is not that sufficient, one point is to keep the paint film in a gel state after the first application.
This may also be due to the etching phenomenon caused by the second coat of paint.

This point is the same even when applying two or more coats; in the case of the first coat, the paint remains on the surface of the base material and gels due to UV irradiation, and is left in that state until the second coat is applied.
This method also involves repeating the process of turning the material into a gelatinous state by irradiating it with ultraviolet rays, and then allowing it to completely harden when the final coat is applied.

Another big advantage of this method is to keep the paint film in the gel state before applying the top coat, as the adhesiveness remains in the gel paint film, so the flow of the paint applied in the later stage can be appropriately suppressed. , it is possible to obtain a painted surface that faithfully reproduces the uneven state of the base.

This is a very effective method if there is an uneven pattern on the base and you want to leave it on the surface after painting.

It can be inferred from the above that one important part of the "method described next" is to keep the previous coating in a gel state, but another important part is that the coating is not applied during the first coating. It is certain that the applied paint penetrates into the base material and is exposed to ultraviolet light, which has fast curing ability, to induce gelation before it disappears from the base material surface.

This does not necessarily mean that the initial paint film will remain in a gel state on the substrate surface, since the point of UV irradiation does not necessarily coincide with the point at which gelation and penetration stop.
It must be assumed that gelation occurs in the presence of a terminal end of the paint that is penetrating into a range that is not deep from at least the surface layer of the base material.

This point is presumed to be another reason for improving the adhesion with the subsequent paint film.

Therefore, the second important part of this method is that the coating film from the first coating has penetrated into the base material from 5 microns to 5,000 microns according to the required performance, and the paint still remains on the surface of the base material. However, it should be noted that in this case, it cannot be determined that the gelled top of the painted film is necessarily on the surface layer, and that it can only be expressed as described above. It is.

The object to be coated that can be used in the present invention is a porous water-absorbing inorganic base material that has many fine voids and has a water absorption amount of several percent to several tens of percent.

Examples of these include cement mortar products, concrete products, artificial stones with patterns made from aggregate using white cement as the binder, and substrates using crushed hardened polyester plates containing artificial pearl foil as aggregate and cement as the binder. , unglazed pottery, gypsum products, such as base materials made of gypsum, or base materials made of gypsum mixed with aggregate or patterned with aggregate;
There are bricks, etc.

Natural porous stones such as Tako stone, Oya stone, instant sandstone, and marble are also suitable materials to be coated, and porous artificial stones made using slag from blast furnaces can also be used.

That is, vehicles for UV-curable coatings suitable for the present invention include spiroacecool resins containing more than one acryloyl group or meccryloyl group.

For example, diarylidenepentaerythritol is the most common spiroacecool compound as a resin resin raw material, which is obtained by the reaction of diarylidenepentaerythritol and an acryloyl group-containing unsaturated alcohol or unsaturated carboxylic acid and is represented by the following general formula. It is representative and sufficient for the purposes of the present invention.

It is particularly suitable for weather resistance and stain resistance.

Furthermore, it also includes a type in which at least one of hydroxyl polyester, hydroxyl polyether, and carboxyl polyester is used in combination and reacted.

In this case, toughness is added to the coating film, which is more preferable for applications requiring such toughness.

The resins referred to in the present invention include various spiroacecool resins alone or mixtures thereof, and monomers reactive with them, such as 1,4-butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and sichenda. It also includes compositions in which monofunctional or polyfunctional monomers such as erythritol polyacrylate, hexanediol diacrylate, styrene, vinyltoluene, and cool styrene are blended with the above-mentioned various resins or mixtures thereof.

For ultraviolet curing, it is necessary to use benzoin, benzoin ethers, or a combination system of benzophenone and amine, which are commonly used as photosensitizers.

- For the third coating, a curing accelerator such as cobalt naphthenate can be used in combination with an organic peroxide that penetrates deep into the base material and becomes a source of radical generation when curing is insufficient due to ultraviolet irradiation.

Furthermore, it goes without saying that fillers and colorants such as dyes and pigments can be optionally used in combination in the present invention as long as the photocurability is not impaired.

The colorant used, such as a pigment, is preferably one that does not absorb ultraviolet rays or one that reflects ultraviolet rays.

There are no particular restrictions on the dye.

Next, examples will be shown below to help understand the present invention, but the present invention is not limited thereto.

Example 1 Synthesis of light-curable spiroacecool resin A A 11-three-bottle flask equipped with a stirrer, a cooling condenser, and a thermometer was equipped with 21 diarylidespentaerythrithritides.
2g, 2-hydroxyethyl acrylate 200.9.
2 g of para-toluenesulfonic acid and 0.29 g of hydroquinone were charged and reacted at 90° C. for 5 hours. As a result of infrared analysis, approximately 90% of free hydroxyl groups disappeared.

4 g of dimethylamine ethanol and 4 g of benzophenone were added to this to synthesize photocurable spiroacecool resin A.

It was pale yellowish brown in color and had a viscosity of about 5 poise.

Gypsum tile painting α: 100 parts of water gypsum, 37 parts of water, 0.5 parts of glass fiber
A 300 mrt x
Pour into a mold of 300 mm x 10 mm and harden.

After curing, when removed from the mold, a gypsum board with an uneven pattern formed on its surface is obtained.

The surface of the gypsum board with this pattern was coated uniformly with a sponge roll impregnated with light-curing spiroacecool resin (5), and immediately transferred to an ultraviolet irradiation device using a high-pressure mercury lamp with an output of 12 kW at a conveyor speed of 10 m. / minute passed,
It turned into a gel.

Gelation time was approximately 10 seconds.

It was coated again with a flow coater to a film thickness of 150 μm, and cured using the same irradiation device at a rate of 2.6 μ/min.

The curing time is approximately 3 seconds. It was possible to obtain a design quill A whose appearance was indistinguishable to the naked eye from ceramics having a pencil hardness of 4 to 5H.

In order to measure the thickness of the cured coating, the coated gypsum board was cut, the cut surface was polished, and the measurement was performed using a reading microscope. As a result, penetration of about 250 to 300μ into the gypsum board with a coating thickness of 220 to 250μ was observed. .

When this paint film was peeled off, the peeling of the paint film occurred between the paint-penetrated layer and the non-penetrated layer.

Separately, after painting with a similar sponge, leave it for 1 hour, the paint film will be completely absorbed into the plaster board, gel under the same conditions, and then apply a top coat and cure, and cracks will appear in the thread film after curing. However, some peeling was observed between the gypsum surface and the cured coating.

Comparative Example 1 Synthesis of Vinyl Ester Resin B Into an 11-three-bottle flask equipped with a stirrer, a thermometer, and a cooling condenser, 350 g of Epikote 827 from Shell as an epoxy resin, 144 g of acrylic acid, 29 g of dimethylamine hydrochloride, and 0.0 g of hydroquinone were added. Prepare 25g, 12
After reacting at 0 to 135°C for 5 hours, the acid value was 4.9.

Next, trimethylolpropane triacrylate 200
After adding 200 g of L-hexanediol diacrylate to obtain a vinyl ester resin, 18 g of benzophenone was added.
g, and dimethylaminoethanol iB were added to produce photocurable vinyl ester resin B.

The viscosity was about 4 poise. A gypsum board was painted under the same conditions as in Example 1 to produce Design Tile B.

Design Tile A Design Quill B was placed indoors in a place exposed to sunlight through window glass and left for 6 months.

Design tile A, which uses light-curable spiroacecool resin A, has a slightly lighter yellow color, although the reason is not clear, and the yellow color has become a little lighter, which improves the appearance. Design Quill B, which uses photocurable vinyl ester resin B, began to turn yellow in less than one month, and turned yellowish brown after six months, resulting in a severe loss of commercial value.

Example 2 Photocurable spiroacecool resin A1 produced in Example 1
00 parts, 50 parts of hexanediol diacrylate and 1.5 parts of benzoin isobutyl ether were added to produce a photocurable spiroacecool resin C.

The viscosity was 2.2 poise. Manufacture of cold-resistant tiles Unglazed tiles fired at around 800℃ have a water absorption rate of 12-
15%, it could not be put to practical use as an exterior material in cold regions because the absorbed water expanded due to freezing after water absorption, resulting in cracks.

Pre-dried 150mrrt x 150mr
Resin C was roll-coated onto an unglazed tile with a size of n x 5 squares, and when a uniform film was formed on the surface, it was passed through the ultraviolet irradiation device used in Example 1 three times at a conveyor speed of 10 m/min. , gelled to a non-sticky state.

The time required at this time was about 30 seconds.

Although we were able to obtain cold-resistant tiles that are resistant to freezing and thawing in the 5th time, we also applied the same resin to a thickness of 100 μm and used the same ultraviolet irradiation equipment used to gel the paint for the 3 m/3 m
By photocuring for 7 to 8 seconds at a conveyor speed of 30 minutes, a cold-resistant tile was obtained that had an appearance exactly like a porcelain tile and had a cured film with a hardness of 4H.

This cold resistant tile is 0℃ x 24 hours and 30℃ x 24 hours.
Passed the test three times for an hour.

On the other hand, unpainted unglazed tiles cracked after just one coat.

When we cut the painted tile and measured the film thickness after polishing the cut surface, the coating film thickness was about 170 μm.
It was observed that the sample had been impregnated and hardened to the extent of μ.

Example 3 Synthesis of light-curable spiroacecool resin 424 g of diarylidene pentaerythritol was placed in a 31-hole flask equipped with a stirrer, thermometer, and reflux condenser.
, 1000 g of hydroxyl polyester with a hydroxyl value of 113 and an acid value of 4.9 synthesized from phthalic anhydride and butanediol-1,4-, hydroxyethyl acrylate 22
0g, paratoluenesulfonic acid 5g, hydroquinone 0.
Add 4g and heat and stir at 80-85 for 5 hours.
As a result of infrared analysis, more than 90 coefficients of hydroxyl groups disappeared.

During the reaction, the contents thickened and became difficult to stir, so 800 g of trimethylolpropane triacrylate, 30 g of acrylic acid, and 100 g of vinyl persatate (manufactured by Shell Chemical, trade name Veova-10) were added and dissolved. Thereafter, the reaction proceeded in a monomer-mixed system.

After the reaction, hexanediol diacrylate 400g1
Dimethylaminoethanol 60g, benzophenone 60g
．． In addition, a photocurable spiroacecool resin with a viscosity of about 5 poise was synthesized.

Comparative Example 2 Synthesis of Unsaturated Acrylic-Urethane Resin E 330 g of 1,6-hexamethylene diisocyanate and 460 g of trimethylolpropane triacrylate were placed in a 21-fourth flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser. Weighed out 400 g of 2-hydroxyethyl acrylate and 2 triethylamine from the dropping funnel.
g of the mixture was added dropwise at an internal temperature of around 60°C.

After the dropwise addition was completed, the reaction was carried out at the same temperature for 3 hours, and as a result of infrared analysis, most of the free hydroxyl groups disappeared.

20 g of benzophenone and 20 g of dimethylaminoethanol were added to this to produce a photocurable unsaturated acrylic-urethane resin E.

Resin E was obtained, having a pale yellow color and a viscosity of about 3 poise.

Manufacture of decorative cement board 300im x 300mm x 15 with granite-like pattern mixed with crushed light brown and black stone pieces of 1-2mm.
Two hardened white cement boards with a diameter of 1.0 mm were made, one of which was spray-coated with resin glue and the other with resin E to a thickness of approximately 300 μm. Immediately after the defoaming was completed, the same equipment as in Example 1 was used. Gelation was carried out at a conveyor speed of 10 m/min.

The required time was about 20 seconds.

Further, it was coated in the same manner and cured at a speed of 2.5 m/min.

Artificial stones with a granite-like appearance were obtained in both cases, which were light yellow in color and had a surface hardness of 3 to 4H for the resin coated board and 3H for the resin E coated board.

The curing time for the second coat was about 7 seconds.

When the resulting artificial stones were cut and the thickness of the coating film after polishing was measured, it was found that the coating thickness was about 250-270μ, and that about 400-600μ had penetrated and hardened into the base material.

Each artificial stone was placed facing south at 45 degrees and subjected to a weather resistance test.

After 10 months of summer, the artificial stone made with light-curing spiroacecool resin did not change its hue, but rather seemed to have become whiter, and its gloss reflection retention rate was 90.
Although the change in surface gloss was not discernible to the naked eye,
The artificial stone using photocurable unsaturated acrylic-urethane resin E had a significant yellowing, and the gloss reflection retention rate was 72%, which was a considerable difference.

Example 4 Synthesis of light-curable spiroacecool resin F 640 g of diarylidene pentaerythritol was placed in a 21-hole flask equipped with a stirrer, thermometer, and reflux condenser.
, 342 g of 2-hydroxypropyl acrylate, 134 g of trimethylolpropane, 3.5 g of p-toluenesulfonic acid, 0.49 g of hydroquinone, and 5 g of phosphorous acid were heated and stirred at 90-95°C for 5 hours. As a result of infrared analysis, It was determined that about 85 units of hydroxyl groups had disappeared.

After the reaction was completed, 5 g of diethylamine was added.

The reaction product (a) was pale yellowish brown and sloppy.

To 100 parts of this reaction product (a), 80 parts of trimethylolpropane triacrylate, 5 parts of acrylic acid, 15 parts of hexanediol acrylate, and 2 parts of benzophenone were added.
A photocurable spiroacecool resin F was synthesized.

The viscosity was about 9 poise. Comparative Example 3 Production of photocurable polyester-acrylate resin G Into a 11-three-bottle flask equipped with a stirrer, thermometer, and reflux condenser, 296 g of phthalic anhydride, 128 g of glycidyl acrylate, and 1.34 g of phenyl glycidyl ether were added.
．． 9. Prepare 7 g of acrylic acid, 2 g of trimethylbenzylammonium chloride, and 0.3 g of hydroquinone,
When the reaction was carried out at 10-120'C, the acid value was 14.9.

Add this to 100g of pentaerythrite triacrylate,
Dissolved in 300 g of hexanediol diacrylate.

A light tan polyester-acrylate resin was obtained.

20 g of benzophenone and 5 g of diethylamine were added to this to obtain a photocurable polyester-acrylate resin G.

The viscosity of this resin G was about 10 poise at room temperature.

Preventing terrazzo aggregate from lifting When terrazzo tiles or terrazzo tiles for pavement are worn down over a long period of time, the hardness and wear reduction rate of the aggregate (seed stone) and cement paste parts are different, so the aggregate comes out and causes the cement to slip out. A phenomenon occurs in which the lower part of the body slumps.

If this phenomenon is further accelerated, the aggregate will be torn off and become crumbly, and the reinforcing wire embedded inside will be exposed.

In order to prevent these phenomena, terrazzo is heated at 110℃ for 2
After drying for 4 hours to an absolutely dry state, each resin E1 and resin G were spray coated to a thickness of 100 μm, and after defoaming, they were immediately irradiated with the ultraviolet irradiation device of Example 1 at a conveyor speed of 8.0 m/min. , gelatinized.

The time required for gelation was approximately 10 seconds. Furthermore, the top coating was similarly cured at a rate of 3 m/min.

The resulting protective coated terrazzo fixes the cement paste and prevents the aggregate from lifting up, making it extremely wear resistant and also has an efflorescence prevention effect, both of which have a significantly improved appearance. Obtained.

In this case, the thickness of the terrazzo impregnated was about 300 μm in both cases.

The surface hardness when the photocurable spiroacecool resin F was coated was 5H1, and the surface hardness when the photocurable polyester-acrylate resin G was coated was 3 to 4H.

When both were left outdoors for a year, the terrazzo coated with Spiroacecool Resin F showed almost no change in color and no cracks, but polyester acrylic resin 1~
The terrazzo coated with Resin G had progressed to yellowing considerably, and there were large racks in three places.

Example 5 To 100 parts of the reaction product (a) produced in Example 4, 30 parts of hexanediol diacrylate and 3 g of penzoin butyl ether were added to synthesize a photocurable spiroacecool resin H.

The viscosity was about 60 poise.

Painting of porous red sandstone Porous red sandstone cut into pieces with a thickness of 16 mrn, a length of 200 mvt, and a width of 600 mm was coated with resin H, and after smoothing the surface uniformly, it was irradiated with ultraviolet rays in the same manner as in Example 1. Gelling is carried out using an apparatus at a conveyor speed of 6.3 m/min.

The time required for gelation was 6 seconds. After gelation, the photocurable unsaturated spiroacecool resin prepared in Example 3 was spray-painted to a thickness of 100 μm, and after waiting until the surface became uniform, the same ultraviolet rays were applied again at a speed of 3 m/min. passed through an irradiation device.

Cure time was 5-6 seconds. The surface of the obtained coated sandstone is beautiful and has high hardness, completely eliminating the drawbacks of sandstone, such as easy surface crumbling and lack of hardness.

When the side surface of the obtained painted stone was polished and the coating thickness was measured, it was 70μ to 300μ, and the inside of the stone was 50μ to 300μ.
It was observed that about 1400 μm of penetration had occurred.

Example 6 100 parts of a black-rimmed spherical material with a diameter of 2 to 5 mm made from slag was mixed with 10 parts of an unsaturated polyester resin containing a hardening agent, and heated to 80°C for 30 minutes at 100 kg/C.
Hold under pressure of TL, 30CrrL×30CrrL×
A porous plate of 1 cfrL was prepared.

The photocurable unsaturated spiroacecool resin H produced in Example 5 was applied to this porous plate by smoothing it with a spatula and then uniformly coated. The gel was allowed to pass through and gel at a speed of 1 minute.

The time required for gelation was approximately 6 seconds.

Further, as a top coat, the photocurable spiroacecool resin A produced in Example 1 was spray coated to a thickness of 100 μm.

Next, irradiation was performed at a speed of 3.3 m/min using an ultraviolet irradiation device using a 12 kW high-pressure mercury lamp.

A wall material with an outstandingly beautiful appearance was obtained.

Surface hardness 4H, cut surface measurement results, coating thickness approximately 100μ
100 to 3000 microns of paint had penetrated into the interior, and was completely cured to the deepest part.

Reference Examples Regarding the painted products described in each example and comparative example, JI
When the smoke generation coefficient was investigated using the flame retardant test prescribed in S-AI-321, the following results were obtained, which significantly emphasized the advantage of the spiroacecool structure in terms of smoke generation.

Claims (1)

[Scope of Claims] 1. On the surface of a porous inorganic base material of a hydrated cured product or a cured product of unglazed pottery or brick or a water-absorbing stone or slag, in a natural environment atmosphere, the porous base material is permeable. A spiroacecool resin paint having more than one photocurable acryloyl group or methacryloyl group is applied and penetrated, and when the paint has penetrated into the base material to a depth of 5 to 5000 μ, ultraviolet rays are irradiated. A method for improving the surface properties of substrates. 2. The method according to claim 1, in which a base material made of gypsum is used as the hydration-curable porous inorganic base material. 3. The method according to claim 1, wherein the hydration-hardening porous inorganic base material is a base material containing cement as a binder and aggregate. 4. The method according to claim 1, in which the hydration-hardening porous inorganic base material uses cement as a binder and is patterned with aggregate used. 5. The method according to claim 1, wherein the hydration-curable porous inorganic base material is a base material made of gypsum as a binder and aggregate mixed therein. 6. The method according to claim 1, which uses gypsum as a binder as the hydration-curable porous inorganic material and uses a substrate patterned with aggregate. 7. The method according to claim 1, in which the porous and water-absorbing stone is any one of Tako stone, Oya stone, and rigid sandstone. 8. The method according to claim 1, in which an artificial stone made of slag is used as the porous and water-absorbing inorganic stone. 9. The method according to claim 1, wherein the hydration-curable porous inorganic base material is a base material containing a hardened polyester board crushed material containing artificial pearl foil as an aggregate and cement as a binder.