JP6530291B2 - Hydraulic polymer cement composition - Google Patents

Description

  The present invention relates to a hydraulic polymer cement composition suitable for a food factory floor where washing with hot water is frequently performed, and in particular, it is excellent in thermal shock resistance due to repeated flowing of hot water and cold water, and impact resistance by falling balls. The present invention relates to a hydraulic polymer cement composition having a thickness of 3 mm to 5 mm applied to a surface of a concrete foundation, and further relates to a hydraulic polymer cement composition excellent in mold resistance.

  Conventionally, as a resin cement composition excellent in hot water resistance, abrasion resistance and impact resistance, polyester polyol and polyphenyl polymethyl polyisocyanate having a molecular weight of 1000 to 3000 and having hydroxyl groups at both ends and having a side chain, and hydraulic cement A resin cement composition has been proposed which is characterized in that it is blended with an aggregate containing the following (Patent Document 1).

Unexamined-Japanese-Patent No. 2004-292209

  However, although the resin cement composition described in Patent Document 1 is excellent in hot water resistance, the cured product is immersed in hot water of 90 ° C. for 28 days, and changes in the appearance are visually evaluated and evaluated as normal. The evaluation method is not an evaluation method that simulates, for example, cleaning with hot water actually performed on a food factory floor, but is at least at least for use as a food factory floor. There is a problem that it is necessary to determine that the evaluation result is good after performing an evaluation method that simulates cleaning with hot water as performed on a food factory floor.

  In addition, the resin cement composition described in Patent Document 1 has a problem that it may be applied to the surface of a concrete foundation and gradually faded in color after hardening, and further, it may be temporarily performed on the food factory floor. There is a problem that the mildew resistance is not sufficient when it is evaluated by the evaluation method that simulates the cleaning with the above-mentioned hot water by simulation.

  The problem to be solved by the present invention is that the coating workability is good even if it is applied to a thickness of 3 mm to 5 mm, which is a little thinner than before, and it is a thermal as practiced on a food factory floor Even if the evaluation method simulating the washing with water is performed, the coating material does not peel off or break due to repeated flowing down of the hot water, and the color tone of the coating film surface gradually fades after curing. Hydraulic polymer which is excellent in thermal shock resistance due to repeated flowing down of the hot water and which does not peel off even if a heavy material falls, while having sufficient mildew resistance To provide a cement composition.

  The invention according to claim 1 is a hydraulic polymer cement composition comprising a water-dispersed polyol, a polyisocyanate, a cement, an aggregate, and water, which is applied to a thickness of 3 mm to 5 mm on a concrete base surface, The water-dispersed polyol comprises castor oil-modified bifunctional polyol, castor oil-modified trifunctional polyol, tetrafunctional polyol having a bisphenol A skeleton, a diluent, an emulsifier and water, and the hydroxyl equivalent of the water-dispersed polyol is 250 to 450 The hydroxyl equivalent of castor oil modified trifunctional polyol is 250 to 450, and the hydroxyl equivalent of tetrafunctional polyol having bisphenol A skeleton is 250 to 450, castor oil modified bifunctional polyol and castor oil modified trifunctional polyol and bisphenol A mixture of tetrafunctional polyols having an A skeleton is a water-dispersed polyol 1 20-40 parts by weight in 0 parts by weight, the diluent contains alkyl sulfonic acid phenyl ester and dioctyl phthalate, and the alkyl sulfonic acid phenyl ester is 5-15 parts by weight in 100 parts by weight of water-dispersed polyol, and phthalic acid Bis (2-butoxyethyl) is 20 to 40 parts by weight in 100 parts by weight of water-dispersed polyol, and the total number of parts of cement and aggregate is 75 to 90 parts by weight in 100 parts by weight of the whole composition. The present invention provides a hydraulic polymer cement composition characterized in that the value obtained by dividing the hydroxyl group equivalent of the above by the NCO equivalent of the polyisocyanate is 2-3.

  The invention according to claim 2 provides the hydraulic polymer cement composition according to claim 1, wherein the polyisocyanate is polymethyl polyphenyl polyisocyanate.

  The invention according to claim 3 further provides a hydraulic polymer cement composition according to claim 1 or 2, further comprising a fungicide comprising a benzimidazole compound.

  The hydraulic polymer cement composition of the present invention has good coating workability even when it is applied to a thickness of 3 to 5 mm, which is slightly thinner than before, and it is also hot water as practiced on food factory floors. It is effective in having sufficient thermal shock resistance that peeling, a crack, etc. do not generate | occur | produce, even if it wash | cleans by. In addition, after curing, the color tone of the coating film surface does not gradually become whitish, and furthermore, there is an effect of having impact resistance such that peeling does not occur even if a heavy material falls.

  In particular, the hydraulic polymer cement composition according to claim 3 has the effect of maintaining mold resistance for a long time even when hot water is washed, and in particular the effect of being excellent in use as a food factory floor is there.

  The present invention will be described in detail below.

  The hydraulic polymer cement composition according to the present invention is a hydraulic polymer cement composition comprising a water-dispersed polyol, a polyisocyanate, a cement, an aggregate and water, which is applied to a surface of a concrete base to a thickness of 3 mm to 5 mm. The water-dispersed polyol comprises castor oil-modified bifunctional polyol, castor oil-modified trifunctional polyol, tetrafunctional polyol having a bisphenol A skeleton, a diluent, an emulsifier and water, and the hydroxyl equivalent of the water-dispersed polyol is 250 to 250 The hydroxyl equivalent of castor oil modified trifunctional polyol is 250 to 450, and the hydroxyl equivalent of tetrafunctional polyol having bisphenol A skeleton is 250 to 450, castor oil modified bifunctional polyol and castor oil modified trifunctional A mixture of a polyol and a tetrafunctional polyol having a bisphenol A skeleton is 20 to 40 parts by weight in 100 parts by weight of dispersed polyol, the diluent contains alkyl sulfonic acid phenyl ester and dioctyl phthalate, and the alkyl sulfonic acid phenyl ester is 5 to 15 parts by weight in 100 parts by weight of water dispersed polyol, Dioctyl phthalate is 20-40 parts by weight in 100 parts by weight of water-dispersed polyol, and the total number of cement and aggregate is 75-90 parts by weight in 100 parts by weight of the whole composition, and the hydroxyl equivalent of water-dispersed polyol is It is a hydraulic polymer cement composition characterized in that the value divided by the NCO equivalent of polyisocyanate is 2 to 3, and the hydraulic polymer cement composition further comprises a fungicide comprising a benzimidazole compound. Hydraulic polymer cement composition characterized in that, if necessary, other than these Pigments and dispersing agents, additives such as defoaming agents can be incorporated.

  As described above, the water-dispersed polyol used in the hydraulic polymer cement composition of the present invention comprises a castor oil modified bifunctional polyol, a castor oil modified trifunctional polyol, a tetrafunctional polyol having a bisphenol A skeleton, a diluent and an emulsifier. And water, the diluent comprising alkyl sulfonic acid phenyl ester and dioctyl phthalate. In particular, 5 to 15 parts by weight in 100 parts by weight of the water-dispersed polyol is preferable, and the composition is coated to a thickness of 3 to 5 mm on a concrete base surface by blending the alkylsulfonic acid phenyl ester. When applied, the resin can be uniformly floated on the surface of the coating material, and the coating workability can be improved. A commercially available alkylsulfonic acid phenyl ester is Mezamol (trade name, manufactured by Bayer).

  The dioctyl phthalate contained in the diluent is preferably 20 to 40 parts by weight in 100 parts by weight of the water-dispersed polyol, and the composition can be made to have a thickness of 3 to 5 mm on the concrete base surface by blending the dioctyl phthalate. The coating workability at the time of coating on the surface becomes good.

  The hydroxyl equivalent of castor oil-modified trifunctional polyol and tetrafunctional polyol having a bisphenol A skeleton mixed in a water-dispersed polyol is preferably 250 to 450, and if the hydroxyl equivalent is less than 250, curing as a hydraulic polymer cement composition becomes fast As the hydroxyl equivalent exceeds 450, the hydraulic polymer cement composition becomes insufficient in strength after curing.

  In addition, the hydroxyl equivalent of the castor oil-modified bifunctional polyol blended in the water-dispersed polyol is the blend of the above-described diluent, water, and emulsifier blended so that the hydroxyl equivalent of the water-dispersed polyol becomes 250 to 450. Adjust by amount.

  As an emulsifier to be used for the water-dispersed polyol, any of synthetic surfactants, resin acid salt surfactants and protein surfactants can be used, and as surfactants, anionic surfactants and cationic surfactants can be used. Surfactants, nonionic surfactants and amphoteric surfactants can be used alone or in combination. The emulsifier is selected from these active agents so that the coating workability of the composition becomes good by the following evaluation method, and the compressive strength of the coating material after curing becomes sufficient. Dare more preferred emulsifiers include alkyl benzene sulfonates.

  The polyisocyanate used in the hydraulic polymer cement composition of the present invention has good workability, and also has high curing ability at low temperature and high strength after curing, so that it is a polymer comprising 4,4'-diphenylmethane diisocyanate. It is preferred to use MDI (polymethyl polyphenyl polyisocyanate) and the NCO equivalent is preferably 100-150. If the NCO equivalent is less than 100, the cured product may swell due to foaming or the like, and the finish may be poor. If the NCO equivalent is more than 150, the strength after curing may be insufficient. Of course, other aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates and the like can also be used, and can be used in combination. As a commercially available polymeric MDI, there is Lupranate M5S (trade name, NCO equivalent 135, manufactured by BASF INOAC polyurethane).

  The value obtained by dividing the hydroxyl equivalent of the water-dispersed polyol by the NCO equivalent of the polyisocyanate is preferably 2 to 3, and if the value is less than 2 and more than 3, the color tone of the present composition may become slightly brownish after curing. .

  The antifungal agent comprising a benzimidazole compound used in the hydraulic polymer cement composition of the present invention is subjected to hot water cleaning because it has high heat stability and pH stability, and contains cement as a composition It is used as a fungicide suitable for the present hydraulic polymer cement composition. As a commercial product, there is Courtside D2 (trade name, manufactured by Nippon Envirochemicals Co., Ltd.) as a 10% water suspension. The compounding amount of the fungicide comprising the benzimidazole compound is preferably 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the whole composition. If the amount is less than 0.1 parts by weight, the antifungal effect is insufficient. If the amount is more than 0.3 parts by weight, the storage stability is lowered and the cost is increased.

  The cement used in the hydraulic polymer cement composition of the present invention is mainly intended to apply a water-based polyurethane composition of the present invention to floor base concrete to impart an aesthetic appearance, so that a specific color tone can be imparted, It is preferred to use white Portland cement. In addition, ordinary portland cement, alumina cement, blast furnace cement, and early strength portland cement can be used in combination. The blending amount of cement is 10 to 15 parts by weight in 100 parts by weight of the whole composition.

  In the aggregate used for the hydraulic polymer cement composition of the present invention, a powder of Geishi powder having a particle diameter of 0.5 to 1.5 mm, borax having a particle diameter of 0.21 to 1.18 mm, and a particle diameter of 0 Used together with .07 to 0.6 mm borax. Gaishi powder is obtained by crushing Geshi broken or discarded in a Gaishi production plant, and has the effect of imparting to the floor the strength, abrasion resistance, heat resistance, etc. possessed by pottery. If the particle diameter is less than 0.5 mm, the coating workability to the floor concrete becomes worse, and if it exceeds 1.5 mm, the dispersibility in the composition and the unevenness of the coating film surface after curing become too large.

  The borax with a particle diameter of 0.21 to 1.18 mm corresponds to borax No. 4 and the borax with a particle diameter of 0.07 to 0.6 mm corresponds to a No. 6 borax. The combined use ratio of the powder of Gaishi powder having a particle diameter of 0.5 to 1.5 mm, borax having a particle diameter of 0.21 to 1.18 mm, and the borax having a particle diameter of 0.07 to 0.6 mm is 0. 9 to 1.1: 3.0 to 4.0: 0.5 to 0.7 is preferable from the viewpoint of coating workability to the floor base concrete, strength development and impact resistance. The ratio of the total amount of garlic powder and these borax to the whole composition is 75 to 90 parts by weight in 100 parts by weight of the whole composition. If the amount is less than 75 parts by weight, the resin floats on the surface of the cured product to lower the slip resistance, and if it exceeds 90 parts by weight, the coating workability becomes poor.

  In addition to the above, it is preferable to blend slaked lime with the hydraulic polymer cement composition of the present invention. The slaked lime absorbs the carbon dioxide gas generated by the urea reaction between the polyisocyanate and water, and the carbon dioxide gas generated until the composition is applied on the floor foundation concrete and hardened hardens the coating film in a specific area. It has the effect of suppressing raising and causing swelling.

  Hereinafter, the present invention will be specifically described in Examples and Comparative Examples.

Example 1
A mixture of castor oil-modified trifunctional polyol having a hydroxyl equivalent of 350, a tetrafunctional polyol having a bisphenol A skeleton having a hydroxyl equivalent of 350, and castor oil modified bifunctional polyol is 30 parts by weight, and mezamol as alkylsulfonic acid phenyl ester Water dispersed polyol A consisting of 10 parts by weight, 25 parts by weight of dioctyl phthalate, 33 parts by weight of water, and 2 parts by weight of emulsifier and having a hydroxyl equivalent of 360 as a whole. 10 parts by weight of (pigment concentration 80% by weight) was added to make the main agent part 100 parts by weight. Further, polymethylpolyphenyl polyisocyanate lupranate MB5S having an NCO equivalent of 135 was used as the polyisocyanate to make a curing agent part 100 parts by weight. In the aggregate, 160 parts by weight of Serben (trade name, manufactured by Okmura Cellam Co., Ltd.) having a particle diameter of 0.5 to 1.5 mm as glaze powder and borax with a particle diameter of 0.21 to 1.18 mm: Tohoku borax 4 No. (product name, manufactured by Tohoku Sasa Co., Ltd.) and 550 parts by weight, and borax with a particle diameter of 0.07 to 0.6 mm: using 100 parts by weight of Tohoku Sesame No. 6 (trade name, manufactured by Tohoku Sasa Co., Ltd.) 100 parts by weight of white Portland cement (manufactured by Pacific Cement Co., Ltd.) was used as an aggregate of 910 parts by weight of aggregate and cement of the hydraulic polymer cement composition of Example 1.

  In the aggregate and cement, cement bone of the hydraulic polymer cement composition of Example 1 was prepared by uniformly mixing in advance the above Geishi powder, two types of borax and white Portland cement, and further adding 40 parts by weight of slaked lime. The material part was 950 parts by weight. 100 parts by weight of the main agent in Example 1 and 100 parts by weight of the curing agent in Example 1 and 950 parts by weight of cement aggregate in Example 1 for coating on floor concrete and evaluating the following evaluation items The mixture was used as the hydraulic polymer cement composition of Example 1.

Example 2
Example 1 2 150 parts by weight of the hydraulic polymer cement composition of Example 1 above and 2 parts by weight of a coated side D2 (10% water suspension) as a fungicide comprising a benzimidazole compound and uniformly mixed Hydraulic polymer cement composition.

Comparative Example 1
Instead of 100 parts by weight of the main component in Example 1, 35 to 40 parts by weight of castor oil-modified trifunctional polyol having a hydroxyl equivalent of 350 and 3 to 8 parts by weight of a tetrafunctional polyol having a bisphenol A skeleton having a hydroxyl equivalent of 350 And 20 to 25 parts by weight of mezamol as alkylsulfonic acid phenyl ester, 30 parts by weight of water, and 90 parts by weight of 100 parts by weight of water-dispersed polyol B having a total hydroxyl equivalent of 750 by 2 parts by weight of an emulsifier. A hydraulic polymer cement composition of Comparative Example 1 was prepared in the same manner as in Comparative Example 1 except that 10 parts by weight of colored toner (pigment concentration: 80% by weight) was added to make the main agent part 100 parts by weight.

Comparative Example 2
Instead of 100 parts by weight of the main component in Comparative Example 1, 48 parts by weight of a mixture of castor oil-modified trifunctional polyol and castor oil-modified bifunctional polyol, 15 parts by weight of dioctyl phthalate, and 30 parts by weight of water; Color toner (pigment concentration: 80% by weight) in 90 parts by weight of 100 parts by weight of water-dispersed polyol C consisting of 2 parts by weight of an emulsifier, and 5 parts by weight of mezamol as alkylsulfonic acid phenyl ester The hydraulic polymer cement composition of Comparative Example 2 was used in the same manner as in Comparative Example 2, except that 100 parts by weight of the main agent was added by adding parts by weight.

Comparative Example 3
30 parts by weight of a mixture of castor oil-modified trifunctional polyol and castor oil-modified bifunctional polyol, 28 parts by weight of dioctyl phthalate, and 30 parts by weight of water instead of 100 parts by weight of the main ingredient in Example 2; 10 parts by weight of mezamol as an alkylsulfonic acid phenyl ester and 90 parts by weight of an aqueous dispersion polyol D having a total hydroxyl equivalent weight of 360 with 2 parts by weight of an emulsifier 10 parts by weight of colored toner (pigment concentration 80% by weight) The hydraulic polymer cement composition of Comparative Example 3 was prepared in the same manner as in Comparative Example 3, except that 100 parts by weight of the main agent was added.

[Evaluation items and evaluation method]

[Compression strength]
The cured products of the hydraulic polymer cement compositions of Example 1 and Example 2 and Comparative Examples 1 to 3 after aging for 7 days at 23 ° C. have a compressive strength (N (N) according to the definition of JIS K 6911 / mm ² ) was measured.

Impact resistance
Example 1, Example 2 and comparison which were uniformly mixed on the surface of a 300 mm x 300 mm x 60 mm thick dried concrete plate (5% or less with a ket moisture meter HI-520 concrete range) at 23 ° C under JIS A5371. The hydraulic polymer cement compositions of Examples 1 to 3 are coated with a gold iron to a thickness of 3 to 5 mm and cured for 7 days, and a steel ball with a height of 1 m to 1 kg is dropped 30 times in the central portion. Those with no abnormality such as cracking or peeling were evaluated as ○, and those with abnormalities such as cracking or peeling were evaluated as x.

Thermal shock resistance
Cut a 300 mm x 300 mm x 60 mm thick dried concrete plate (less than 5% with a Kett moisture meter HI-520 concrete range) of JISA5371 into quarters to make a 150 mm x 150 mm x 60 mm thick test plate, A joint portion of 10 mm in depth and 10 mm in width is provided on the surface of the test plate and 5 mm inward from the four sides of the kokuguchi. While the hydraulic polymer cement composition of Example 1, Example 2, Comparative Example 1 to Comparative Example 3 uniformly mixed in the joint portion at 23 ° C. is filled, it is applied to a thickness of 3 to 5 mm, and is applied for 7 days To cure. After that, repeat 5 cycles of 95 ° C hot water at the center of the test body and then 10 cycles of cold water at 20 ° C for 1 cycle. 4000 cycles are repeated as one cycle. Those in which an abnormality occurred were evaluated as x.

[Adhesive]
Example 1, Example 2 and comparison which were uniformly mixed on the surface of a 300 mm x 300 mm x 60 mm thick dried concrete plate (5% or less with a ket moisture meter HI-520 concrete range) at 23 ° C under JIS A5371. The hydraulic polymer cement compositions of Examples 1 to 3 are coated with a gold iron to a thickness of 3 to 5 mm and cured for 7 days, and the hydraulic polymer cement composition of 40 × 40 mm portion by a mechanical strength tester. The adhesion strength between the object and the concrete plate was measured. As for the state of destruction, the base concrete 100% cohesive failure was evaluated as ○, and the other was evaluated as x.

[Anti-mold]
The cured product of the hydraulic polymer cement composition of Example 1, Example 2 and Comparative Example 1 to Comparative Example 3 after 7 days of aging at 23 ° C. was subjected to five divisions of hot water at 95 ° C. and then at 20 ° C. The thermal shock was applied 250 times, where 1 cycle of cold water was allowed to flow down for 10 minutes, and the test specimen after that was subjected to JIS Z 2911 mold resistance test method (plastic product test (method A: dry method). Place the porcelain sinter on which the test fungus mixed spores are attached and dried on the test specimen (5 cm × 5 cm) inside, place the glass plate and cover and incubate at 26 ± 2 ° C for 4 weeks to observe the appearance of mycelial growth. The observed and evaluated method is as follows: Method A medium is mineral salt agar medium, and test bacteria are Aspergillus niger, Penicillium pinophilum, Paecilomyces vario tii, Trichoderma virens, and Chaetomium globosum.
0: No mold growth observed with naked eye and under a microscope.
1: The growth of mold is observed with the naked eye and can be clearly confirmed under a microscope.
2: Mold growth is observed with the naked eye, and the area of the growth portion is less than 25% of the total area of the sample.
3: Mold growth was observed with the naked eye, and the area of the growth portion was 25% to less than 50% of the total area of the sample.
4: Mycelium grows well, and the area of the growth part is 50% or more of the total area.
5: Mycelial growth is intense and covers the entire surface of the sample.

[Painting workability]
Example 1, Example 2 and comparison which were uniformly mixed on the surface of a 300 mm x 300 mm x 60 mm thick dried concrete plate (5% or less with a ket moisture meter HI-520 concrete range) at 23 ° C under JIS A5371. The application of the hydraulic polymer cement compositions of Examples 1 to 3 to a thickness of 3 to 5 mm with a gold iron was evaluated for ease of application. A sample with good coating workability was evaluated as ○, and a sample with low fluidity of the composition and not uniformly spread on the surface of a concrete slab was evaluated as x.

[Coating film surface finish]
Example 1, Example 2 and comparison which were uniformly mixed on the surface of a 300 mm x 300 mm x 60 mm thick dried concrete plate (5% or less with a ket moisture meter HI-520 concrete range) at 23 ° C under JIS A5371. The hydraulic polymer cement compositions of Examples 1 to 3 were each coated with a gold iron in a thickness of 3 to 5 mm, and the state of the coated film surface after aging at 23 ° C. for 7 days was visually evaluated. A state in which the entire coating film surface was covered with the resin in a uniform state was evaluated as ○, and a state in which the resin was covered in a nonuniform state was evaluated as x.

[Color tone stability]
The hydraulic polymer cement compositions of Example 1 and Example 2 and Comparative Examples 1 to 3 uniformly mixed on a floor base concrete and coated with a gold iron to a thickness of 3 to 5 mm and cured. It is confirmed visually that the color tone (colored state) of the surface is good, and this state is taken as the initial color tone. The color tone of the coating film surface is again observed visually after leaving at 23 ° C. for 28 days, and the color tone of the initial color tone is changed and whitened is regarded as x, and the color tone of the initial color tone is maintained without whiteness. evaluated.

[Evaluation results]
The evaluation results are shown in Table 1.

Claims (3)

  A hydraulic polymer cement composition comprising a water-dispersed polyol, a polyisocyanate, a cement, an aggregate, and water which is applied to a thickness of 3 mm to 5 mm on a surface of a concrete foundation, wherein the water-dispersed polyol is castor oil modified It is composed of a bifunctional polyol, a castor oil modified trifunctional polyol, a tetrafunctional polyol having a bisphenol A skeleton, a diluent, an emulsifier and water, and the hydroxyl equivalent of the water-dispersed polyol is 250 to 450. The hydroxyl equivalent is 250 to 450, and the hydroxyl equivalent of the tetrafunctional polyol having a bisphenol A skeleton is 250 to 450, and the castor oil modified bifunctional polyol, the castor oil modified trifunctional polyol, and the tetrafunctional polyol having a bisphenol A skeleton The mixture is 20 to 40 in 100 parts by weight of water-dispersed polyol Parts by weight, the diluent comprises alkyl sulfonic acid phenyl ester and dioctyl phthalate, wherein the alkyl sulfonic acid phenyl ester is 5 to 15 parts by weight in 100 parts by weight of the water dispersed polyol, and dioctyl phthalate is 100 parts by weight water dispersed polyol 20 to 40 parts by weight in total, and the total number of parts of cement and aggregate is 75 to 90 parts by weight in 100 parts by weight of the whole composition, a value obtained by dividing the hydroxyl equivalent of water-dispersed polyol by NCO equivalent of polyisocyanate The hydraulic polymer cement composition characterized in that is 2-3.   The hydraulic polymer cement composition according to claim 1, wherein the polyisocyanate is polymethylpolyphenyl polyisocyanate. The hydraulic polymer cement composition according to claim 1 or 2, further comprising a fungicide comprising a benzimidazole compound.