Use of an inorganic, room-temperature curing organosiloxane composition as an anti-slip floor coating agent.

Abstract

To provide a floor coating agent that contains mainly a one-pack type room temperature-curable organosiloxane composition, which contains no organic solvent, is usable in do-it-yourself carpentering, and is free from a danger of slipping on it even when walking on nylon stocking wearing feet.MEANS FOR SOLVING THE PROBLEM: A slip-resistant floor coating agent comprises a non-solvent room temperature-curable composition containing a liquid organopolysiloxane and a curing agent, including 97-92 wt.% of a liquid organopolysiloxane (A) selected from the group consisting of a methyl silicone oligomer (A1) and a methyl / phenyl silicone oligomer (A2), 8-3 wt.% of a curing agent (B), and 0-5 wt.% of a crosslinking agent (100 wt.% as a whole), where a weight ratio of the methyl silicone oligomer (A1) and the methyl / phenyl silicone oligomer (A2) is in the following range: 75-55 wt.% of the methyl silicone oligomer (A1) and 45-25 wt.% of the methyl / phenyl silicone oligomer (A2).SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to an anti-slip floor coating agent (floor coating agent) mainly composed of silicone resin, and more particularly to the use of a one-component, moisture-curing organosiloxane composition as an anti-slip floor coating agent that eliminates the risk of slipping even when walking while wearing nylon stockings.

[0002] The floor coating agent of the present invention possesses anti-slip properties without impairing the inherent properties of silicone resin, such as stain resistance, adhesion resistance, graffiti resistance, and water repellency. Therefore, it can be used safely and does not stress pets, making it advantageous for use in a wide range of fields, including nursing homes and hospitals. Furthermore, the silicone floor coating agent of the present invention can be advantageously used not only on flooring but also on stairs, handrails, and other applications where it is necessary to eliminate the risk of slipping. [Background technology]

[0003] Flooring materials encompass a wide variety of options, including flooring, plywood, laminate flooring, tiles, and carpets for homes and shops, as well as flooring for hospitals, gyms, sports facilities, raised access floors, roads, and ship decks. They are classified into numerous categories based on material, function, and application. The properties, performance, and functions required of these flooring materials vary greatly depending on the material and application. While the requirements for stone and metal flooring differ from those for wood and plastic flooring, generally required properties, performance, and functions include durability, safety, stain resistance, scratch resistance, chemical resistance, and impact resistance. For hospitals and pet areas, additional requirements include antibacterial properties, deodorizing effects, and viral resistance, as well as compatibility with underfloor heating, gloss, and ease of maintenance.

[0004] There are four types of floor coatings commonly used to protect residential flooring: glass floor coatings, UV floor coatings, silicone floor coatings, and urethane floor coatings. Glass floor coatings offer excellent chemical resistance and are resistant to pet urine. UV floor coatings offer excellent water resistance and are suitable for kitchen and dining room floors. Silicone floor coatings are non-slip and safe for the elderly and pets. Urethane floor coatings are highly resistant to friction and are useful for preventing scratches caused by dragging chairs.

[0005] In any flooring material, anti-slip properties are required. The characteristic of not slipping when people or animals walk on it is generally called "anti-slip properties." This "anti-slip property" is defined by various standards depending on the application field. In the field of "floor coating," a moderate friction characteristic (hereinafter referred to as anti-slip property) is required so that people or animals do not stumble or slip and fall when walking on it. In other words, it is desirable to have neither excessive friction nor insufficient friction. There are physical methods such as etching with chemical solutions to impart "anti-slip properties," but chemical methods that treat the coating film itself to have anti-slip properties are more common.

[0006] [Patent Document 1] (Japanese Patent Publication No. 2004-123982) describes a floor coating curable composition that maintains the characteristics of an acrylic silicone coating, comprising a copolymer (A) component whose main chain is substantially made of a vinyl polymer and which has at least one silicon group bonded to a hydrolyzable group in the molecule and also has an amino group, a curing catalyst (B) component, a silane coupling agent (C) component, and a weak solvent (D) component. This floor coating curable resin composition contains a copolymer (A) component having a silyl group bonded to a hydrolyzable group as a base resin that is curable at room temperature in the presence of moisture. However, more than 50% by weight of the units constituting the main chain of the copolymer (A) component are formed from acrylic monomer units.

[0007] [Patent Document 2] (Japanese Patent Publication No. 2005-220332) describes an anti-slip treatment agent for preventing slippage on mineral floor surfaces in various facilities such as swimming pools, bathrooms, kitchens, entrances, halls, toilets, ramps, and bridges. The anti-slip treatment agent in Example 1 of this patent publication is a white paste obtained by adding 0.15 parts of zanthan gum (polysaccharide) and 30 parts of magnesium chloride (inorganic powder) to 10 parts of water, mixing and stirring thoroughly to form a slurry, then adding 43.35 parts of hydrochloric acid and stirring for about 1.5 hours, then adding 15 parts of acidic ammonium fluoride (inorganic powder), 1 part of organopolysiloxane, and 0.5 parts of surfactant and stirring for about 2 hours. However, the main component of this anti-slip treatment is an inorganic mineral acid, and therefore it cannot be used in ordinary households.

[0008] There are two main chemical methods used to impart anti-slip properties to floor coatings used to protect general residential flooring: one involves adding various friction-enhancing agents to the floor coating agent, and the other involves selecting an anti-slip floor coating agent whose coating film itself has appropriate frictional properties.

[0009] As an example of the former, [Patent Document 2] (Japanese Patent Publication No. 2007-191672) describes the addition of microballoons to a two-component epoxy resin paint (at a ratio of 10 parts by volume to 100 parts by volume of the paint component). This method increases costs because it involves adding friction-improving materials to the vehicle (resin coating).

[0010] An example of the latter is [Patent Document 3] (Japanese Patent No. 6749009). The floor anti-slip agent described in this patent consists of a silicone resin dissolved and dispersed in a solvent. This silicone resin has a weight-average molecular weight of 1000 or more, and is in M ​​units (R1R2R3SiO 1 / 2 ) and Q units (SiO 4 / 2 ) is characterized by being composed of the above, with the amount added being 0.1 wt% to 5.0 wt%. In Example 1 of this patent, 1% by weight of decyltrimethoxysilane and 3% by weight of trimethylsiloxysilicate are dissolved in 95.75% by weight of ethanol. Most of the floor anti-slip agent of this patent is ethanol, and the solvent will evaporate during construction.

[0011] Silicon floor coating agents are known to have excellent "anti-slip properties". However, most commercially available silicon floor coating agents are solutions in which silicone resin is dissolved in a solvent as described in [Patent Document 3], or mixtures of silicone resin and acrylic resin, etc.

[0012] In solvent-based silicon floor coating agents, the solvent will evaporate during construction, which is not desirable from the perspective of environmental protection. Mixing silicone resin and acrylic resin, etc. to form a water-soluble dispersion or emulsion results in a high price, making it difficult for the general public to easily use it for DIY. Some floor coating agents obtained by dispersing silicone resin in water have problems with recoatability. When recoating after once coating, the coating agent peels off, making uniform recoating difficult.

[0013] Floor coating agents made of silicon compositions mainly composed of inorganic substances were also considered to have no recoatability. The inventors of the present invention attempted to use a floor coating agent made of a silicon composition mainly composed of inorganic substances as a silicon floor coating agent.

[0014] [Patent Document 4] (Japanese Patent Publication No. 7-72250, Patent No. 2137192) discloses a solventless room temperature curable organosiloxane composition with a reduced ratio of organic groups and a significantly increased ratio of Si-O bonds. This solventless room temperature curable organosiloxane composition is composed of the following (A) to (C): (A) Liquid organopolysiloxane (B) Crosslinking agent, (C) Curing catalyst. The above liquid organopolysiloxane (A) has the following general formula (1):

[0015] TIFF0007886512000001.tif35122

[0016] (where: R 1 is a hydrogen atom, a C1 - C5 alkyl group or an acyl group; R 2 ~R 6 are each a group selected from a hydrogen atom, an OR 1 group or a monovalent hydrocarbon group, the same or different, and n is a number from 1 to 15) It consists of one or more compounds represented by the formula, and its silicon component content expressed on the basis of SiO2 oxide is 50% by weight or more. <000E103>The cross - linking agent (B) is represented by the following general formula (2) or (3): R 7 p M·(OR1) 3-p ‥‥‥‥‥(2) R 7 <E000011>Q·(OR1) 4-m ‥‥‥‥‥(3) (where: M is an aluminum or boron element; Q is a silicon, titanium or zirconium element; R 1 is a hydrogen atom, a C1 - C5 alkyl group, an acyl group or an oxime group; R 7 is a group selected from a hydrogen atom, an OR 1 group or a monovalent hydrocarbon group; p is 1 or 2; m is an integer from 1 to 3) It consists of one or more organometallic compounds represented by the formula. The curing catalyst (C) is one or more metal - containing organic compounds of zinc, cobalt, aluminum or tin elements. The above solvent - free room - temperature curing organosiloxane composition contains a catalyst reaction blocking agent, and contains 40% by weight or more of all the metal element components contained in the above three - component mixture composition, expressed on the basis of MO y / 2 (M is an aluminum, boron, silicon, titanium or zirconium element, and y is the valence of the metal element).

[0017] This solvent - free room - temperature curing organosiloxane composition is commercially available under the name of "Ceraton" and is widely used especially as a surface coating for steel structures and tunnel structures. However, it has not been used as an anti - slip floor coating agent.

[0018] Other patents exist for the use of room-temperature curable organopolysiloxane compositions as coating agents. [Patent Document 5] (Japanese Patent Publication No. 2007231182) describes a room-temperature curable polyorganosiloxane composition comprising the following (A) to (E) as essential components: (A) Polyorganosiloxane having a viscosity of 0.1 to 1,000 Pa·s at 25°C and both ends sealed with triarcoxysilyl groups: 5 to 95% by mass, (B) A polyorganosiloxane having a viscosity of 0.1 to 1,000 Pa·s at 25°C and both ends sealed with dialkoxy monoorganosilyl groups: 95 to 5% by mass per 100 parts by mass of polyorganosiloxane, (C) General formula (1) below

[0019] TIFF0007886512000002.tif2687

[0020] (In the formula, R 1 , R 2 and R 3 (where is a monovalent saturated hydrocarbon group, X is an oxygen atom or a divalent hydrocarbon group, and n is a positive number such that the viscosity at 25°C is 0.005 to 100 Pa·s) 1 to 50 parts by mass of a single-terminated trialkoxy polyorganosiloxane curing agent, (D) Specific surface area of ​​50 m 2 Silica powder of 1 to 50 parts by mass, 1g or more (E) Titanium chelate catalyst: 0.1 to 15 parts by mass. However, this room-temperature curable polyorganosiloxane composition is intended for use in various fields such as sealing materials for building materials, adhesives in the electrical and electronic fields, and the transportation industry, and its use as an anti-slip floor coating agent is not mentioned.

[0021] [Patent Document 6] (Japanese Patent Publication No. 2009167420) describes a room-temperature curable organopolysiloxane composition that hardens by a condensation reaction consisting of the following (A) to (D): (A) The viscosity at 25°C is 100 to 500,000 mPa·s, and one molecule contains the general formula; (X) aR 1 3Si-(wherein X is a hydroxyl group or a hydrolyzable group, R 1 Organopolysiloxane (100 parts by weight) containing an average of 1.5 or more terminal groups represented by (where is a monovalent hydrocarbon group or a halogen atom-substituted monovalent hydrocarbon group, and a is 1, 2, or 3), (B) Silane or siloxane oligomer (0.01 to 40 parts by weight) containing three or more silicon atom bonded hydrolyzable groups in one molecule. (C1) Flame retardant agent consisting of a platinum compound (amount of platinum compound equivalent to 1 to 2,000 ppm in the composition in terms of platinum metal) (C2) At least one formula, -(R 2 )(R 3 )SiO-(R 2 )(R 3 )SiO-(wherein, R 2 R is an aryl group, 3 An organosiloxane containing an aryl group and an alkenyl group, having a bond represented by (which is an alkenyl group), with 8 or fewer silicon atoms in one molecule {in an amount of 2 moles or more per mole of platinum atoms in the (C1) component} and (D) Inorganic powder (5 to 300 parts by weight). This room-temperature curable organopolysiloxane composition is also intended for use as a coating agent, sealant, or adhesive for electrical and electronic components, and its use as an anti-slip floor coating agent is not described.

[0022] [Patent Document 7] (Japanese Patent Publication No. 2015110792) describes a room-temperature curable alkoxy-curable polysiloxane composition containing the following components (a) to (d): (a) Hydroxyl-terminated polyorganosiloxanes, (b) Polyfunctional alkoxysilanes, and (c) Organic titanium compounds having the following general formula I or II, or multipolymers thereof having a degree of polymerization of 2 to 10, (i) Organic titanium compound I having the following general formula I: TIFF0007886512000003.tif1787

[0023] (In the formula, n is any integer between 1 and 4, R 1 R is a saturated monovalent hydrocarbon group having 1 to 16 carbon atoms. 2 R is a saturated divalent hydrocarbon group having 1 to 16 carbon atoms, 3 (A is a saturated monovalent hydrocarbon group having 1 to 32 carbon atoms, where the hydrocarbon group includes both linear and branched structures.) (ii) Organic titanium compounds II having the following general formula II: TIFF0007886512000004.tif1792

[0024] (In the formula, m is any integer between 2 and 4, R 4 R is a saturated monovalent hydrocarbon group having 1 to 16 carbon atoms. 5 R is a saturated divalent hydrocarbon group having 1 to 16 carbon atoms, 6 (A is a saturated monovalent hydrocarbon group having 4 to 32 carbon atoms, where the hydrocarbon group can be both linear and branched.) (d) Catalyst (optional component) This room-temperature curable alkoxy-curable polysiloxane composition is directly used as a sealant, adhesive, and coating material for applications in the building, electronics, electrical, and automotive sectors. However, this patent does not describe its use as an anti-slip floor coating agent.

[0025] As described above, to the best of the applicant's knowledge, no room-temperature curable polyorganosiloxane compositions have been found to be used as anti-slip floor coating agents. In fact, when an inorganic-based silicone composition is used as a floor coating agent, it does not exhibit the same excellent "anti-slip properties" as commercially available general solvent-type or emulsion-type silicone floor coating agents. The reason for this is unknown, but it is thought that because the cured product has a high silicon content, its inorganic properties are strongly expressed, and it does not become a floor coating agent with excellent anti-slip properties, repaintability, flexibility, and transparency.

[0026] The inventors attempted to use an inorganic-based silicone composition as a floor coating agent. Surprisingly, the inventors discovered that a specific ratio of a specific component in the composition described in [Patent Document 4], which is commercially available under the name "Ceraton," can be used as a silicone floor coating agent with excellent anti-slip properties, repaintability, flexibility, and transparency. In other words, simply using the solvent-free, room-temperature curing organosiloxane composition described in [Patent Document 4] as a silicone floor coating agent does not result in a silicone floor coating agent with the desired excellent properties, but the inventors discovered that a specific ratio of a specific component can be used as a silicone floor coating agent with excellent anti-slip properties, flexibility, and transparency, thus completing the present invention. Contrary to the expectation that inorganic-based silicone compositions generally have no or low anti-slip properties, the inventors discovered that certain types of solvent-free, room-temperature curing organosiloxane compositions can become floor coating agents with excellent anti-slip properties, flexibility, and transparency. [Prior art documents] [Patent Documents]

[0027] [Patent Document 1] Japanese Patent Publication No. 2004-123982 [Patent Document 2] Japanese Patent Publication No. 2007-191672 [Patent Document 3] Patent No. 6749009 specification [Patent Document 4] Special Publication No. 7-72250 [Patent Document 5] Japanese Patent Publication No. 2007231182 [Patent Document 6] Japanese Patent Publication No. 2009167420 [Patent Document 7] Japanese Patent Publication No. 2015110792 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0028] Therefore, the object of the present invention is to provide a floor coating agent with excellent anti-slip properties using a solvent-free, room-temperature curable organosiloxane composition having a silicon component content of 50% by weight or more, expressed on a basis of SiO2 oxide. Another object of the present invention is the use of an inorganic, room-temperature curable organosiloxane composition having a specific composition as an anti-slip floor coating agent. [Means for solving the problem]

[0029] The first object of the present invention is an anti-slip floor coating agent comprising a solvent-free, room-temperature curing composition containing a liquid organopolysiloxane and a curing agent, The following ingredients (A) and (B) in the following weight ratio: (A) At least one liquid organopolysiloxane consisting of a methyl-based silicone oligomer (A1) and a methyl / phenyl-based silicone oligomer (A2), 97-92% by weight (B) Hardener 8-3% by weight The anti-slip floor coating agent is characterized by containing the following, and the weight ratio of methyl-based silicone oligomer (A1) to methyl / phenyl-based silicone oligomer (A2) in the above liquid organopolysiloxane (A): (A1) Methyl-based silicone oligomer 75-55% by weight (A2) Methyl / phenyl-based silicone oligomer, 45-25% by weight.

[0030] The anti-slip floor coating agent of the present invention may further contain a crosslinking agent other than the curing agent (B) in a ratio of 0 to 5% by weight.

[0031] In one preferred embodiment of the present invention, the methyl-based silicon oligomer (A1) described above is a mixture of an oligomer of medium polymerization (A11) and an oligomer of high polymerization (A12), and the weight ratio of the oligomer of medium polymerization (A11) to the oligomer of high polymerization (A12) is preferably 1 / 1.5 to 2.5.

[0032] A second aspect of the present invention is the use of a one-component, room-temperature curable liquid organosiloxane composition that does not contain organic solvents as a floor coating agent for flooring surfaces, The above one-component, room-temperature curing organosiloxane composition contains the following components (A) to (C) in the following weight ratios (100% by weight in total): (A) Liquid organopolysiloxane 97-92% by weight (B) Hardener 8-3% by weight (C) Crosslinking agent other than hardener: 0-5% by weight and include, The use is characterized by the liquid organopolysiloxane (A) containing (A-1) and (A-2) in the following ratios: (A-1) Methyl-based silicone oligomer 75-55% by weight (A-2) Methyl / phenyl-based silicone oligomer, 45-25% by weight.

[0033] The methyl-based silicone oligomer (A1) described above is a mixture of an oligomer of medium polymerization (A11) and an oligomer of high polymerization (A12), and it is preferable that the weight ratio of the oligomer of medium polymerization (A11) to the oligomer of high polymerization (A12) is 1 / 1.5 to 2.5. [Brief explanation of the drawing]

[0034] [Figure 1] Conceptual diagram of the experimental apparatus used to evaluate the "slip resistance" of the flooring material of the present invention. [Figure 2] This graph shows the results obtained when calculating the Stricbeck curve using the experimental setup shown in [Figure 1], with wooden plywood tiles as Sample 1. [Figure 3]This graph shows the results obtained when the Stricbeck curve was calculated using the experimental setup shown in [Figure 1], with ceramic tiles as Sample 1. [Figure 4] This graph shows the results obtained when calculating the Stricbeck curve using the experimental setup shown in [Figure 1], with granite used as sample 1. [Figure 5] A conceptual experimental diagram illustrating the slipperiness of a sloping ramp when walking on it with feet wearing nylon (registered trademark) stockings. [Best Mode for Carrying Out the Invention]

[0035] The inorganic, non-slip, solvent-free, room-temperature curable organosiloxane composition of the present invention is a composition in a specific ratio from the composition described in [Patent Document 4]. Therefore, the components of the composition of the present invention can basically be selected from the components described in [Patent Document 4]. In other words, the present invention has found a composition with excellent anti-slip properties, flexibility, and transparency from among the compositions described in [Patent Document 4]. Accordingly, the reaction mechanism of the composition of the present invention and the contents of each component of the composition can be found by referring to the specification of [Patent Document 4], and the contents described in [Patent Document 4] (Japanese Patent Publication No. 7-72250) constitute a part of the specification of this application.

[0036] The term "polymer" encompasses oligomers and includes both homopolymers and copolymers. In this specification, the term "silicon" refers to polysiloxane polymers or oligomers based on a structure in which silicon and oxygen atoms are arranged alternately, and in this specification, "silicon" and "siloxane" are used interchangeably.

[0037] The term "organopolysiloxane" is used as a general term for substances having Si-O bonds (siloxane bonds), and in this specification, it refers to oligomers having alkoxysilyl groups and reactive functional groups, which may also have silanol functional groups. The silicon content of the organopolysiloxane used in this invention, expressed on a basis of SiO2 oxide, is 50% by weight or more. This silicon content is calculated from its molecular formula.

[0038] In this invention, the liquid organopolysiloxane (A) maintains its liquid state, and without adjusting the viscosity with a diluent, the viscosity is 3000 centipoise or less, or the kinematic viscosity at 25°C is 100 mmHg. 2 A low molecular weight polysiloxane compound with a molecular weight of less than / s, and whose weight-average molecular weight is generally 10 2 ~10 5 It's an order.

[0039] The liquid organopolysiloxane (A) of the present invention comprises a methyl-based silicone oligomer (A1) and a methyl / phenyl-based silicone oligomer (A2). Each silicone oligomer (A1) and (A2) is generally widely used and readily available on the market.

[0040] The liquid organopolysiloxane (A) of the present invention can be composed of TD units, which consist of a siloxane compound having a side chain group of a methyl or phenyl group, a D unit having two functional groups, or a T unit having three functional groups, either alone or in combination thereof. While the methyl-based silicon oligomer (A1) can also be represented by a general formula, this would be complex, so in this specification, the methyl-based silicon oligomer (A1) refers to a silicon oligomer having a methyl group and an alkoxy group, particularly a methoxy group, and is, for example, the oligomer shown below (the subscripts a, b, c, d, e, f, g, etc. in the structural formula below are numerical values ​​from 0 to 100, and the viscosity is 3000 centipoise or less or the kinematic viscosity at 25°C is 200 mmHg). 2 (Selected to be less than or equal to / s)

[0041] TIFF0007886512000005.tif143170

[0042] The kinematic viscosity of the organopolysiloxane of the present invention is 10 to 350 mmHg. 2 The interval is / s, preferably 10-300 mm 2 / s, more comfortable 10~100mm 2 The value is / s. Kinematic viscosity is measured at 25°C using an Ostwald viscometer.

[0043] Similarly, methyl / phenyl-based silicon oligomers (A2) refer to silicon oligomers having methyl and phenyl groups and alkoxy groups, particularly methoxy groups, such as the following oligomers (the subscripts a, b, c, d, e, f, g, etc. in the structural formula below are numerical values ​​from 0 to 100, and the viscosity is 10,000 centipoise or less or the kinematic viscosity at 25°C is 300 mmHg). 2 (Selected to be less than or equal to / s)

[0044] TIFF0007886512000006.tif6581

[0045] The silicon content of the solvent-free, room-temperature curable organosiloxane composition of the present invention is 50% by weight or more, expressed on a basis of SiO2 oxide. This silicon content is calculated from its molecular formula.

[0046] In the application of the present invention (anti-slip floor coating agent), the ratio of (A1) to (A2) is important, and any ratio deviating from the following range is unsuitable for use as an anti-slip floor coating agent in the application of the present invention: (A1) Methyl-based silicone oligomer 75-55% by weight (A2) Methyl / phenyl-based silicone oligomer, 45-25% by weight. Anti-slip properties cannot be obtained if the weight ratio of (A1) in liquid organopolysiloxane (A) is less than 55% by weight. Furthermore, problems with coating performance arise if the weight ratio of (A1) exceeds 75% by weight.

[0047] The curing agent (B) can be widely used from among those known as curing agents for silicon oligomers. The term curing agent refers to a compound that promotes the curing of liquid organopolysiloxane (A), and may include a curing catalyst, coupling agent, or crosslinking agent. That is, a crosslinking agent or coupling agent that also functions as a curing catalyst can be used as curing agent (B). In addition to the curing agent (B) of the solvent-free, room-temperature curable organosiloxane composition of the present invention, a crosslinking agent may be further included. This crosslinking agent can be selected from those described in [Patent Document 4]. However, the use of a crosslinking agent is not essential for the applications of the present invention.

[0048] The curing agent (B) can be an organometallic compound comprising one or more combinations of tin, titanium, aluminum, silicon, or zirconium compounds having a functional group consisting of an alkoxy group, an acyloxy group, or an oxime group. Such curing agents are readily available on the market as curing agents for silicon oligomers.

[0049] Examples of organotin catalysts include, but are not limited to, dibutyltin diacetate, bis(acetoxydibutyltin)oxide, bis(lauroxydibutyltin)oxide, dibutyltin bisacetylacetoner, dibutyltin bismaleate monobutyl ester, dioctylbismaleate monobutyl ester, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, dioctyltin diversate, dibutyltin oxide, and dioctyltin oxide.

[0050] Examples of titanium-based catalysts include, but are not limited to, diisopropoxytitanium bis(acetylacetonate), titanium tetra(acetylacetonate), dioctanoxytitanium dioctanate, diisopropoxytitanium bis(ethylacetoacetate), tetra-n-butyl titanate (Tn-BT), tetraisobutyl titanate (Ti-BT), tetra-t-butyl titanate (Tt-BT), tetraisopropyl titanate (Ti-PT), tetraisooctyl titanate (TOT), diisobutylbis(acetylacetonate) titanate (DIBAT), diisopropylbis(acetylacetonate) titanate (DIPAT), diisopropylbis(ethylacetoacetate) titanate, and dibutylbis(ethylacetoacetate) titanate.

[0051] Examples of aluminum compounds include, but are not limited to, aluminum acetylacetone, aluminum bis(ethyl acetate) monon-normal butyrate, aluminum ethyl acetate din-normal butyrate, and aluminum tris(ethyl acetate).

[0052] Examples of coupling agents include, but are not limited to, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.

[0053] The curing agent (B) may be one of the above compounds used alone or two or more used in combination. In particular, it is preferable to use tin compounds such as dioctyl tin dilaurate and dioctyl tin divar satate, which have excellent reactivity; titanium compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, and titanium diisopropoxybis(ethyl acetate) and their hydrolysates; and aluminum compounds such as acetylacetone aluminum, aluminum bis(ethyl acetate) monon-normal butyrate, aluminum ethyl acetate din-normal butyrate, and aluminum tris(ethyl acetate) and their hydrolysates.

[0054] The composition of the present invention may optionally contain other compounds, such as organopolysiloxanes or silane compounds other than those mentioned above, for the purpose of adjusting the viscosity of the curable composition to improve workability, or for the purpose of adjusting the curability of the composition, the hardness, flexibility, adhesion, etc., of the resulting coating film.

[0055] The ratio of liquid organopolysiloxane (A) to hardener (B) is as follows: Liquid organopolysiloxane (A) 97-92% by weight Hardener (B) 8-3% by weight If the ratio of hardener (B) is less than 3% by weight, curing will be insufficient or take too long. Conversely, if it exceeds 8% by weight, undesirable results cannot be obtained.

[0056] The solvent-free, room-temperature curable organosiloxane composition of the present invention may further contain the following optional components (C) and (D) in addition to (A) and (B) above: (C) Catalytic reaction blocking agent (D) Reaction retarder (curing retarder) These components (C) and (D) are optional components, and detailed descriptions of their types, amounts used, etc., can be found in [Patent Document 4] (Japanese Patent Publication No. 7-72250). In the applications of the present invention, it is preferable not to use these components in order to ensure transparency.

[0057] The composition of the present invention may further contain, as needed, various known additives that can be added to room-temperature curable organopolysiloxane compositions, such as pigments, flame retardants, heat resistance improvers, adhesion promoters, thixotropy imparters, and friction modifiers, as long as they do not impair the objectives of the present invention, particularly anti-slip properties and transparency.

[0058] The room-temperature curable composition of the present invention is a one-component type, has low viscosity, and offers excellent workability even without the use of a solvent, making it suitable for use as a coating agent.

[0059] The solvent-free, room-temperature curable organosiloxane composition of the present invention can be prepared by mixing components (A) and (B) (and, if necessary, other additive components) in a container under moisture-free conditions at room temperature for at least 30 minutes until a homogeneous solution is obtained.

[0060] The one-component, room-temperature curing organosiloxane composition of the present invention has one-component storage properties and shows no substantial change even when left at room temperature for 6 months, and can be used as a floor coating agent as is. The application method is not particularly limited, and known methods such as coating using a brush or roll, or spraying can be used. For example, the above one-component, room-temperature curing organosiloxane composition can be applied to the surface of the flooring material and spread evenly with a roll, brush, or soft cloth.

[0061] The one-component, room-temperature curing organosiloxane composition floor coating agent of the present invention hardens at 25°C in approximately 120 hours due to atmospheric moisture (water) (hardness approximately 4H). "Water" refers to water mixed with other organic compounds such as atmospheric moisture, vapor, liquid water, ice, or organic solvents, but atmospheric moisture is preferred. The effective amount of water is sufficient to cause the composition to harden. The resulting cured film exhibits excellent hardness and crack resistance, as well as anti-slip properties.

[0062] The performance of the flooring material of the present invention can be evaluated based on "anti-slip performance" and "coating performance." Evaluation of anti-skid performance The slip resistance of the flooring material of the present invention was evaluated using (1) a "foot-treading" slip test and (2) an inclined slope test door.

[0063] (1) "Step-on slip test" Figure 1 is a conceptual diagram of the experimental apparatus used to evaluate the "slip resistance" of the flooring material of the present invention. In this experiment, a Stricbeck curve is obtained, and the coefficient of friction (μ) is measured based on it. In the experimental apparatus of Figure 1, sample 1 is fixed to a support 7, and the elastic material 2 is slid over sample 1 from left to right using a slider 4, allowing for the investigation of whether the frictional force (F) changes depending on the presence or absence of the coating agent 3 applied to sample 1. The elastic material 2 is fixed to the slider 4 via an inclined stage 5, and a vertical load (P) is applied to the support 7 using a Z-stage 6.

[0064] Figures 2 to 4 show the results of obtaining Stricbeck curves by changing the material of Sample 1. In each figure, the vertical axis is the coefficient of friction (μ), and the horizontal axis is the S value (m). The S value represents these driving conditions, and S = μ·V / P' (where μ is viscosity (Pa·s), V is velocity (m / s), and P is pressure (Pa)). The coefficient of friction depends on the viscosity, velocity, and pressure of the surface. In practice, the coefficient of friction (μ) was determined by keeping the viscosity (μ) and pressure (P) constant and changing the velocity (V), plotting it on the Stricbeck curve, and then determining the coefficient of friction (μ) from the relationship: coefficient of friction (μ) = frictional force (F) / vertical load (P).

[0065] In the experiment simulating the "stomping" motion, the elastic material 2 is not in contact with sample 1 at the start of the measurement. As the elastic material 2 moves from left to right, the Z-stage 6 is raised to bring the elastic material 2 into contact with sample 1, and the vertical load (P) is increased to a predetermined contact pressure. This measurement method simulates the motion when a person steps on the floor. In this case, the left side of the horizontal axis in each figure plots the case of slow speed, and the right side plots the case of fast speed.

[0066] The case where flooring agent 3 was applied to sample 1 and the case where it was not applied were compared. If the increase in the coefficient of friction (μ) was large (it became less slippery), it was classified as having anti-slip properties "present," and if the increase in the coefficient of friction (μ) was small (there was no change in slip resistance or only a small change), it was classified as having anti-slip properties "absent."

[0067] (2) Inclined slope test Figure 5 is a conceptual diagram of an experiment (stocking test) in which slipperiness was investigated by actually walking on an inclined slope with an angle of approximately 30°. In this experiment, women aged 10 to 60 years old (22) (weighing approximately 20 to 65 kg) with no problems walking were tested to see if they could climb on a sample wooden plywood flooring material (11) set on an inclined floor (12) with an angle of 30° while wearing nylon® stockings or socks. The results were evaluated as "not slippery" or "slippery" when compared with and without the application of floor coating agent E1.

[0068] Paint performance (coating performance) Floor coatings require the following properties for the resulting coating film: adhesion (peel strength), crack resistance, repaintability, water resistance, long-term durability, chemical resistance, scratch resistance, stain resistance, heat resistance, UV resistance, and aesthetic appeal. The floor coating agent of the present invention fully satisfies the above-mentioned general performance requirements for floor coatings.

[0069] Since the application workability of the floor coating agents of the present invention differs depending on the composition, only the evaluation results of "application workability" due to differences in composition are shown here. Paintability was evaluated by experienced painters based on the characteristics necessary to obtain a smooth paint film surface (appropriate viscosity, appropriate drying time, and ease of application), and was rated as excellent, good, average, or poor. Painting workability "Excellent" = Painting is extremely easy. "Good" = Easy to paint. "Normal" = Painting work is slightly difficult "Inferior" = Painting work is difficult.

[0070] The floor coating agent covered by this invention can be used in any application such as houses, shops, hospitals, sports gyms, gymnasiums, raised access floors, roads, and ships, but for the sake of simplicity, residential flooring will be used as an example below. However, the floor coating agent of this invention can be used on flooring materials in shops, hospitals, sports gyms, gymnasiums, raised access floors, roads, ships, and the like. [Examples]

[0071] The following describes embodiments of the present invention. Materials used In the examples and comparative examples, commercially available materials shown in [Table 1] were used as the liquid organopolysiloxane A (silicone oligomers A1 and A2) and curing agent B.

[0072] [Table 1] (Note) A11 (Shin-Etsu Chemical Co., Ltd. KR-500), a methyl-based silicone oligomer with a medium polymerization degree. A12 (Shin-Etsu Chemical Co., Ltd. X-40-9225), high polymerization methyl-based silicon oligomer A13 (DOWSIL AY42-163) is a methyl-based silicon oligomer with a specific gravity of 1.07. A14 (DOWSIL SR2402) is a methyl-based silicon oligomer with a specific gravity of 1.16.

[0073] Example 1 Preparation of the floor coating agent of the present invention Commercially available silicone oligomers A11 and A21, as shown in [Table 1], were used as silicone oligomers A1 and A2, and commercially available curing agent B11, as shown in [Table 1], was used as curing agent B in the following weight ratios. Silicone oligomer A11 55% by weight Silicone oligomer A21 40% by weight Hardener B11 5% by weight

[0074] Materials A11, A21, and B11 were placed in a container and mixed under reduced pressure at room temperature for 30 minutes until a homogeneous solution was obtained. The mixture was then cured at room temperature for 48 hours to prepare the room-temperature curable organosiloxane compositions of the present invention. Each of the resulting compositions was single-component and showed no substantial change even after being left at room temperature for 6 months. These room-temperature curable organosiloxane compositions were used as floor coating agent E1.

[0075] Floor coating agent E1 was applied evenly to a sample flooring material of wooden plywood using a roller, and left for 24 hours to allow the coating to harden. The results of evaluating the properties of the resulting cured coating film are as follows.

[0076] Anti-slip performance (1) "Step-on slip test" The "slip resistance" was investigated using the experimental apparatus shown in [Figure 1]. In the experiment, the coefficient of friction (μ) was determined for both cases: when the above floor coating agent E1 was applied to a sample wooden plywood flooring material (1), and when it was not applied. Experimental conditions: Elastic material mounting angle = 0° Vertical load (P)=25 kPa Relative slip velocity V = 0.01 to 1.80 m / s)

[0077] Figure 2 shows the results. Figure 2 represents the Stricbeck curve, with the horizontal axis representing the S value (S = μ·V / P') representing the driving conditions, and the vertical axis representing the coefficient of friction (μ). Figure 2 shows that when the relative sliding speed is slow (on the left side of the horizontal axis in Figure 2), i.e., "when pressing down", the coefficient of friction (μ) is higher when floor coating agent E1 is applied compared to when it is uncoated. On the right side of the horizontal axis in Figure 2 (when the relative sliding speed is fast, in the fluid lubrication region), i.e., "after sliding has started", there is no difference in the coefficient of friction with or without the floor coating agent.

[0078] In this invention, slippage during "stepping" is a problem, so the floor coating agent E1 of this invention has "good" anti-slip properties in the "stepping" slip test.

[0079] Figures 3 and 4 show the results of slip tests when the material of sample flooring (1) was changed to "ceramic tile" and "granite," respectively. These materials (Figure 3 for ceramic tile) and Figure 4 for granite) exhibit similar effects to those in Figure 2.

[0080] (2) Inclined slope test The results of the nylon® stocking test using the equipment shown in [Figure 5] indicated that all participants were able to climb without relying on the safety railing (23) in practice, thus indicating that the stockings were "non-slip."

[0081] Paint performance The "applicability" of floor coating agent E1 was "good".

[0082] Examples 2-4 The same procedure as in Example 1 was repeated, but the type of silicone oligomer A was changed to the following combination while keeping the composition ratio the same: Example 2 = A12 and A22 Example 3 = A13 and A23 Example 4 = A14 and A24 Specifically, silicone oligomer A11 was replaced with A12, A13, or A14, and silicone oligomer A21 was replaced with A22, A23, or A24. The obtained floor coating agents E2, E3, and E4 were applied to the same sample flooring material as in Example 1, and the coating films were cured. The properties of the cured coating films were then evaluated. The results are summarized in [Table 2]. The results from Examples 2-4 demonstrate that the same results can be obtained even when the type of lycorn oligomer is changed.

[0083] Comparative Examples 1-4 In Comparative Examples 1-4, the same procedure as in Examples 1-4 was repeated, but the weight ratio of silicone oligomers A11 and A21 was changed to the following ratio. Silicone oligomer A11 35% by weight Silicone oligomer A21 60% by weight The type of silicone oligomer A in Comparative Examples 1-4 is the same as in Examples 1-4: Comparative Example 1 = A11 and A21 Comparison Example 2 = A12 and A22 Comparative Example 3 = A13 and A23 Comparative Example 4 = A14 and A24 The obtained floor coating agents C1 to C4 were applied to the same sample flooring material as in Example 1, the coating films were cured, and the properties of the cured coating films were evaluated. The results are summarized in [Table 2]. In Comparative Examples 1-4, the increase in the coefficient of friction (μ) was small and the change in slip resistance was small for floor coating agents C1-C4, so the result of the "stepping" slip test was "no anti-slip properties".

[0084] Examples 5-8 The same procedure as in Examples 1-4 was repeated by changing the weight ratio of silicone oligomer A11 to silicone oligomer A21 as follows: Silicone oligomer A11 65% by weight Silicone oligomer A21 30% by weight The type of silicone oligomer A in Examples 5-8 is the same as in Examples 1-4: Example 5 = A11 and A21 Example 6 = A12 and A22 Example 7 = A13 and A23 Example 8 = A14 and A24 The obtained floor coating agents E5 to E8 were applied to the same sample flooring material as in Example 1, the coating film was cured, and the properties of the cured coating film were evaluated. The results are summarized in [Table 2]. The results of Examples 5-8 demonstrate that the same results as in Example 1 can be obtained when the composition of the ricone oligomer falls within the definition of the present invention.

[0085] Examples 9-12 Similar to Examples 5-8, the same procedure as in Example 1 was repeated, but with the ratio of silicone oligomer A11 to silicone oligomer A21 changed to the following weight ratio: Silicone oligomer A11 50% by weight Silicone oligomer A21 45% by weight The type of silicone oligomer A in Examples 9-12 is the same as in Examples 1-4: Example 9 = A11 and A21 Example 10 = A12 and A22 Example 11 = A13 and A23 Example 12 = A14 and A24 The results are summarized in [Table 2]. The results of Examples 9 to 12 also show that the same results as in Example 1 can be obtained when the composition of the ricone oligomer falls within the definition of the present invention.

[0086] Examples 13-16 The same procedure as in Examples 1-4 was repeated, but hardener B11 was replaced with hardener B2. The type of silicone oligomer A in Examples 13-16 is the same as in Examples 1-4: Example 13 = A11 and A21 Example 14 = A12 and A22 Example 15 = A13 and A23 Example 16 = A14 and A24 The obtained floor coating agents E13 to E16 were applied to the same sample flooring material as in Example 1, the coating film was cured, and the properties of the cured coating film were evaluated. The results are summarized in [Table 2]. The results of Examples 13-16 demonstrate that the same results as in Example 1 can be obtained even when the type of curing agent is changed.

[0087] Comparative Examples 5-8 The same procedure as in Comparative Examples 1-4 was repeated, but with hardener B11 replaced by hardener B12. The type of silicone oligomer A in Comparative Examples 5-8 is the same as in Examples 1-4: Comparative Example 5 = A11 and A21 Comparative Example 6 = A12 and A22 Comparative Example 7 = A13 and A23 Comparative Example 8 = A14 and A24 The results are summarized in [Table 2]. The results for Comparative Examples 5-8 were the same as those for Comparative Example 1 even when the type of curing agent B was changed, indicating that respecting the composition of the silicone oligomer is important in order to obtain the effects (anti-slip properties) of the present invention.

[0088] Comparative Example 9 The same procedure as in Comparative Example 1 was repeated, but the ratio of silicone oligomer A11 to silicone oligomer A21 was changed to the following weight ratio: Silicone oligomer A11 45% by weight Silicone oligomer A21 50% by weight The result of the "foot-slip test" for floor coating agent C9 in Comparative Example 9 was "no" anti-slip properties.

[0089] Example 17 The same procedure as in Example 1 was repeated, but silicone oligomer A was changed. Specifically, instead of using only silicone oligomer A11, a combination of silicone oligomer A11 (a methyl-based silicone oligomer of medium polymerization) and silicone oligomer A12 (a methyl-based silicone oligomer of a certain polymerization degree) was used as silicone oligomer A, and the weight composition ratio was changed as follows: Silicone oligomer A11 14% by weight Silicone oligomer A12 41% by weight Silicone oligomer A21 40% by weight Hardener B11 5% by weight The obtained floor coating agent E17 was applied to the same sample flooring material as in Example 1, the coating film was cured, and the properties of the cured coating film were evaluated using the same evaluation method as in Example 1. The anti-slip performance of Example 17 was the same as that of Example 1, but the paintability of floor coating agent E17 was rated as "excellent".

[0090] Example 18 The same procedure as in Example 17 was repeated, but the weight composition ratio of silicone oligomer A11 (methyl-based silicone oligomer of medium polymerization) and silicone oligomer A12 (methyl-based silicone oligomer of a certain polymerization degree) was changed as follows: Silicone oligomer A11 17% by weight Silicone oligomer A12 38% by weight Silicone oligomer A21 40% by weight The properties of the cured coating film obtained from the floor coating agent E18, which contained 5% by weight of the curing agent B11, were evaluated using the same evaluation method as in Example 1. The paintability of floor coating agent E18 in Example 18 also received an "excellent" rating.

[0091] The results above are summarized in [Table 2]. [Table 2]

[0092] The results from Examples 1 to 16 show that the composition of the floor coating agent of the present invention exhibits excellent anti-slip properties and floor coating performance, making it advantageous for use as an anti-slip floor coating agent. On the other hand, the results from Comparative Examples 1 to 9 show that problems with anti-slip properties arise when the weight ratio of silicone oligomers A1 and A2 falls outside the range of the present invention.

[0093] The results of Examples 17 and 18 show that by setting the weight ratio of the medium-polymerization oligomer (A11) to the high-polymerization oligomer (A12) to 1 / 1.5 to 2.5, the paintability of the resulting floor coating agent can be improved to "excellent" without compromising its anti-slip properties.

Claims

1. The following ingredients (A) and (B) in the following weight ratio: (A) A liquid organopolysiloxane comprising at least one of the following: a silicon oligomer having a methyl group and an alkoxy group (hereinafter referred to as methyl-based silicon oligomer (A1)) and a silicon oligomer having a methyl group, a phenyl group and an alkoxy group (hereinafter referred to as methyl / phenyl-based silicon oligomer (A2)), in an amount of 97-92% by weight. (B) Hardener 8-3% by weight The above liquid organopolysiloxane (A) contains the following, and the weight ratio of methyl-based silicone oligomer (A1) to methyl / phenyl-based silicone oligomer (A2) is within the following range. Anti-slip floor coating agent characterized by: (A1) Methyl-based silicone oligomer 75-55% by weight (A2) Methyl / phenyl-based silicone oligomer, 45-25% by weight.

2. The anti-slip floor coating agent according to claim 1, wherein the methyl-based silicone oligomer (A1) is a mixture of an oligomer of medium polymerization (A11) and an oligomer of high polymerization (A12), and the weight ratio of the oligomer of medium polymerization (A11) to the oligomer of high polymerization (A12) is 1 / 1.5 to 2.

5.

3. The anti-slip floor coating agent according to claim 1, further comprising a crosslinking agent other than a hardening agent in a ratio of 0 to 5 parts by weight.

4. The use of a one-component, room-temperature curing organosiloxane composition, which is free of organic solvents and can be cured at room temperature, as a floor coating agent for flooring surfaces, The above one-component, room-temperature curing organosiloxane composition comprises the following components (A) to (C) in the following weight ratios (100% by weight in total): (A) Liquid organopolysiloxane 97-92% by weight (B) Hardener 8-3% by weight (C) Crosslinking agent other than hardener: 0-5% by weight and include, The liquid organopolysiloxane (A) is characterized by containing (A1) and (A2) in the following ratios: (A1) Silicon oligomer having a methyl group and an alkoxy group (hereinafter referred to as methyl-based silicon oligomer) 75-55% by weight (A2) Silicon oligomer having methyl groups, phenyl groups, and alkoxy groups (hereinafter referred to as methyl / phenyl-based silicon oligomer) 45 to 25% by weight.

5. The use according to claim 4, wherein the methyl-based silicone oligomer (A1) described above is a mixture of an oligomer of medium polymerization (A11) and an oligomer of high polymerization (A12), and the weight ratio of the oligomer of medium polymerization (A11) to the oligomer of high polymerization (A12) is 1 / 1.5 to 2.5.

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