Use of room temperature-curable organosiloxane composition, containing mainly inorganic substance, as slip-resistant 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) containing a silicone resin as a main component, and in particular to the use of a one-component moisture-curable organosiloxane composition as an anti-slip floor coating agent that does not pose a risk of slipping even when walking while wearing nylon stockings.

[0002] The floor coating agent of the present invention has anti-slip properties without impairing the inherent properties of silicone resin such as stain resistance, adhesion resistance, graffiti resistance, and water repellency, so it can be used safely and does not cause stress to pets, and can be advantageously used in a wide range of fields including nursing homes and hospitals. In addition to flooring, the silicone floor coating agent of the present invention can be advantageously used in applications that require the elimination of slippery hazards such as stairs and handrails. [Background technology]

[0003] Flooring (floor materials) includes a wide variety of materials, including flooring for homes and stores, plywood, laminate floors, tiles, and carpets, as well as floors for hospitals, sports gyms, gymnasiums, OA floors, roads, and ship decks, and is classified into many categories based on material, function, use, etc. The properties, performance, and functions required of such flooring materials are diverse depending on the material and use, and the requirements for stone and metal flooring materials differ from those for wood and plastic flooring materials, but the properties, performance, and functions generally required of flooring materials include durability, safety, stain resistance, scratch resistance, chemical resistance, impact resistance, etc. For hospitals and pet use, antibacterial properties, deodorizing effects, virus resistance, etc. are also required, as well as compatibility with floor heating, gloss, ease of maintenance, etc.

[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 are highly resistant to chemicals and pet urine. UV floor coatings are highly water resistant and suitable for kitchen and dining room floors. Silicone floor coatings are non-slip and safe for the elderly and pets. Urethane floor coatings are resistant to friction and are useful for preventing scratches caused by dragging chairs.

[0005] Anti-slip properties are required for all flooring materials. The property of not slipping when humans or animals walk on it is generally called "anti-slip properties". This "anti-slip properties" is defined by various standards for each field of application. In the field of "floor coatings", appropriate friction properties (hereinafter referred to as anti-slip properties) are required so that humans or animals do not stumble or slip and fall when they walk on it. In other words, it is desirable to have neither excessive nor insufficient friction. There are physical methods such as etching with chemical solutions to impart "anti-slip properties", but chemical methods are commonly used to treat the coating film itself so that it has anti-slip properties.

[0006] [Patent Document 1] (JP Patent Publication 2004-123982) describes a floor paint curable composition that maintains the characteristics of an acrylic silicone paint and is composed of a copolymer (A) component whose main chain is substantially made of a vinyl polymer, has at least one silicon group bonded to a hydrolyzable group in the molecule, and has an amino group, a curing catalyst (B), a silane coupling agent (C), and a weak solvent (D). This floor paint curable resin composition contains a copolymer (A) component that has a silyl group bonded to a hydrolyzable group as a base resin that has curability at room temperature in the presence of moisture. However, 50% by weight or more of the units constituting the main chain of the copolymer (A) component are formed from acrylic monomer units.

[0007] [Patent Document 2] (JP Patent Publication 2005-220332 A) describes an anti-slip treatment agent for preventing slippage on mineral floors in various facilities such as swimming pools, bathrooms, kitchens, entrances, halls, toilets, slopes, bridges, etc. The anti-slip treatment agent in Example 1 of this patent publication is a white paste obtained by adding 0.15 parts of xanthan gum (polysaccharide) and 30 parts of magnesium chloride (inorganic powder) to 10 parts of water, thoroughly mixing and stirring to form a slurry, adding 43.35 parts of hydrochloric acid and stirring for about 1.5 hours, adding 15 parts of acidic ammonium fluoride (inorganic powder), 1 part of organopolysiloxane, and 0.5 parts of a surfactant, and stirring for about 2 hours. However, the main ingredient of this anti-slip treatment agent is an inorganic mineral acid, and therefore 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: adding various friction-imparting agents to the floor coating, and selecting an anti-slip floor coating whose coating film itself has suitable friction properties.

[0009] An example of the former is [Patent Document 2] (JP Patent Publication No. 2007-191672), in which microballoons are added to a two-component epoxy resin paint (at a ratio of 10 parts by volume per 100 parts by volume of the paint components). This method increases costs because the friction-imparting material is added to the vehicle (resin paint).

[0010] An example of the latter is [Patent Document 3] (Patent No. 6749009). The floor anti-slip agent described in this patent is made by dissolving and dispersing a silicone resin in a solvent. This silicone resin has a weight average molecular weight of 1000 or more and is composed of M units (R1R2R3SiO 1 / 2 ) and Q units (SiO 4 / 2 ) and the amount of the additive is 0.1 wt% to 5.0 wt%. In Example 1 of this patent, 1 wt% of decyltrimethoxysilane and 3 wt% of trimethylsiloxysilicate are dissolved in 95.75 wt% of ethanol. The floor anti-slip agent in this patent is mostly ethanol, and the solvent evaporates during application.

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

[0012] Solvent-based silicone floor coating agents evaporate the solvent during application, which is undesirable from the perspective of protecting the global environment. Water-soluble dispersions or emulsions made by mixing silicone resin with acrylic resin, etc., are expensive, making them difficult for the average person to use as a do-it-yourselfer. Some floor coating agents that disperse silicone resin in water have issues with repaintability, and when applying a second coat after a first coat, the coating agent is repelled, making it difficult to apply a uniform coat again.

[0013] Floor coating agents made of inorganic silicone compositions were also thought to be unable to be repainted. The present inventors attempted to use floor coating agents made of inorganic silicone compositions as silicone floor coating agents.

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

[0015] TIFF2024028264000002.tif35122

[0016] (In the formula: R 1 is a hydrogen atom or a C1 to C5 alkyl or acyl group; R 2 ~R 6 are hydrogen atoms, OR 1 or monovalent hydrocarbon groups, n is a number from 1 to 15. The silicon content of the compound represented by the formula (I) is 50% by weight or more, expressed on an SiO2 oxide basis. The crosslinking agent (B) is represented by the following general formula (2) or (3): R 7 p M·(OR1) 3-p ...(2) R 7 m Q·(OR1) 4-m ...(3) (Wherein: M is aluminum or boron element; Q is silicon, titanium or zirconium element; R 1 is a hydrogen atom or a C1 to C5 alkyl group, an acyl group, or an oxime group; R 7 is a hydrogen atom, OR 1 a group selected from a group consisting of a cyclic group, a cyclic group, or a monovalent hydrocarbon group; p is 1 or 2; m is an integer from 1 to 3) The organic metal compound is one or more of the following: The curing catalyst (C) is an organic compound containing one or more metals selected from the group consisting of zinc, cobalt, aluminum and tin. The above-mentioned solventless room temperature curing organosiloxane composition contains a catalytic reaction blocking agent, and all of the metal element components contained in the above-mentioned three-component mixed liquid composition are made of MO. y / 2 It contains 40% by weight or more of these elements expressed on an oxide basis (M is aluminum, boron, silicon, titanium, or zirconium element, and y is the valence of the metal element).

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

[0018] There are other patents which use room temperature curable organopolysiloxane compositions as coating agents. [Patent Document 5] (JP 2007231182 A) describes a room-temperature curable polyorganosiloxane composition containing the following (A) to (E) as essential components: (A) a polyorganosiloxane having a viscosity at 25°C of 0.1 to 1,000 Pa s and both ends capped with trialkoxysilyl groups: 5 to 95% by mass, (B) a polyorganosiloxane having a viscosity at 25°C of 0.1 to 1,000 Pa s and both ends capped with dialkoxymonoorganosilyl groups: per 100 parts by mass of a polyorganosiloxane consisting of 95 to 5% by mass, (C) The following general formula (1)

[0019] TIFF2024028264000003.tif2687

[0020] (In the formula, R 1 , R 2 and R 3 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), (D) Specific surface area is 50m 2 / g or more of silica powder: 1 to 50 parts by mass, (E) Titanium chelate catalyst: 0.1 to 15 parts by mass. However, this room-temperature-curable polyorganosiloxane composition is intended for use in a variety of fields, such as as a sealing material for building materials, and as an adhesive in the electrical and electronic fields and the transportation field, and there is no mention of its use as an anti-slip floor coating agent.

[0021] [Patent Document 6] (JP 2009167420 A) describes a room-temperature-curable organopolysiloxane composition that cures by a condensation reaction and is composed of the following (A) to (D): (A) A compound having a viscosity of 100 to 500,000 mPa s at 25°C and containing, in one molecule, a compound represented by the general formula: (X)aR 1 3Si- (wherein X is a hydroxyl group or a hydrolyzable group, and R 1 is a monovalent hydrocarbon group or a halogen atom-substituted monovalent hydrocarbon group, and a is 1, 2, or 3), (B) a silane or siloxane oligomer (0.01 to 40 parts by weight) containing three or more silicon-bonded hydrolyzable groups per molecule (C1) A flame retardant comprising a platinum compound (the amount of the platinum compound in the composition is 1 to 2,000 ppm in terms of platinum metal) (C2) At least one compound of the formula, -(R 2 )(R 3 )SiO-(R 2 )(R 3 )SiO-(wherein, R 2 is an aryl group, R 3 is an alkenyl group), and containing an aryl group and an alkenyl group and having 8 or less silicon atoms per molecule {in an amount of 2 moles or more per mole of platinum atoms in component (C1)}, (D) Inorganic powder (5 to 300 parts by weight). This room-temperature curable organopolysiloxane composition is also intended to be used as a coating agent, sealant, or adhesive for electric and electronic parts, and there is no mention of its use as an anti-slip floor coating agent.

[0022] [Patent Document 7] (JP 2015110792 A) describes a room-temperature curable alkoxy-cured polysiloxane composition containing the following components (a) to (d): (a) a hydroxyl-terminated polyorganosiloxane; (b) a polyfunctional alkoxysilane, and (c) an organotitanium compound having the following general formula I or II, or a multipolymer thereof having a degree of polymerization of 2 to 10: (i) an organotitanium compound I having the following general formula I: TIFF2024028264000004.tif1787

[0023] (In the formula, n is an integer between 1 and 4, and R 1 is a saturated monovalent hydrocarbon radical having 1 to 16 carbon atoms, and R 2 is a saturated divalent hydrocarbon radical having 1 to 16 carbon atoms, R 3 is a saturated monovalent hydrocarbon radical having 1 to 32 carbon atoms, where the hydrocarbon radical includes both straight-chain and branched ones. (ii) an organotitanium compound having the following general formula II: TIFF2024028264000005.tif1792

[0024] (In the formula, m is an integer between 2 and 4, and R 4 is a saturated monovalent hydrocarbon radical having 1 to 16 carbon atoms, and R 5 is a saturated divalent hydrocarbon radical having 1 to 16 carbon atoms, R 6 is a saturated monovalent hydrocarbon radical having 4 to 32 carbon atoms, where the hydrocarbon radical includes both straight-chain and branched ones. (d) Catalyst (optional component) The room temperature curable alkoxy-cured polysiloxane compositions are used directly as sealants, adhesives, and coating materials for applications in the construction, electronics, electrical, and automotive sectors, but the patent does not mention their use as anti-slip floor coatings.

[0025] As mentioned above, the applicant has not found any room temperature curable polyorganosiloxane composition used as an anti-slip floor coating agent. In fact, when an inorganic silicone composition is used as a floor coating agent, it does not show excellent "anti-slip properties" unlike commercially available general solvent-based or emulsion-based silicone floor coating agents. The reason for this is unclear, but it is thought that the cured product has a high silicon content, so that the 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 present inventors have attempted to use a floor coating agent of a silicone composition mainly composed of inorganic substances as a silicone floor coating agent. Surprisingly, the present inventors have found that a specific ratio of specific components in the composition described in the above [Patent Document 4], which is commercially available under the name of "Ceraton", can be used as a silicone floor coating agent excellent in anti-slip properties, repaintability, flexibility and transparency. That is, the present inventors have found that a specific ratio of specific components can be used as a silicone floor coating agent excellent in anti-slip properties, flexibility and transparency, even if the solventless room temperature curing organosiloxane composition described in the above [Patent Document 4] is simply used as a silicone floor coating agent, which does not have the desired excellent properties, and thus completed the present invention. The present inventors have found that a specific type of solventless room temperature curing organosiloxane composition can be used as a floor coating agent excellent in anti-slip properties, flexibility and transparency, contrary to the expectation that silicone compositions mainly composed of inorganic substances generally have no anti-slip properties or have low anti-slip properties. [Prior art documents] [Patent documents]

[0027] [Patent Document 1] JP 2004-123982 A [Patent Document 2] JP 2007-191672 A [Patent Document 3] Patent No. 6749009 specification [Patent Document 4] Special Publication No. 7-72250 [Patent Document 5] JP 2007231182 A [Patent Document 6] JP 2009167420 A [Patent Document 7] JP 2015110792 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0028] Therefore, an object of the present invention is to provide a floor coating agent having excellent anti-slip properties, which uses a solventless, room temperature curing organosiloxane composition having a silicon content of 50% by weight or more expressed on an SiO2 oxide basis. Another object of the present invention is to use the room temperature curable organosiloxane composition mainly composed of an inorganic substance 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 to provide an anti-slip floor coating agent comprising a solventless room temperature curing composition containing a liquid organopolysiloxane and a curing agent, The following components (A) and (B) are mixed in the following weight ratio: (A) 97 to 92% by weight of at least one liquid organopolysiloxane consisting of a methyl-based silicone oligomer (A1) and a methyl / phenyl-based silicone oligomer (A2) (B) Hardener 8 to 3% by weight and wherein the weight ratio of the methyl-based silicone oligomer (A1) to the methyl / phenyl-based silicone oligomer (A2) in the liquid organopolysiloxane (A) is within the following range: (A1) Methyl silicone oligomer 75-55% by weight (A2) Methyl / phenyl silicone oligomer 45 to 25% by weight.

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

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

[0032] The second object of the present invention is to provide a method for applying a one-component, room-temperature-curable liquid organosiloxane composition containing no organic solvent, which can be cured at room temperature, to a floor coating agent for a flooring surface, comprising: The one-part room temperature curable organosiloxane composition contains the following components (A) to (C) in the following weight ratios (total 100% by weight): (A) Liquid organopolysiloxane 97 to 92% by weight (B) Hardener 8 to 3% by weight (C) Crosslinking agent other than curing agent: 0 to 5% by weight Including, The liquid organopolysiloxane (A) is characterized in that it contains the following (A-1) and (A-2) in the following ratio: (A-1) Methyl silicone oligomer 75-55% by weight (A-2) Methyl / phenyl-based silicone oligomer: 45 to 25% by weight.

[0033] The methyl silicone oligomer (A1) is a mixture of an oligomer (A11) having a medium degree of polymerization and an oligomer (A12) having a high degree of polymerization, and the weight ratio of the oligomer (A11) to the oligomer (A12) having a high degree of polymerization is preferably 1 / 1.5 to 2.5. [Brief description of the drawings]

[0034] [Figure 1] FIG. 1 is a schematic diagram of an experimental device used to evaluate the "slip resistance" of the flooring material of the present invention. [Diagram 2] This is a graph showing the results of determining the Stricbeck curve using the experimental apparatus of [Figure 1] and a wooden plywood tile as sample 1. [Diagram 3]1 is a graph showing the results of determining the Stricbeck curve using the experimental apparatus of [Figure 1] and a ceramic tile as sample 1. [Figure 4] This is a graph showing the results of determining the Stricbeck curve using the experimental apparatus of [Figure 1] and granite as sample 1. [Diagram 5] A conceptual diagram of an experiment in which feet wearing nylon (registered trademark) stockings were actually walked up an inclined slope to examine slipperiness. BEST MODE FOR CARRYING OUT THEINVENTION

[0035] The non-slip, solventless, room temperature curable organosiloxane composition based on inorganic substances of the present invention is a composition with a specific ratio among the compositions described in [Patent Document 4], so 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 is a composition that has excellent anti-slip properties, flexibility, and transparency among the compositions described in [Patent Document 4]. Therefore, the reaction mechanism of the composition of the present invention and the contents of each component of the composition can be referred to the specification of [Patent Document 4], and the contents described in [Patent Document 4] (JP Patent Publication No. 7-72250) form a part of the specification of this application.

[0036] The term "polymer" encompasses oligomers, including both homopolymers and copolymers. As used herein, the term "silicon" refers to polysiloxane polymers or oligomers based on alternating silicon and oxygen atoms, and "silicon" and "siloxane" are used interchangeably herein.

[0037] The term "organopolysiloxane" is used as a general term for a substance having a Si-O bond (siloxane bond), and in this specification means an oligomer having an alkoxysilyl group and a reactive functional group, which may have a silanol functional group. The silicon content of the organopolysiloxane used in the present invention is 50% by weight or more, expressed on a SiO2 oxide basis. This silicon content is calculated from the molecular formula.

[0038] In the present invention, the liquid organopolysiloxane (A) maintains a liquid state, and has a viscosity of 3,000 centipoise or less or a kinetic viscosity of 100 mm at 25° C. without adjusting the liquid viscosity with a diluent. 2 / s or less, and its weight average molecular weight is generally 10 2 ~10 5 This is 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 of the silicone oligomers (A1) and (A2) is widely used and easily available on the market.

[0040] The liquid organopolysiloxane (A) of the present invention can be composed of TD units consisting of a single or combination of siloxane compounds having a side chain group of methyl or phenyl, a D unit having two functional groups, and a T unit having three functional groups. The methyl-based silicone oligomer (A1) can also be expressed by a general formula, but this becomes complicated, so in this specification, the methyl-based silicone oligomer (A1) means a silicone oligomer having a methyl group and an alkoxy group, particularly a methoxy group, and is, for example, an oligomer such as the one shown below (the subscripts a, b, c, d, e, f, g, etc. in the following structural formula are numerical values ​​of 0 to 100, and the viscosity is 3000 centipoise or less, or the kinetic viscosity at 25°C is 200 mm 2 / s)

[0041] TIFF2024028264000006.tif143170

[0042] The kinematic viscosity of the organopolysiloxane of the present invention is 10 to 350 mm 2 / s, preferably 10 to 300 mm 2 / s, more preferably 10 to 100 mm 2 The kinematic viscosity is measured at 25°C in an Ostwald viscometer.

[0043] Similarly, the methyl / phenyl-based silicone oligomer (A2) refers to a silicone oligomer having a methyl group, a phenyl group, and an alkoxy group, particularly a methoxy group, such as the following oligomer (the subscripts a, b, c, d, e, f, g, etc. in the following structural formula are numbers from 0 to 100, and the viscosity is 10,000 centipoise or less or the kinetic viscosity at 25°C is 300 mm 2 / s)

[0044] TIFF2024028264000007.tif6581

[0045] The solventless, room temperature curable organosiloxane composition of the present invention has a silicon content of 50% by weight or more, expressed in terms of SiO2 oxide, which is calculated from the molecular formula.

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

[0047] The curing agent (B) can be widely used from among those known as curing agents for silicon oligomers. The term curing agent means a compound that accelerates the curing of the liquid organopolysiloxane (A), and includes a curing catalyst and may also include a coupling agent or a crosslinking agent. In other words, a crosslinking agent or a coupling agent that also functions as a curing catalyst can be used as the curing agent (B). The solventless room temperature curing organosiloxane composition of the present invention can further contain a crosslinking agent in addition to the curing agent (B). 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 application of the present invention.

[0048] The hardener (B) can be an organometallic compound consisting of one or a combination of two or more tin, titanium, aluminum, silicon or zirconium compounds having functional groups consisting of alkoxy, acyloxy or oxime groups. Such hardeners are readily available on the market as hardeners 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 bismaleic acid monobutyl ester, dioctyl bismaleic acid monobutyl ester, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, dioctyltin diversatate, dibutyltin oxide, and dioctyltin oxide.

[0050] Examples of titanium 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 the aluminum compound include, but are not limited to, aluminum acetylacetonate, aluminum bis(ethylacetoacetate) mono-normal butyrate, aluminum ethylacetoacetate di-normal butyrate, and aluminum tris(ethylacetoacetate).

[0052] 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, or two or more of them may be used in combination. In particular, it is preferable to use tin compounds such as dioctyltin dilaurate and dioctyltin diversatate, which have excellent reactivity, titanium compounds such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetra t-butoxytitanium, and titanium diisopropoxybis(ethylacetoacetate) and their hydrolysates, and aluminum compounds such as aluminum acetylacetonate, aluminum bis(ethylacetoacetate) mono-normal butyrate, aluminum ethylacetoacetate di-normal butyrate, and aluminum tris(ethylacetoacetate) and their hydrolysates.

[0054] If necessary, the composition of the present invention may further 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 or the hardness, flexibility, adhesion, etc. of the resulting coating film.

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

[0056] The solventless room temperature curable organosiloxane composition of the present invention may further contain the following optional components (C) and (D) in addition to the above-mentioned (A) and (B): (C) Catalytic reaction blocking agent (D) Reaction retarder (hardening retarder) These components (C) and (D) are optional components, and the types, amounts used, etc. of these components can be found in [Patent Document 4] (JP-B-7-72250). In order to ensure transparency in the applications of the present invention, it is preferable not to use these components.

[0057]

[0043] If necessary, the composition of the present invention may further contain various known additives that can be added to room temperature curable organopolysiloxane compositions, such as pigments, flame retardants, heat resistance improvers, adhesion promoters, thixotropy imparting agents, and friction modifiers, so long as the objectives of the present invention, particularly the anti-slip properties and transparency, are not impaired.

[0058] The room-temperature curable composition of the present invention is a one-component type, has a low viscosity, and has excellent workability even without the use of a solvent, and therefore can be suitably used as a coating agent.

[0059] The solventless, room temperature curable organosiloxane composition of the present invention can be prepared by mixing the above-mentioned components (A) and (B) (and other additive components, if necessary) in a container protected from moisture for 30 minutes or more at room temperature until a homogeneous solution is obtained.

[0060] The one-part room temperature curing organosiloxane composition of the present invention has one-part storage stability, and even if it is left at room temperature for 6 months, it will not change substantially and can be used as a floor coating agent as it is. The application method is not particularly limited, and known methods such as coating with a brush, roll, etc., or spraying can be used. For example, the one-part room temperature curing organosiloxane composition is simply applied to the surface of the floor material and spread evenly with a roll, brush, or soft cloth.

[0061] The floor coating agent of the one-part room temperature curing organosiloxane composition of the present invention cures after about 120 hours at 25°C with atmospheric moisture (water) (hardness of about 4H). By "water" it is meant atmospheric moisture, steam, liquid water, ice, or water mixed with other organic compounds such as organic solvents, with atmospheric moisture being preferred. An effective amount of water is an amount sufficient to cause curing of the composition. The resulting cured coating has excellent hardness and crack resistance, and also exhibits anti-skid properties.

[0062] The performance of the flooring agent of the present invention can be evaluated from the viewpoints of "anti-slip performance" and "paint performance (coating performance)". Evaluation of anti-skid performance The anti-skid performance of the flooring materials of the present invention was evaluated in (1) a "step-in" slip test and (2) an inclined slope test.

[0063] (1) "Stepping in" 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 friction coefficient (μ) is measured based on the curve. In the experimental apparatus of [Figure 1], a sample 1 is fixed to a support 7, and an elastic material 2 is slid from left to right on the sample 1 using a slider 4, and it is possible to examine whether the friction force (F) changes depending on the presence or absence of a coating agent 3 applied to the 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 [Figure 4] show the results of determining the Stricbeck curve by changing the material of Sample 1. The vertical axis of each figure is the friction coefficient (μ), and the horizontal axis is the S value (m). The S value represents these driving conditions, and is expressed as S = μ·V / P' (μ is viscosity (Pa·s), V is speed (m / s), and P is pressure (Pa)). The friction coefficient depends on the surface viscosity, speed, and pressure. In practice, the viscosity (μ) and pressure (P) were kept constant, and the friction coefficient (μ) was determined by changing the speed (V), which was then plotted on the Stricbeck curve, and the friction coefficient (μ) was determined from the relationship: friction coefficient (μ) = frictional force (F) / normal load (P).

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

[0066] A comparison was made between the case where flooring agent 3 was applied to sample 1 and the case where it was not applied, and when there was a large increase in the coefficient of friction (μ) (less slippery), it was judged as having anti-slip properties, and when there was a small increase in the coefficient of friction (μ) (no change or only a small change in slipperiness), it was judged as having no anti-slip properties.

[0067] (2) Inclined slope test [Figure 5] is a conceptual diagram of an experiment (stocking test) in which slipperiness was examined by actually walking on an inclined slope with an inclination angle of approximately 30°. In this experiment, it was examined whether women (22) aged 10 to 60 (weighing approximately 20 to 65 kg) with no walking problems could climb on a wooden plywood sample flooring material (11) set on an inclined floor (12) with an angle of 30° while wearing nylon (registered trademark) stockings or socks. The results were compared between cases where floor coating agent E1 was applied and cases where it was not applied, and rated as "not slippery" or "slippery."

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

[0069] Since the floor coating agent of the present invention exhibits different paintability depending on the composition, only the evaluation results of "paintability" due to the difference in composition are shown here. The paintability was evaluated by experienced painters based on the characteristics required to obtain a smooth paint surface (appropriate viscosity, appropriate drying time, ease of application) and was rated as excellent, good, fair or poor. Painting workability "Excellent" = Extremely easy painting "Good" = Easy to paint "Average" = Painting is a little difficult "Poor" = Difficult to paint

[0070] The floor coating agent of the present invention can be used for any purpose such as houses, stores, hospitals, sports gyms, gymnasiums, OA floors, roads, ships, etc., but for the sake of simplicity, the following description will be given using a residential floor material as an example. However, the floor coating agent of the present invention can be used for floor materials of stores, hospitals, sports gyms, gymnasiums, OA floors, roads, ships, etc. EXAMPLES

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

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

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

[0074] These materials A11, A21 and B11 were placed in a container, mixed at room temperature under reduced pressure for 30 minutes until a homogeneous solution was obtained, and then aged at room temperature for 48 hours to prepare the room temperature curing organosiloxane composition of the present invention. Each of the obtained compositions had one-part storage stability, and did not change substantially even after being left at room temperature for 6 months. This room temperature curing organosiloxane composition was used as floor coating agent E1.

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

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

[0077] The results are shown in Figure 2. Figure 2 shows the Stricbeck curve, with the horizontal axis representing the S value (S = μ·V / P') which indicates 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 "stepping on", the coefficient of friction (μ) is higher when floor coating agent E1 is applied than when no coating is applied. On the right side of the horizontal axis in Figure 2 (when the relative sliding speed is fast, in the hydrodynamic lubrication region), i.e., "after it begins to slide", there is no difference in the coefficient of friction with or without the floor coating agent.

[0078] In the present invention, slippage during "stepping" is an issue, so the floor coating agent E1 of the present invention has a "yes" anti-slip property in the "stepping" slip test.

[0079] In addition, [Figure 3] and [Figure 4] show the results of slip tests when the material of the sample flooring material (1) was changed to "ceramic tile" and "granite." These materials (ceramic tile, [Figure 3]) and (granite, [Figure 4]) show the same effect as [Figure 2].

[0080] (2) Inclined slope test The results of the nylon stocking test in the facility shown in FIG. 5 were "non-slip" since virtually all participants were able to climb without relying on the safety railing (23).

[0081] Painting performance The "paintability" of floor coating agent E1 was rated "good."

[0082] Examples 2 to 4 The same procedure as in Example 1 was repeated, but the composition ratio was the same, and the type of silicone oligomer A was changed to the following combination: Example 2 = A12 and A22 Example 3 = A13 and A23 Example 4 = A14 and A24 That is, silicone oligomer A11 was replaced by A12, A13 or A14, respectively, and silicone oligomer A21 was replaced by A22, A23 or A24, respectively. The obtained floor coating agents E2, E3 and E4 were applied to the same sample floor 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 2 to 4 show that the same results can be obtained even if the type of ricone oligomer is changed.

[0083] Comparative Examples 1 to 4 In Comparative Examples 1 to 4, the same procedures as in Examples 1 to 4 were repeated, but the weight ratio of the 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 to 4 was the same as that in Examples 1 to 4: Comparative Example 1 = A11 and A21 Comparative 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 floor 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]. In Comparative Examples 1 to 4, floor coating agents C1 to C4 showed little increase in friction coefficient (μ) and little change in slipperiness, and therefore the results of the "step-in" slip test showed "no" slip resistance.

[0084] Examples 5 to 8 The same operations as in Examples 1 to 4 were repeated, except that the ratio by weight of Silicone Oligomer A11 and Silicone Oligomer A21 was changed to the following: Silicone Oligomer A11 65% by weight Silicone Oligomer A21 30% by weight The type of silicone oligomer A in Examples 5 to 8 was the same as in Examples 1 to 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 floor 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 to 8 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.

[0085] Examples 9 to 12 As in Examples 5 to 8, the same procedure as in Example 1 was repeated, except that the ratio of Silicone Oligomer A11 to Silicone Oligomer A21 was 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 to 12 was the same as in Examples 1 to 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 those of Example 1 can be obtained when the composition of the ricone oligomer falls within the definition of the present invention.

[0086] Examples 13 to 16 The same procedure as in Examples 1 to 4 was repeated, but the curing agent B11 was replaced by the curing agent B2. The type of silicone oligomer A in Examples 13 to 16 was the same as in Examples 1 to 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 floor 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 to 16 show that the same results as in Example 1 can be obtained even if the type of curing agent is changed.

[0087] Comparative Examples 5 to 8 The same operations as in Comparative Examples 1 to 4 were repeated except that the curing agent B11 was replaced by the curing agent B12. The type of silicone oligomer A in Comparative Examples 5 to 8 was the same as that in Examples 1 to 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 of Comparative Examples 5 to 8 were the same as those of Comparative Example 1 even though the type of curing agent B was changed, indicating that it is important to respect the composition of the silicone oligomer in order to obtain the effect (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 "step-in slip test" for floor coating agent C9 of Comparative Example 9 was "no" anti-slip properties.

[0089] Example 17 The same procedure as in Example 1 was repeated, but the silicone oligomer A was changed. That is, not only the silicone oligomer A11 was used as the silicone oligomer A, but also a combination of the silicone oligomer A11 (a methyl-based silicone oligomer with a medium degree of polymerization) and the silicone oligomer A12 (a methyl-based silicone oligomer with a degree of polymerization) was used, and the weight composition ratio was changed to the following: 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 onto the same sample floor 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 coating workability of floor coating agent E17 was rated "excellent."

[0090] Example 18 The same procedure as in Example 17 was repeated, but the weight composition ratio of Silicone Oligomer A11 (a methyl-based silicone oligomer with a medium degree of polymerization) and Silicone Oligomer A12 (a methyl-based silicone oligomer with a degree of polymerization) was changed as follows: Silicone Oligomer A11 17% by weight Silicone Oligomer A12 38% by weight Silicone oligomer A21 40% by weight Hardener B11 5% by weight The resulting floor coating agent E18 was evaluated for the properties of the cured coating film using the same evaluation method as in Example 1. The coating workability of the floor coating agent E18 of Example 18 was also rated "excellent."

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

[0092] The results of Examples 1 to 16 show that the composition of the floor coating agent of the present invention is excellent in anti-slip properties and floor coating performance, and can be advantageously used as an anti-slip floor coating agent. On the other hand, the results of Comparative Examples 1 to 9 show that problems with anti-slip properties occur when the weight ratio of silicone oligomers A1 and A2 deviates from the range of the present invention.

[0093] The results of Examples 17 and 18 show that when the weight ratio of the oligomer (A11) with a medium degree of polymerization to the oligomer (A12) with a high degree of polymerization is set to 1 / 1.5 to 2.5, the paintability of the resulting floor coating agent can be made "excellent" without impairing the anti-slip properties.

Claims

1. The following components (A) and (B) in the following weight ratios: (A) At least one liquid organopolysiloxane composed of a methyl-based silicone oligomer (A1) and a methyl / phenyl-based silicone oligomer (A2) 97 to 92% by weight (B) Curing agent 8 to 3% by weight containing, and the weight ratio of the methyl-based silicone oligomer (A1) and the methyl / phenyl-based silicone oligomer (A2) in the above liquid organopolysiloxane (A) being within the following range: An anti-slip floor coating agent, characterized in that: (A1) Methyl-based silicone oligomer 75 to 55% by weight (A2) Methyl / phenyl-based silicone oligomer 45 to 25% by weight.

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

5.

3. The anti-slip floor coating agent according to claim 1, further containing a cross-linking agent other than the curing agent in a ratio of 0 to 5 parts by weight.

4. Use as a floor coating agent for the surface of a floor material of a one-component room-temperature curable liquid organosiloxane composition that does not contain an organic solvent and can be cured at room temperature, wherein the one-component room-temperature curable liquid organosiloxane composition contains the following components (A) to (C) in the following weight ratios (100% by weight in total): (A) Liquid organopolysiloxane 97 to 92% by weight (B) Curing agent 8 to 3% by weight (C) Cross-linking agent other than the curing agent 0 to 5% by weight containing, characterized in that the liquid organopolysiloxane (A) contains the following (A1) and (A2) in the following ratios: (A1) Methyl-based silicone oligomer 75 to 55% by weight (A2) Methyl / phenyl-based silicone oligomer 45 to 25% by weight.

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

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