JP2002194335A - Building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a building material treated with a treating agent and having water- and oil-repellent properties and persistence thereof and weather resistance. SOLUTION: This building material is treated with a treating agent comprising a fluorine-containing phosphoric acid compound repellent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building material having a long lasting water and oil repellency and a high moisture permeability formed by applying a treating agent containing a fluorine-containing phosphoric acid compound repellent to a porous substrate. The building material of the present invention further has weather resistance and acid rain resistance.

[0002]

2. Description of the Related Art Repellents which are coated on building materials to exhibit water repellency and are used for various purposes are widely used, for example, in the fields of construction and building materials. When a building material absorbs water, the base material shrinks due to the absorption of the water, and the building material breaks or cracks. However, building materials that contain a lot of water like wood need to release moisture from the inside. In other words, it is necessary to prevent moisture from the outside but release moisture from the inside. This is also true for cement-based building materials. In addition, the current water repellent is generally of a solvent type, but is desired to be water-based due to environmental problems.

As the water repellent, paints, organosilicon compounds and the like have been used, but they are not sufficient in terms of water repellency, durability and moisture permeability. To improve this,
Various proposals have been made.

JP-A-6-228489 describes coating a substrate with an aqueous fluororesin. The contact angle of water is 100 ° or less, and the water repellency is not sufficient. Further, since the base material is wetted with water because a coating film is formed on the surface, a natural feeling of the base material itself cannot be obtained. In addition, a base material such as wood cannot escape the internal moisture. JP-A-62-197369 describes using an emulsion in which an organic silane compound is dispersed in water. However, silane is hydrolyzable, and the storage stability of the emulsion is poor. Further, it is difficult to disperse in water, and when it is made into an emulsion, the emulsifier is contained in a large amount, so that the water repellency is not sufficient. When the amount is too small, the emulsion is separated into silane and water, and uniform coating cannot be performed.

JP-A-6-248259 describes the use of fluorine-containing silicon compounds. However, as in JP-A-62-197369, silane is hydrolyzable, and the storage stability of the emulsion is poor. Further, since the composition contains an emulsifier, high water repellency cannot be obtained. Further, fluorine-containing silicon compounds are difficult to synthesize and expensive. JP 57-23662 describes the use of fluorinated acrylate polymers. Fluorinated acrylate polymers have low permeability and insufficient adhesion,
Further, the weather resistance is not so good, and there is no durability in long-term use.

JP-A-50-142628 discloses that a phosphoric acid compound having a perfluoroalkyl group is used to impart antifouling properties. However, this publication does not describe the use of the composition in a porous substrate, and is insufficient in terms of water and oil repellency and moisture permeability. The example of this publication describes that a fluorine-containing phosphoric acid compound is applied to a vinyl chloride exhaust duct,
Since the exhaust duct made of vinyl chloride is not a porous substrate, the phosphoric acid compound is not sufficiently fixed, and there is no sustained water / oil repellency.

[0007] In the construction of houses, there is an increasing use of the construction method by fitting boards and roofs, and the demand for building materials used in this construction method is increasing. In a house with good airtightness, if air conditioning is complete,
Condensation forms at the boundaries and inside of the walls that block the outside air and the room. Due to the formation of dew, mold is generated, and deterioration of the wall base material is promoted. In addition, when concrete molded on site is painted immediately after molding, there is a problem that water inside hardly escapes and strength is hardly obtained. Therefore, water vapor permeability as well as waterproofness is required for building materials. Conventional building materials did not have good waterproofness and good water vapor permeability.

[0008]

An object of the present invention is to provide a building material which has been treated with a treating agent and has water and oil repellency, its durability and weather resistance. Another object of the present invention is to provide a building material protected by a water / oil repellent, which has waterproofness, water vapor permeability and fungicidal properties.

[0009]

Conventionally, it has been proposed to apply to a building material by paying attention to the antifouling property of the treating agent. However, the present invention provides a method for applying a specific treatment to a porous building material. By applying a fluorine-containing phosphoric acid compound as an agent,
It has been found that excellent durability of water and oil repellency and water vapor permeability can be obtained. The present invention provides a building material obtained by applying a treatment agent containing a fluorine-containing phosphoric acid compound to a porous substrate.

The treating agent may contain a fluorine-containing phosphoric acid compound, a surface conditioner, and water. The treating agent may further include an organosilicon compound. The treatment agent is preferably in the form of a solution, but may be in the form of a dispersion. The fluorinated phosphoric acid compound has a perfluoroalkyl group and a perfluoroalkenyl group. The carbon number of the perfluoroalkyl group and the perfluoroalkenyl group in the fluorinated phosphoric acid compound is from 1 to 21, for example, from 3 to 1
9, especially 5-18.

[0011] The fluorine-containing phosphate compound of the formula _{(1): [Rf- (O} ) n] m PO (OR) 3-m (1) [ wherein, Rf is a straight chain of 1 to 21 carbon atoms, or It is a monovalent group having a branched perfluoroalkyl group or perfluoroalkenyl group, m represents an integer of 1 to 3, and n represents an integer of 0 or 1. R represents H or a linear or branched alkyl group having 1 to 21 carbon atoms. Compounds represented by, or the formula _{(2): [Rf- (O} ) n] m PO (OX) 3-m (2) [ wherein, Rf is a 1-21 carbon linear or branched Pa -
It is a monovalent group having a fluoroalkyl group or a perfluoroalkenyl group, m represents an integer of 1 to 3, and n represents an integer of 0 or 1. X represents an alkali metal or an ammonium group which may be substituted with an alkyl group or a hydroxyalkyl group. ] It may be the compound shown by these. The fluorine-containing phosphoric acid compound may be, for example, a fluorine-containing phosphate.

In compounds (1) and (2), m
May be 1 or 2. n may be 0 or 1. The (hydroxy) alkyl group in the X group of the compound (2) may have 1 to 6 carbon atoms.

The compound (1) includes the following (or a mixture thereof). _{[C 8 F 17 CH 2 CH} 2 O] 2 PO [OH] [C 8 F 17 CH 2 CH (OH) CH 2 O] PO [OH] 2 [C 6 F 13 CH 2 CH 2 O] 2 PO [ _{OC 2 H 5] [C 10} F 21 CH 2 CH 2 O] 2 PO [OH] [C 8 F 17 SO 2 N (CH 3) CH 2 O] 2 PO [OH] [C 8 F 17 SO 2 N _{(C 2 H 5) CH 2} CH 2 O] PO [OC 2 H 5] 2 [C 16 F 33 CH 2 CH 2 O] PO [OC 8 H 17] 2 [C 8 F 17 CH 2 CH 2 O] _{3 PO [C 12 F 25 CH} 2 CH 2 O] 2 PO [OH] [C 8 F 17 SO 2 N (C 2 H 5) CH 2 CH 2 O] PO (OH) [OC 2 H 5] 2 [ _{C 10 F 21 CH 2 CH 2} O] PO [OH] 2 [C 8 F 17 CH 2 CH (OH) CH 2 O] 2 PO [OC 3 H 7] [C 8 F 17 CH 2 CH 2 CH 2] PO [OH] ₂ [C ₁₀ F ₂₁ CH ₂ CH ₂ CH ₂ ] PO [OC ₂ H ₅ ] ₂

[0014]

Embedded image

The compound (2) is as follows (or a mixture thereof). _{[C 8 F 17 CH 2 CH} 2 O] 2 PO [ONH 2 (C 2 H 4 OH) 2] [C 8 F 17 CH 2 CH (OH) CH 2 O] PO [ONH 2 (C 2 H 4 OH ) ₂ ] ₂ [C ₆ F ₁₃ CH ₂ CH ₂ O] ₂ PO [ONH ₂ (C ₂ H ₄ OH) ₂ ] [C ₁₀ F ₂₁ CH ₂ CH ₂ O] ₂ PO [ONH (C ₂ H ₄ OH) ) ₃ ] [C ₁₂ F ₂₅ CH ₂ CH ₂ O] ₂ PO [ONH (C ₂ H ₅ ) ₃ ] [C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ O] ₂ PO [ONH ₂ (C _{2 H 4 OH) 2] [C} 8 F 17 SO 2 N (C 2 H 5) CH 2 CH 2 O] PO [ONH 2 (C 2 H 4 OH) 2] 2 [C 16 F 33 CH 2 CH 2 O _{] PO [ONH 2 (C 2} H 4 OH) 2] 2 [C 16 F 33 CH 2 CH 2 O] PO [ONH 2 (C 2 H 5) 2] 2 [C 8 F 17 CH 2 CH 2 O] ₂ PO [ONH ₄ ] [C ₁₀ F ₂₁ CH ₂ CH ₂ O] PO [ONH ₄ ] ₂ [C ₁₂ F ₂₅ CH ₂ CH ₂ O] ₂ PO [ON (C ₂ H ₅ OH) ₃ ] [C _{12 F 25 CH 2 CH 2 O]} 2 PO [ONH (C 2 H 5 OH) 2] [C 8 F 17 CH 2 CH (OH) CH 2 O] 2 PO [ONa] [C 8 F 17 CH 2 CH ( _{OH) CH 2 O] 2 PO} [OKa]

[0016]

Embedded image And so on.

Of the above compounds, compound (1) is n
Is 1, for example, it can be synthesized by reacting an alcohol having a perfluoro group with POCl ₃ and washing with water. That is, mRf-OH + POCl ₃ → [Rf-O] _m PO (Cl) _3-m [Rf-O] _m PO (Cl) _3-m + (3-m) H ₂ O → [Rf-O] _m PO (OH) _3-m can be synthesized.

Of the above compounds, compound (1) is n
Is 1, for example, an alcohol having an Rf group and POCl ₃
After reacting, the compound can be synthesized by washing with water. That is, mRf-OH + POCl ₃ → [Rf-O] _m PO (Cl) _3-m [Rf-O] _m PO (Cl) _3-m + (3-m) ROH → [Rf-O] _m PO (OR) _3-m [where R represents a linear or branched alkyl group having 1 to 18 carbon atoms. ] Can be synthesized.

Further, among the above compounds, compound (2)
Can be synthesized by the following reaction when n is 1. [Rf-O] _m PO (OH) _3-m + XOH → [Rf-O] _m PO (OX) _3-m [where X is an alkali metal. Or [Rf-O] _m PO (OH) _3-m + NR '(R'')(R''') →
[Rf-O] _m PO (ONR'R "R"') _3-m [where R', R ", R '" represents a hydrogen atom, an alkyl group or a hydroxyalkyl group. Regarding the actual synthesis of these compounds, specific synthesis methods are described in, for example, JP-A-64-6196.

The treating agent may contain either compound (1) or compound (2) or both. The amount of the fluorinated phosphoric acid compound is generally 0.05 to 20% by weight, preferably 0.3% by weight, based on the treating agent.
To 10% by weight.

It is preferable that the treating agent contains an organosilicon compound in addition to the fluorine-containing phosphoric acid compound. The organosilicon compound has the general formula (I):

Embedded image

[In the formula, R ¹ⁿ represents a saturated alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, they may be the same or different. R ²ⁿ represents a hydrogen atom or a saturated alkyl group having 1 to 5 carbon atoms, and when nn is 2 or more, they may be the same or different. nn is 1
Represents an integer of from 9 to 9. ] Is preferable.

The saturated alkyl group having 1 to 18 carbon atoms represented by R ¹ⁿ is not particularly restricted but includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, octyl. And a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, etc., which may be linear or branched.

The hydrogen atom or the saturated alkyl group having 1 to 5 carbon atoms represented by R ²ⁿ is not particularly limited.
For example, methyl group, ethyl group, propyl group, butyl group,
Pentyl groups and the like can be mentioned, and these may be linear or branched. The above nn is an integer of 1 to 20. Particularly, nn is preferably 1.

As the organosilicon compound represented by the formula (I), more specifically, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyl Trimethoxysilane, hexyltrimethoxysilanol, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane Silane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane Heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tetradecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, etc. Among them, methyltrimethoxysilane, methyltriethoxysilane, and hexyltriethoxysilane are preferable.

Further, dimers of organosilicon compounds and the like also include
It can be used as the organosilicon compound used in the present invention, and examples of such a compound include those in which nn is 2 in the general formula (I). Further, nn may be an integer up to 20.

The organosilicon compound is preferably in the form of an aqueous dispersion emulsified in water. Such emulsification can be performed by a conventionally known method, for example,
Examples thereof include a method using an emulsifier. The emulsifier is not particularly limited, and examples thereof include a nonionic emulsifier and an anionic emulsifier.

The nonionic emulsifier is not particularly limited. For example, common nonionic emulsifiers include glycerol monostearate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate,
Examples thereof include polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, fluoroalkyl ethylene oxide and polyalkyl-modified polydimethylsiloxane.

The anionic emulsifier is not particularly restricted but includes, for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenyletherdisulfonate, and the like.

The proportion of the emulsifier in the aqueous dispersion of the organosilicon compound is not particularly limited, but may be 0.01 to 20% by weight.
Is preferred. Any of the above nonionic emulsifiers and any of the above anionic emulsifiers may be used alone or in combination, or a nonionic emulsifier and an anionic emulsifier may be used in combination.

The method of emulsifying the organosilicon compound using the emulsifier is not particularly limited. For example, water is added dropwise to the mixture of the organosilicon compound and the emulsifier little by little while stirring the mixture with a homomixer or the like at a high speed. Can be emulsified.

When an organosilicon compound is added, the following effects can be obtained. The water and oil repellency of the fluorinated phosphoric acid compound increases. By forming a permeable layer on the substrate, the water- and oil-repellency of the fluorine-containing phosphoric acid compound is increased, and the water absorption resistance can be increased. Thus, deterioration of the base material can be prevented, and the life can be further extended. The amount of the organosilicon compound added is
It is preferably from 0.5 to 50% by weight, preferably from 1 to 20% by weight, based on the treating agent. When the content is 0.5% by weight or more, the penetration of water into the substrate (water absorption) becomes lower. When the content is 50% by weight or less, the water repellency and moisture permeability of the fluorinated phosphoric acid compound are more favorably maintained.

The treating agent may contain a fluorine-containing resin. In general, a fluorine-containing resin can be contained in a treating agent by blending an aqueous dispersion of the fluororesin with the treating agent. The aqueous dispersion of the fluorine-containing resin generally contains an emulsifier. As emulsifiers, ionic and / or
Alternatively, non-ionic emulsifiers can be used.

Examples of the fluorine-containing resin include (1) a copolymer of a fluoroolefin and a vinyl monomer, (2) a homopolymer of one fluoroolefin, and (3) a copolymer of two or more fluoroolefins. Examples of the polymer include (4) a polymer in which an acrylic resin is seed-polymerized on the polymer (1), (2) or (3).

The fluoroolefin is preferably an olefin having 2 to 4 carbon atoms having at least one fluorine atom. Examples of the fluoroolefin include vinyl fluoride (VF), vinylidene fluoride (VdF), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), and hexafluoropropylene (H
FP) and the like.

The vinyl monomer is a monomer containing no fluorine atom. Ethylene as a vinyl monomer,
Olefins such as propylene, vinyl ethers such as cyclohexyl vinyl ether and hydroxybutyl vinyl ether, alkenyls such as ethyl allyl ether, vinyl acetates, vinyl esters such as Veova 9 (manufactured by Shell), and ethylenically unsaturated carboxylic acids such as crotonic acid. And the like.

The acrylic resin is not particularly limited as long as it is a polymer whose main chain is constituted by a hydrocarbon chain derived from acrylic acid and / or methacrylic acid. Usually, a homopolymer of an acrylic monomer, Copolymers of an acrylic monomer and another monomer having an ethylenically unsaturated double bond copolymerizable therewith can be exemplified. The acrylic monomer is not particularly limited as long as it contains acrylic acid and / or methacrylic acid, and examples thereof include acrylic acid, alkyl acrylate, methacrylic acid, and alkyl methacrylate.
The alkyl (meth) acrylate is not particularly limited, and examples thereof include (meth) acrylic esters having 1 to 18 carbon atoms in the alkyl group. For example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-methacrylate
Examples include ethylhexyl and 2-hydroxyethyl methacrylate. A method of seed polymerizing an acrylic resin with a fluoroolefin polymer is disclosed in JP-A-9-2629.
40.

In the treating agent, the amount of the fluorine-containing resin is preferably 0.5 to 100 parts by weight of the treating agent in solid content.
10 to 10 parts by weight, more preferably 1 to 5 parts by weight.
When the amount is 0.5 part by weight or more, the durability of the water / oil repellency is favorably increased, while when the amount is 10 parts by weight or less, the initial water / oil repellency is good. By using a fluorine-containing resin,
Since the durability of the water and oil repellency and the initial water and oil repellency are increased, the effect of protecting the base material is improved.

As described above, the treating agent of the present invention comprises (a)
A fluorine-containing phosphoric acid compound, (b) a fluorine-containing phosphoric acid compound and an organic silicon compound, (c) a fluorine-containing phosphoric acid compound and a fluorine-containing resin, or (d) a fluorine-containing phosphoric acid compound, an organic silicon compound and Contains fluorinated resin.

The surface conditioner is a chemical that lowers the surface tension of the treatment agent and improves the wettability and permeability of the treatment agent to the substrate. Examples of the surface conditioner include a hydroxyl group-containing compound (eg, alcohol), a silicone compound, and the like.
It is preferable that the surface conditioner be easily volatilized at normal temperature and normal pressure. The boiling point of the surface conditioner may be 300 ° C. or less at 1 atm, for example, 40 to 200 ° C.

Examples of the hydroxyl group-containing compound include alcohols, hydroxyl group-containing ethers and the like. The alcohol may be a monohydric alcohol, a polyhydric alcohol (for example, a dihydric alcohol). Examples of monohydric alcohols are
Hydrocarbon-based alcohols (eg, fluorine-free alcohols such as methanol, ethanol, propanol, isopropanol, and acetylene-based alcohols), and fluorinated alcohols (eg, 2,2,3,3,3-pentafluoropropanol, 2,2) , 3,3,4,4,5,5-
Octafluoropentanol). Examples of polyhydric alcohols are glycols, especially hydrocarbon glycols. Examples of glycols are ethylene glycol, diethylene glycol.

The hydroxyl group-containing ether is a monoalkylene glycol or a polyalkylene glycol.
An ether compound having one hydroxyl group in which two hydroxyl groups are substituted with an alkoxy group is preferable. The alkylene glycol constituting the monoalkylene glycol and the polyalkylene glycol is generally ethylene glycol and propylene glycol. The monoalkylene glycol and polyalkylene glycol are generally preferably composed of 1 to 20 molecules of ethylene glycol or propylene glycol. The alkoxy group in the hydroxyl group-containing ether preferably has 1 to 10 carbon atoms. Examples of alkoxy are methoxy, ethoxy, propoxy, butoxy, pentoxy. An example of a hydroxyl group containing ether is diethylene glycol monobutyl ether.

The hydroxyl group-containing compound (especially alcohol) may have 1 to 18, preferably 1 to 10, especially 1 to 5, carbon atoms. The silicone compound is Si-O
A compound having a unit, such as dimethyl silicone. The amount of the surface conditioning agent is 0.5-5 to the treatment agent.
0% by weight, preferably 1-20% by weight, for example 1-10
% By weight.

The substrate used in the present invention preferably contains a cationic substance. Cationic substances are divalent or higher (eg, divalent, trivalent or tetravalent) metal ions,
It may be a cationic group-containing polymer. Examples of metal ions include calcium (Ca), magnesium (Mg), aluminum (Al), chromium (Cr), zirconium (Z
r), metal ions such as titanium (Ti). The cationic substance is contained in a metal compound, for example, a metal salt. As compounds of divalent or higher valent metals, chlorides, nitrates, sulfates and hydroxides are preferred.

Examples of the cationic group-containing polymer include polyethyleneimine, polyamine-modified products, and polyamidepolyamine-epichlorohydrin reactants.
In addition, cation-modified polyacrylamide, melamine-formaldehyde resin, urea-formaldehyde resin, urea-formaldehyde resin, dicyandiamide-
Formaldehyde resins and the like can also be exemplified. The cationic group-containing polymer is preferably a water-soluble polymer.

The substrate is used in an amount of 0.05 to 90 based on the weight of the substrate.
It is preferred to contain, by weight, for example 1 to 70% by weight of the metal compound and / or the cationic group-containing polymer. The cement base contains calcium and aluminum as cationic substances. Fluorine-containing phosphoric acid compounds are easily immobilized on cement-based substrates containing calcium, aluminum, etc., because the hydroxyl group bonded to the phosphorus atom and the divalent or higher valent metal are ionically bonded to form an insolubilized substance. good.

When the substrate does not contain a cationic substance,
Before or after the application of the fluorinated phosphoric acid compound, the building material of the present invention can be produced by applying a cationic substance to the substrate. Woodwork-based materials generally do not contain cationic substances. Before or after applying the treating agent to the woodwork-based substrate, an aqueous solution of a divalent or higher-valent metal compound such as an aqueous solution of aluminum chloride or an aqueous solution of a cationic polymer may be applied and fixed.

In that case, 0.01 to 20% by weight of the base material
A cationic substance can be immobilized by applying a solution (for example, an aqueous solution) of a metal compound or a cationic polymer at a concentration of 20 to 1000 g / m ² and then drying. The fixing method may be any method such as painting and dipping. Drying may be performed at room temperature, but may be performed at about 80 to 200 ° C. When producing a particle board such as a particle board, a base material and a cationic substance may be mixed and pressed.

Although the building material treated with the phosphoric acid compound has water repellency and thus has an antifungal effect, the treating agent may contain a conventionally used antifungal agent. The fungicides that can be used are chlorine, organic sulfur / nitrogen, organic chlorine, organic tin, nitrile, phenol, isothiazoline,
All fungicides such as benzimidazoles can be used.
The antifungal agent is preferably dissolved or dispersed in water or alcohol. The amount of the fungicide is 0.0
It may be from 01 to 5% by weight.

This treating agent is diluted with a lot of water.
If the hardness of the water used is high, the fluorine-containing phosphoric acid compound may precipitate as a phosphate, and in order to prevent it, an anionic surfactant or a nonionic surfactant,
Alternatively, both may be added.

Examples of the anionic surfactant include alkyl benzene sulfonic acid, alkyl benzene sulfonate, alkyl sulfate, alkenyl succinate, fatty acid salt, alkyl sulfonate, polyoxyethylene alkyl ether sulfonate, alkyl naphthalene sulfone. Sun salt, monoalkyl or dialkyl phosphate. Examples of the salt include a sodium salt, a potassium salt, an ammonium salt, and a substituted ammonium salt (the substitution includes an alkyl group and a hydroxyalkyl group, and the number of substitution may be 1 to 3).

Examples of the nonionic surfactant include polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene fatty acid ester. The surfactant is preferably added at 0.5 to 20% by weight based on the fluorine-containing phosphoric acid compound. When the amount of the surfactant is in this range, good dispersion of the fluorine-containing phosphoric acid compound and good water / oil repellency can be obtained. If necessary, the treating agent may contain an antifreezing agent, a viscosity adjusting agent, an ultraviolet absorber, an antioxidant, a pH adjusting agent, an antifoaming agent, a preservative, a flame retardant and the like.

In the present invention, a treating agent is applied to a substrate to impart waterproofness to building materials. The building material has water vapor permeability and antibacterial and antifungal properties in addition to waterproofness. The substrate may be a cement-based substrate, a gypsum-based substrate, a woodwork-based substrate, or a porcelain-based substrate. The porosity of the porous substrate (the ratio of the volume of the pores to the total volume including the pores of the substrate) is, for example, 2 to 2.
It may be 80%, especially 5-50%. Examples of cementitious substrates are concrete, mortar, molded concrete boards or siding boards. Examples of the molded concrete board include a precast concrete board (PC board), a fiber reinforced concrete board (FRC board), a lightweight cellular concrete board (ALC board), an extruded cement board, and the like.
Examples of the siding board include a flexible board, a calcium silicate board, a hard wood chip cement board, an asbestos cement perlite board, and a slate board. An example of the gypsum base material is gypsum board.

Examples of woodwork-based substrates include solid wood (for example, hinoki, drill, cedar, pine), plywood (for example, wood chip plywood, fiber reinforced wood chip plywood), veneer laminate (LVL), and assembly Wood, particle board (particle board),
Fiberboard, cork, wood wool cement board, wood chip cement board, pulp cement board, medium density fiber board (MDF), gradient strand board (OSB), and wafer board (WB). Examples of porcelain-based substrate is a tile or the like. Examples of clay-based substrates are tiles, bricks and the like.

The building material of the present invention can be used as an interior material or an exterior material. The building material is a building board, a building board, or the like. The building materials can be used for walls, roofs, pillars, indoor walls, indoor top plates (for example, kitchen top plates), inner walls of bathrooms, inner and outer walls of parking lots, joints of boards and tiles, furniture, and the like. The coating with the treating agent may be provided on the front surface (the outdoor facing side of the building material) and / or the back surface (the indoor facing side of the building material). The surface of the building material that is exposed to the weather may have a treatment agent coating, or the surface of the building material that faces indoors without exposure to the weather may have a treatment agent coating. Particularly good persistence of water and oil repellency and water vapor permeability are obtained when the back surface is coated with a treatment agent. The treating agent of the present invention may be coated on the inside of a building.

The building material of the present invention can be obtained by applying a treating agent to a substrate. The amount of treatment agent is 20 to 100
It may be applied at 0 g / m ² , preferably 50 to 500 g / m ² . The application may be performed once or may be divided into a plurality of times. As the application method, brush application, spray, roller, impregnated with soaked in waste, etc.
Any method such as dipping may be used, and the excess may be wiped off as necessary. Next, the treating agent is dried.
Drying may be performed at room temperature or may be performed at 80 to 250 ° C. In the case of a ceramic building material such as a siding board, a treatment agent can be applied before the autoclave curing at the time of manufacturing the building material to perform autoclave curing. Before hot pressing even woodwork plywood, a treating agent may be applied.

[0057]

EXAMPLES Examples of the present invention will be described below, but these are merely specific examples of the present invention, and the present invention is not limited thereto. In the following, parts and percentages are unless otherwise specified.
Parts by weight and% by weight.

In the following examples, the following method was used for conducting the test. The color change of the substrate was observed before and after the application of the substrate color change treating agent. ○: unchanged from the color of the substrate △: slightly changed from the color of the substrate ×: changed to the wet color of the substrate

Storage stability The treatment liquid was allowed to stand at room temperature for one week, and the uniformity of the liquid was visually evaluated. ○: The liquid is uniform ×: The contact angle at which the liquid is separated The contact angle was measured using a CA-DT type measuring device manufactured by Kyowa Interface Science Co., Ltd.
It was measured by the droplet method. More than 150 degrees is the measurement limit of the contact angle meter. In addition, even when water drops were repelled and could not be measured on the test plate and measurement was impossible, the angle was set to 150 ° or more. The water repellency of the water repellency test plate was measured according to JIS L1092. The higher the score, the higher the water repellency.

Water Drop Spot Test 1 g of water was placed on the test plate and allowed to stand for 2 hours, and then the permeation of water into the test plate and the rolling of water when the plate was inclined at 45 ° from the horizontal were visually observed. . ：: Water does not roll down without penetrating △: Water does not roll down without penetrating ×: Water does not roll down and does not roll

[0061] As shown in moisture resistance Figure 1, with a roof in a water bath at 50 ° C., so that the processing surface of the test plate facing the water bath,
A test plate was attached to the inside of the roof. After performing an operation of continuously applying steam to the treated surface for one week, the contact angle was measured, and the impregnation property with water was visually judged. The contact angle was measured by a droplet method using a CA-DT type measuring device manufactured by Kyowa Interface Science Co., Ltd. The penetration property was evaluated according to the following criteria. ：: not permeated. Color not applicable to base material: △: Partially infiltrated, part of base material wet color ×: Sink, part of base material wet color

1 g of a sulfuric acid aqueous solution having 5% acid resistance was placed on a test plate, and allowed to stand at 25 ° C. for 1 hour. The test plate was washed with water and dried at 25 ° C. for 2 hours. Thereafter, the contact angle of water at the portion where the aqueous sulfuric acid solution was placed was measured by a droplet method using a CA-DT type measuring device manufactured by Kyowa Interface Science Co., Ltd. The contact angle was measured using a weather-resistant sunshine weatherometer (Suga Test Machine) under a test condition of JIS K5400 for 500 hours.
The contact angle was measured using a Kyowa Interface Science Co., Ltd.
It was measured by the droplet method.

An epoxy resin is applied to the back and side surfaces of the treated surface of the water absorption test plate,
Sealing was performed to prevent water from entering. After the test plate was immersed in water at room temperature for 7 days, the surrounding water was removed with a dry rag and the weight was measured. The water absorption ratio was expressed as the ratio of the weight increase when the weight increase of the test plate prepared in Comparative Example 4 was set to 1.

An epoxy resin is applied to the back and side surfaces of the treated surface of the moisture permeability test plate,
Sealing was performed to prevent moisture from entering. The test plate was then
The sample was placed in a thermo-hygrostat at 95 ° C. and a relative humidity of 95%, and allowed to stand for 4 hours. The test plate was taken out and immediately weighed. The moisture absorption was determined according to the following formula: moisture absorption (%) = (weight of test plate after moisture absorption-weight of test plate before moisture absorption) / (weight of test plate before moisture absorption) × 100. This is a test conducted under high-temperature and high-humidity conditions in order to confirm sustainability, assuming indoor use.

Example 1 A treating solution containing 2% by weight of [C ₈ F ₁₇ CH ₂ CH ₂ O] PO [ONH ₄ ] ₂ (Compound 1) and 10% by weight of isopropyl alcohol (IPA) (Compound 1, IPA and Aqueous solution consisting of water)
It was created. Spray coating of this treatment agent solution on a flexible board (15 cm long x 7 cm wide x 0.3 cm thick) (coating amount: 200
g treating solution / m ² ) and left at room temperature for 3 days. The test shown in Table 1 was performed on this test plate. The results are shown in Table A.

Example 2 Fluorine-containing phosphoric acid compound was converted to [C ₈ F ₁₇ CH ₂ CH ₂ O] PO [ON
H ₄ ] ₂ (Compound 1) Instead of 2% by weight, [C ₈ F ₁₇ CH ₂ CH
₂ O] ₂ PO [ONH ₂ (C ₂ H ₄ OH) ₂ ] (Compound 2) The same procedure as in Example 1 was repeated except that the amount was 2% by weight. The results are shown in Table A.

Example 3 Fluorine-containing phosphoric acid compound was converted to [C ₈ F ₁₇ CH ₂ CH ₂ O] PO [ON
H ₄ ] ₂ (Compound 1) [C ₂ F ₅ (CF ₂ CF ₂ ) n]
CH ₂ CH ₂ O] PO [ONa] ₂ (compound 3) [n is 3, 4,
5, 6 (molar ratio of each compound is 5: 3: 2: 1)], and the same procedure as in Example 1 was repeated. The results are shown in Table A.

Example 4 [C ₆ F ₁₃ CH ₂ CH ₂ O] PO [OH] ₂ (compound 4) 2% by weight and nonionic surfactant Emulgen 930 (manufactured by Kao) 0.2
Wt% and isopropyl alcohol (IPA) 10 wt
%, Except that a treating agent liquid containing 0.1% (emulsion in an aqueous medium) was used. The results are shown in Table A.

Example 5 A fluorinated phosphoric acid compound was prepared using [C ₈ F ₁₇ CH ₂ CH ₂ O] PO [ON
[C ₈ F ₁₇ CH ₂ CH ₂ ] instead of H ₄ ] ₂ (Compound 1) 2% by weight
The same procedure as in Example 1 was repeated, except that PO [ONH ₄ ] ₂ (compound 5) was 2% by weight. The results are shown in Table A.

Example 6 The procedure of Example 1 was repeated, except that 1% by weight of an acetylene alcohol Surfynol SF61 (manufactured by Air Products) was added to the treating solution instead of 10% by weight of isopropyl alcohol. The results are shown in Table A.

Example 7 A fluorinated alcohol (2,2,3,3,3-pentafluoropropanol) was used in place of isopropyl alcohol at a concentration of 2% based on the treating solution.
The same procedure as in Example 1 was repeated, except that it was inserted. The results are shown in Table A.

Example 8 Instead of a flexible board, a lightweight cellular concrete (ALC) board (length 70 mm × width 150 mm × thickness 37 m)
The same procedure as in Example 1 was repeated, except that m) was used. The results are shown in Table A.

Example 9 Instead of a flexible board, wooden plywood (length 70 mm)
× 150 mm in width × 10 mm in thickness). First, a polyamide polyamine-epichlorohydrin reactant having a solid concentration of 1% (WS-57 manufactured by Nippon PMC Co., Ltd.) was applied to wood plywood.
0) was coated at 100 g / m ² . Thereafter, drying was performed at 80 ° C. for 2 minutes to prepare a plywood. Thereafter, the same procedure as in Example 1 was repeated. The results are shown in Table A.

Example 10 The same procedure as in Example 9 was repeated, except that wood plywood not coated with the polyamide polyamine-epichlorohydrin reactant (WS-570 manufactured by Nippon PMC Co., Ltd.) was used. The results are shown in Table A.

Example 11 The same procedure as in Example 1 was repeated, except that the amount of the fluorinated phosphoric acid compound in the treating solution was changed to 1% by weight instead of 2% by weight. The results are shown in Table A.

Example 12 The same procedure as in Example 1 was repeated, except that a treating agent solution containing only 2% by weight of compound 1 and no isopropanol was used. The results are shown in Table A.

Example 13 An aqueous dispersion of n-hexyltriethoxysilane (n-hexyltriethoxysilane / dodecylbenzenesulfonic acid) was added to a solution containing compound 2 (fluorine-containing phosphoric acid compound) obtained in Example 2. (Emulsified dispersion of sodium / water = 50/5/45) was added to obtain a treating agent liquid, and the same procedure as in Example 1 was repeated. In the obtained treating solution, the amount of the fluorinated phosphoric acid compound was 2% by weight based on the treating solution, and the amount of n-hexyltriethoxysilane was 10% by weight based on the treating solution. . Result A
It is shown in the table.

Example 14 Aqueous dispersion of n-hexyltriethoxysilane in a liquid containing compound 4 (fluorinated phosphoric acid compound), nonionic surfactant (Emulgen 930) and IPA obtained in Example 4 Compound (n-hexyltriethoxysilane / sodium dodecylbenzenesulfonate / water = 50/5/45)
The same procedure as in Example 1 was repeated, except that an emulsified dispersion of In the obtained treating solution, the amount of the fluorinated phosphoric acid compound was 2% by weight based on the treating solution, and the amount of n-hexyltriethoxysilane was 5% by weight based on the treating solution. . The results are shown in Table A.

Example 15 The same procedure as in Example 13 was repeated, except that the treating solution further contained a fluorine-containing resin. That is, the first embodiment
The treating agent solution obtained by adding the fluorine-containing resin solution to the treating agent solution used in 3 was applied to a flexible board. The fluorinated resin liquid was obtained by adding butyl carbitol acetate as a film-forming aid to the aqueous fluorinated resin dispersion at 15% by weight based on the solid resin. In the treating agent solution used in this example, the amount of the fluorine-containing phosphoric acid compound was 2% by weight based on the treating agent solution, and the amount of n-hexyltriethoxysilane was 10% by weight based on the treating agent solution. And the amount of the fluorine-containing resin was 1% by weight based on the treating agent liquid. The results are shown in Table A.

The aqueous fluororesin dispersion was obtained as follows. 500 ml of deionized water, 0.5 g of ammonium perfluorooctanoate, polyoxyethylene lauryl ether, a nonionic non-fluorinated surfactant (MYS25, manufactured by Nikko Chemicals), in a pressure-resistant reaction vessel equipped with a stirrer having a content of 1 liter, charge, nitrogen pressed, repeatedly degassed, after removing the dissolved air, was continuously fed a VdF, 3
After the reaction was performed for 0 hour, the inside of the tank was returned to normal temperature and normal pressure to complete the reaction, and an aqueous dispersion containing VdF polymer particles was obtained. Next, 70 g of the aqueous dispersion was placed in a 200-ml four-necked flask equipped with a stirring blade, a cooling pipe, and a thermometer.
And JS2 (Sanyo Chemical) as a surfactant
And, RS30 (Sanyo Kasei) was added in an amount of 0.5% by weight based on the solid content. The mixture was heated in a water bath with stirring. When the tank temperature reached 80 ° C., the solid content of the VdF polymer was 10%.
Emulsion obtained by emulsifying a monomer mixture of 40 parts by weight of methyl methacrylate / butyl acrylate / acrylic acid in a 96/2/2 weight ratio with respect to 0 parts by weight with a 0.5% by weight aqueous solution of JS2 (Sanyo Chemical). And 8 parts by weight of a 50% by weight aqueous solution of RMA450M (Japanese emulsifier) was added dropwise over 1 hour. Immediately thereafter, 20 ml of a 0.1% by weight aqueous solution of ammonium persulfate was continuously dropped over 3 hours. Three hours later,
Raise the temperature in the bath to 85 ° C, hold it for 1 hour, then 80 ° C,
The emulsion was concentrated at 180 mmHg until the solid content of the emulsion became 52% by weight. Thereafter, the mixture was cooled, adjusted to pH 7 with aqueous ammonia, and filtered through a 300-mesh wire net to obtain an aqueous dispersion containing blue-white fluorine-containing seed polymer particles.

Comparative Example 1 Water repellent Tight Silane Super (Toyo Ink: 60% active ingredient) in which a silane compound was dispersed in water with an emulsifier (“Si
System. ) Was repeated, except that) was used. The results are shown in Table A. Comparative Example 2 Unidyne TG, a perfluoroacrylate-based repellent
The same procedure as in Example 1 was repeated, except that 2% by weight of -410 (manufactured by Daikin Industries, Ltd.) solution (abbreviated as "RfAc-based") was used. The results are shown in Table A.

Comparative Example 3 Methyl methacrylate / butyl acrylate (75/2
Emulsion polymerization using 5% by weight of emulsifier Emulgen 950 (manufactured by Kao: polyoxyethylene nonylphenyl ether) and 1% of Perex OT-P (manufactured by Kao: sodium dialkyl sulfosuccinate) using ammonium persulfate as an initiator. CS12 (manufactured by Chisso Corporation: 2, 2,
Same as Example 1 except that 5% of 4-trimethylpentanediol-1,3-monoisobutyrate) was used and the solid content was reduced to 40% with water (abbreviated as “AcEm system”). The procedure was repeated. The results are shown in Table A.

Comparative Example 4 A similar test was performed using a flexible board to which the treatment liquid was not applied. The results are shown in Table A. Comparative Example 5 Using lightweight cellular concrete without applying the treating agent liquid,
A similar test was performed. The results are shown in Table A.

Comparative Example 6 A similar test was performed using wood plywood to which the treating agent solution was not applied. The results are shown in Table A. Comparative Example 7 Fluorine-containing phosphoric acid compound was converted to [CF ₃ (CF ₂ CF ₂ ) ₃ CH ₂ O] ₂ POOH
A treating agent solution containing 10% by weight of (Compound 6) and 10% of IPA was prepared, and 200 g / m ^{2 was} applied to a vinyl chloride substrate. Drying was left at room temperature for 3 days. The results are shown in Table A.

[0085]

[Table 1] Table A

[0086]

[Table 2]

[0087]

[Table 3]

Example 16 The same procedure as in Example 15 was repeated, except that 2% of diethylene glycol monobutyl ether (surface modifier) was added to the treating solution obtained in Example 15 (based on the treating solution). Was. The results are shown in Table B.

Example 17 Fluorine-containing phosphoric acid compound (compound 2) 4% (solid content)
Fluorine-containing resin (same as used in Example 15)
4% (solid content), n-hexyltriethoxysilane 10
%, And the same procedure as in Example 15 was repeated, except that a treating solution containing 2% of diethylene glycol monobutyl ether (surface conditioner) was used. The results are shown in Table B.

Example 18 Fluorine-containing phosphoric acid compound (compound 2) 8% (solid content)
Fluorine-containing resin (same as used in Example 15)
8% (solid content), n-hexyltriethoxysilane 20
%, And the same procedure as in Example 15 was repeated, except that a treating solution containing 4% of diethylene glycol monobutyl ether (surface conditioner) was used and the coating amount of the treating solution was 100 g / m ² . The results are shown in Table B.

Example 19 Instead of a flexible board, an untreated wood plywood (70 mm long × 150 mm wide × 10 mm thick) was prepared by reacting a polyamide polyamine-epichlorohydrin reactant having a solid concentration of 1% (WS-manufactured by Nippon PMC Co., Ltd.). 570) to 100 g / m
The same procedure as in Example 17 was repeated, except that two plywoods obtained by ^two coatings and drying at 80 ° C. for 2 minutes were used.
The results are shown in Table B.

[0092]

[Table 4] Table B

The following can be seen from the above Examples and Comparative Examples. (1) The building material of the present invention has a high contact angle, a high score in a water repellency test, and is not impregnated in a water drop spot test. (2) Since the building material of the present invention does not produce a wet color, the base material can be utilized without changing the color of the base material. (3) Since the building material of the present invention has high moisture resistance, it is durable against water and water vapor and has a long lasting water repellency. (4) Since the building material of the present invention has high acid resistance, it has water repellency persistence to an external environment such as acid rain. (5) Since the building material of the present invention has good weather resistance, it has good water-repellent weather resistance. (6) The building material of the present invention does not impair the water vapor permeability of the porous substrate. (7) Since the building material of the present invention has waterproofness against water droplets and water vapor permeability, it has waterproofness to the inside of a house or the inside of a wall and can discharge moisture. This makes it difficult for dew condensation to occur at the boundary or inside of the wall, and can prevent generation of mold and deterioration of the base material.

[0094]

The building material of the present invention has water and oil repellency, its durability, weather resistance and acid rain resistance. Further, the building material of the present invention has waterproofness, air permeability, and mold resistance. Since the building material of the present invention has waterproofness and water vapor permeability and thus has prevention of dew condensation inside the building and good acid resistance and weather resistance, it can be suitably used even outdoors exposed to wind, rain and sunlight.

[Brief description of the drawings]

FIG. 1 is a view showing an apparatus used for measuring moisture resistance in Examples and Comparative Examples.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 123/02 123/02 127/12 127/12 E04B 1/66 E04B 1 / 66 A (72) Inventor Yasuo Itami 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works F-term (reference) 2E001 DA01 DB04 HF01 HF05 4F100 AA04B AA05B AC03A AD00A AE01A AE06A AH06B AK02BAK02J AK02BAK02J AK52B AL01B AL05B AP00A BA02 DJ00A GB07 JB06 JD04 4H020 BA11 BA21 BA36 4J038 CB001 CD091 CG001 CQ001 JC20 JC24 JC30 MA08 MA10 NA07 PB05 PC03 PC04 PC06

Claims (19)

[Claims] 1. A building material obtained by applying a treatment agent containing a fluorine-containing phosphoric acid compound to a porous substrate. 2. The building material according to claim 1, wherein the porous substrate contains a cationic substance. 3. The building material according to claim 1, wherein the treating agent contains a fluorine-containing phosphoric acid compound, a surface conditioner, and water. 4. The fluorine-containing phosphoric acid compound represented by formula (1) or (2): [Rf- (O) _n ] _m PO (OR) _3-m (1) A monovalent group having 21 linear or branched perfluoroalkyl groups or perfluoroalkenyl groups, m represents an integer of 1 to 3, and n represents an integer of 0 or 1. R represents H or a linear or branched alkyl group having 1 to 21 carbon atoms. Or _{[Rf- (O) n] m} PO (OX) 3-m (2) [ wherein, Rf is a 1-21 carbon linear or branched Pa -
M represents a monovalent group having a fluoroalkyl group or a perfluoroalkenyl group, m represents an integer of 1 to 3, and n represents an integer of 0 or 1. X represents an alkali metal or an ammonium group which may be substituted with an alkyl group or a hydroxyalkyl group. ] The building material of Claim 1 shown by these. 5. The building material according to claim 1, wherein the treating agent contains an organosilicon compound in addition to the fluorine-containing phosphoric acid compound. 6. An organosilicon compound represented by the general formula (I): [In the formula, R ¹ⁿ represents a saturated alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, they may be the same or different. R ²ⁿ represents a hydrogen atom or a saturated alkyl group having 1 to 5 carbon atoms, and when nn is 2 or more, they may be the same or different. nn represents an integer of 1 to 9. The building material according to claim 5, which is represented by the following formula: 7. The building material according to claim 5, wherein the organosilicon compound in the aqueous dispersion is added to a treating agent containing a fluorine-containing phosphoric acid compound. 8. The building material according to claim 1, wherein the treating agent contains a fluorine-containing resin in addition to the fluorine-containing phosphoric acid compound. 9. The fluororesin comprises (1) a copolymer of a fluoroolefin and a vinyl monomer, (2) a homopolymer of one fluoroolefin, and (3) a copolymer of two or more fluoroolefins. The building material according to claim 8, wherein the building material is a polymer in which an acrylic resin is seed-polymerized with (4) the polymer (1), (2) or (3). 10. The building material according to claim 1, wherein the treating agent contains an organosilicon compound and a fluorine-containing resin in addition to the fluorine-containing phosphoric acid compound. 11. The building material according to claim 1, wherein the porous substrate is a cement-based substrate, a gypsum-based substrate, a woodwork-based substrate, a porcelain-based substrate, or a clay-based substrate. 12. The building material according to claim 11, wherein the cement base material is concrete, mortar, molded concrete plate or siding board. 13. The woodworking substrate is made of solid wood, plywood, laminated veneer (LVL), laminated wood, particle board, fiber board, cork, wood wool cement board, wood chip cement board, pulp cement board, medium Density fiberboard (MDF), slope strand board (OSB), wafer board (WB)
The building material according to claim 11, which is: 14. The building material according to claim 2, wherein the cationic substance is a metal ion or a cationic group-containing polymer. 15. The building material according to claim 2, wherein a cationic substance is applied to the base material before or after the application of the fluorine-containing phosphoric acid compound. 16. The building material according to claim 1, wherein the building material is a building board. 17. A method for waterproofing a building material, comprising applying a treating agent containing a fluorine-containing phosphoric acid compound to a porous substrate. 18. A method of using the building material according to claim 1 in a building wall, roof, pillar, indoor wall, indoor top plate, furniture. 19. A method for treating the back surface or the front surface of the building material according to claim 1, wherein the fluorine-containing phosphoric acid compound is treated.