JPH07179849A - Impregnatable waterproofing composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. which gives an inorg. material antialgal and/or antibacterial properties, capability not to absorb water, and permanent water repellency. CONSTITUTION:This compsn. mainly comprises 50.0-99.4wt.% organosilicon compd. represented by the formula (wherein each R<1> is independently a 1-18C monovalent hydrocarbon group; each R<2> is independently a 1-4C monovalent hydrocarbon group; and 0.2<=a<=1.5, 1<=b<=3, and 0<=c<=1 provided 1<a+b+c<=4), 40.0-0.5wt.% acrylic-silicone graft copolymer obtd. by the radical polymn. of an organopolysiloxane compd. having a radical-polymerizable group with a radical-polymerizable monomer mainly comprising an acrylate and/or a methacrylate, and 10.0-0.1wt.% antialgal and/or antibacterial agent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an impregnating composition,
In particular, the present invention relates to an impregnable waterproofing agent composition suitable for imparting water absorption preventive property, water repellency, antialgal property, antifungal property to an inorganic material.

[0002]

2. Description of the Related Art Conventionally, as an impregnable waterproofing agent composition, an organoalkoxysilane or a hydrolyzate thereof or a cohydrolyzate of the silane and another organosilicon compound having a hydrolyzable silyl group is used as a main component. Are known (JP-A-63-236581 and JP-A-1-44673).
No. 1,212,287, West German Patent No. 2,02
9,446, 2,258,901, US Pat. Nos. 4,433,013 and 4,455,172).

Compositions of this type include cement concrete, mortar, blocks, slate, bricks, tiles,
A durable waterproof layer is formed by impregnating the pores of an inorganic material such as a roof tile, stone material, gypsum, etc., and three-dimensionally combining with the substrate in the pores. Therefore, it is particularly excellent in durability and reliability as compared with conventionally known organic polymer-based waterproofing materials using epoxy resin, acrylic resin, urethane resin, etc. and methyl-siliconate aqueous solution-based water repellent materials. Therefore, it is widely used as a waterproofing agent for inorganic materials.

However, the impregnating waterproofing agent composition based on these organoalkoxysilanes or their derivatives does not have the effect of suppressing the growth of algae and molds, and therefore, with the passage of time, the composition may be affected by algae and molds. There was a drawback that the object to be treated became dirty. On the other hand, many substances are already known as agents having the effect of suppressing the growth of algae and molds, but even if conventional agents are applied to the surface of the material to be treated, they are simply treated. Since it only adheres to the surface of the material, it exhibits an effect in the initial stage, but since it is extracted by moisture such as rainfall and removed from the surface of the inorganic material, the drug effect on the surface of the material to be treated disappears.

The above-mentioned drawbacks are caused by the combined use of an organosilicon compound represented by the following chemical formula 2 and an algae control agent, particularly an algae control agent having a hydrolyzable silyl group in the molecule (Japanese Patent Laid-Open No. 5-17
No. 1046) or an organic silicon compound having an alkoxy group with an antifungal agent (JP-A-3-191145).

[Chemical 2] In the formula, R ¹ is the same or different monovalent hydrocarbon group having 1 to 18 carbon atoms, R ² is the same or different monovalent hydrocarbon group having 1 to 4 carbon atoms, and a is 0.2 ≦ a ≦ 1.5, b is 1 ≦ b
≦ 3 and c are 0 ≦ c ≦ 1 and 1 <a + b + c ≦ 4.
However, in these cases, the durability of the water repellency imparted to the surface of the material to be treated is insufficient, and thus there is a drawback that stains such as water stains occur in the long term.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above-mentioned drawbacks, the present inventors have found that good results can be obtained by further combining an acrylic-silicone graft copolymer. The present invention has been found out. Therefore, an object of the present invention is to provide an impregnable waterproofing agent composition capable of imparting algae-proof and / or mildew-proof, water-absorption-preventing and water-repellent excellent durability to an inorganic material. To do.

[0007]

The above objects of the present invention are as follows.
(A) Organosilicon compound 50.0 to 9 represented by the following chemical formula 3
Acrylic obtained by radical polymerization of 9.4% by weight of (B) an organopolysiloxane compound having one radical-polymerizable group in one molecule and a radical-polymerizable monomer mainly containing acrylate and / or methacrylate.
Silicone-based graft copolymer 40.0 to 0.5% by weight, and (C) algal and / or antifungal agent 10.0 to
This has been achieved by an impregnating waterproofing agent composition characterized in that 0.1% by weight is used as a main component.

[0008]

[Chemical 3] In the above formula, R ¹ is the same or different and has 1 to 18 carbon atoms.
Valent hydrocarbon group, R ² has the same or different number of carbon atoms from 1 to 4
Represents a monovalent hydrocarbon group, and a is 0.2 ≦ a ≦ 1.5, b
Is 1 ≦ b ≦ 3, c is 0 ≦ c ≦ 1, and 1 <a + b + c ≦ 4
Is. It is particularly preferable that R ¹ is a monovalent hydrocarbon group having 3 to 14 carbon atoms.

Specific examples of R ¹ include n-propyl group,
Examples include n-butyl group, s-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and n-tetradecyl group. Specific examples of R ² include a methyl group, an ethyl group, a propyl group, a butyl group and the like. a represents the amount of monovalent hydrocarbon groups bonded to the silicon atom. When a is less than 0.2, impregnation performance, water repellency and waterproof performance of the composition of the present invention are deteriorated, and when it exceeds 1.5, durability of the composition is deteriorated, so that 0.2 ≦ a ≦ 1. 0.5 is preferable, and 0.5 ≦ a ≦ 1.2 is particularly preferable.

B represents the amount of an OR ² group bonded to a silicon atom, particularly an alkoxy group. When b is less than 1, the durability of the composition decreases, so 1 ≦ b ≦ 3 is preferable,
It is particularly preferable that 1.5 ≦ b ≦ 3. c represents the amount of hydroxyl groups bonded to the silicon atom. When c exceeds 1, the stability of this compound decreases, so 0 ≦ c ≦ 1 is preferable, and 0 ≦ c ≦ 0.8 is particularly preferable.

The organosilicon compound as the component (A) may be a monomer (monomer) or a polymeric organopolysiloxane, but if the molecular weight exceeds 2000, impregnation into the substrate will be impaired. Therefore, the molecular weight is 20
It is preferably 00 or less. The organosilicon compounds may be used alone or as a mixture of two or more kinds.

Next, the acrylic-silicone-based graft polymer as the component (B) is a radical polymer mainly composed of an organopolysiloxane compound having one radical polymerizable group in one molecule and an acrylate and / or a methacrylate. Radical monomer, more preferably, an alkoxysilane compound having a radically polymerizable group is radically polymerized.

Here, the organopolysiloxane compound having one radical-polymerizable group in one molecule is a radical-polymerizable group such as acryl, methacryl, styryl, cinnamic acid ester, vinyl or allyl in one molecule. It is not particularly limited as long as it has one, but is easy to copolymerize with a radical polymerizable monomer mainly containing acrylate and / or methacrylate, easy to synthesize the organopolysiloxane compound itself, and impregnation of the present invention. From the viewpoint of water repellency when used as a water-resistant waterproofing agent composition, a radical-polymerizable silicone macromonomer represented by the following chemical formula 4 is preferable.

[0014]

[Chemical 4] In the formula, R ³ is a hydrogen atom or a methyl group, R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms which may be interrupted by an oxygen atom, R ⁵ is a methyl group or a trimethylsiloxy group,
R ⁶ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, n is 3 to 2
00 is an integer and m is an integer of 1 to 3.

Specific examples of R ⁴ include --CH ₂ -,-
_{(CH 2) 2 -, -} (CH 2) 3 -, - CH 2 (C
_{H 3) CHCH 2 -, -} (CH 2) 6 -, - (CH 2)
_{12 -, - (CH 2)} 2 -O- (CH 2) 3 -, - (CH
_{2) 2 -O- (CH 2)} 2 -O- (CH 2) 3 - and the like.

Specific examples of R ⁶ include --CH ₃ , --CH
_{2 CH 3, -CH 2 CH 2} CH 3, -CH 2 CH 2 CH
₂ CH _{3 and the} like are exemplified. n represents an integer of 3 to 200, preferably 6 to 100. When n is less than 3, sufficient water repellency cannot be obtained, and when n exceeds 200, the film-forming property of the resulting acrylic silicone-based graft copolymer is poor and the durability of water repellency is poor.

The above radical-polymerizable silicone macromonomer is subjected to a dehydrochlorination reaction of a (meth) acrylate-substituted chlorosilane compound represented by the following chemical formula 5 and a terminal hydroxyl group-containing dimethylpolysiloxane compound represented by the following chemical formula 6 according to a conventional method. Alternatively, it can be obtained by subjecting the compound represented by the above Chemical Formula 5 to a dimethylpolysiloxane compound represented by the following Chemical Formula 7 and having Li at the terminal, in accordance with a conventional method. However, the synthesis method is not limited to these.

[0018]

[Chemical 5]

[Chemical 6]

[Chemical 7] Specific examples of the radical-polymerizable silicone macromonomer represented by Chemical Formula 4 include compounds represented by Chemical Formulas 8 and 9 below.

[Chemical 8]

[Chemical 9]

Next, acrylate and / or methacrylate means an ester compound of (meth) acrylic acid, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth).
Alkyl (meth) acrylates such as acrylate and 2-ethylhexyl (meth) acrylate, hydroxyalkyl (meth) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. ) Acrylates;

Fluorine-substituted alkyl (meth) acrylates such as trifluoropropyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl. Examples thereof include epoxy group-containing (meth) acrylates such as methyl (meth) acrylate.

In the present invention, the fact that the acrylate and / or methacrylate is the main component means that the total amount of the above-mentioned acrylate and / or methacrylate in the radical polymerizable monomer copolymerized with the above radical polymerizable silicone macromonomer is It means that it accounts for 50% by weight or more of the whole radical-polymerizable monomer. this is,
This is because if the amount of acrylate and / or methacrylate is less than 50% by weight, the film formability becomes insufficient and the durability of water repellency deteriorates.

Examples of the compound other than acrylate and / or methacrylate of the radical-polymerizable monomer of the present invention include (meth) acrylic acid, acrylamide, styrene, styrene derivatives, fumaric acid, maleic acid, their derivatives, acrylonitrile and vinylpyrrolidone. , Vinyl acetate, vinyl alkyl ethers, polyoxyalkylene having one radical-polymerizable group in the molecule, radical-polymerizable macromonomers such as polycaprolactone, and the like.

The acrylic-silicone graft copolymer of the present invention further has a water repellency by using an alkoxysilane compound having a radically polymerizable group represented by the following chemical formula 10 or chemical formula 11 as a copolymerization component. It has excellent durability.

[Chemical 10]

[Chemical 11] In the formula, X is a radically polymerizable group, R ⁷ may be interrupted by an oxygen atom, a divalent hydrocarbon group having 1 to 12 carbon atoms, and R ⁸ and R ⁹ each have 1 to 4 carbon atoms. Monovalent hydrocarbon, 1 represents an integer of 1 to 3.

Specific examples of X include the groups shown in the following chemical formulas 12 and 13.

[Chemical 12]

[Chemical 13] R ⁷ is the same as R ⁴ and R ⁸ and R ⁹ are R ²
Is the same as.

Specific examples of the alkoxysilane compound having a radically polymerizable group include the compounds shown in Chemical formulas 14 to 16 below.

[Chemical 14]

[Chemical 15]

[Chemical 16]

As the component (B) in the present invention, the copolymerization ratio of the organopolysiloxane compound, the radical-polymerizable monomer mainly containing acrylate and / or methacrylate, and the alkoxysilane compound having a radical-polymerizable group is a weight ratio. Ratio (5-80) / (20-95)
/ (0-30), preferably (10-50) /
(30 to 85) / (5 to 20).

If the amount of the organopolysiloxane compound is less than 5, sufficient water repellency cannot be obtained. An alkoxysilane having a radically polymerizable group has an effect of improving the durability of water repellency, but even if it exceeds 30, no further effect can be expected and the stability of the copolymer is deteriorated. To do.

Copolymerization is carried out by using organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauroyl peroxide; 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisiso. It is carried out in the presence of an ordinary radical polymerization initiator such as an azo compound such as butyronitrile, and any of the solution polymerization method, emulsion polymerization method, suspension polymerization method, and bulk polymerization method can be applied. is there.

In this case, a chain transfer agent such as butyl mercaptan, dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, carbon tetrachloride or α-methylstyrene dimer may be used as the molecular weight modifier. In the present invention, among these polymerization methods, the solution polymerization method is particularly preferable from the viewpoint that it is easy to adjust the molecular weight of the resulting acrylic-silicone graft copolymerization to the optimum range.

As the solvent used in this case, aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate, n-butyl acetate and isobutyl acetate. Kinds; ethanol, isopropanol,
One or a mixture of two or more selected from alcohols such as n-butanol, isobutanol and the like can be mentioned. Polymerization temperature is 50-180 ° C, especially 60-120 ° C
It is preferable that it is within the range, and under this temperature condition, the polymerization reaction can be completed in about 5 to 10 hours.

The acrylic-silicone graft copolymer thus produced has a polystyrene-equivalent weight average molecular weight of 5,000 to 500,000 by GPC.
And particularly preferably in the range of 10,000 to 100,000. When the weight average molecular weight is less than 5,000, the film-forming property becomes insufficient and thus the water repellency is inferior in durability. When it exceeds 500,000, the component (A) which is another component of the composition of the present invention. And the compatibility with the component (C) becomes poor.

Next, the algae-preventing agent of the component (C) constituting the impregnable waterproofing agent composition of the present invention can be used without particular limitation as long as it is a substance having an algae-preventing action.
In the combination with the organosilicon compound as the component (A) and the acrylic-silicone graft copolymer as the component (B), 3- (3,4-
Dichlorophenyl) -1,1-dimethylurea, 3-
(3,4-dichlorophenyl) -1-methoxy-1-methylurea, 1,1-dimethyl-3-phenylurea,
3- (4-chlorophenyl) -1,1-dimethylurea, 3- (4-chlorophenyl) -1-methyl-1-
(1-Methyl-2-propynyl) urea, 1-butyl-
3- (3,4-dichlorophenyl) -1-methylurea, 1- (2-methylcyclophenyl) -3-phenylurea, 3- (5-tert-butylisoxazol-3-yl) -1,1-dimethyl What are commonly called urea compounds, such as urea;

Tetrachloromethylsulfonylpyridine,
3-iodo-2-propynylbutyl carbamate, 2-
Methyl-thio-4-tert-butenylamino-6-
Cyclopropylamino-5-triazine, 2- (4-thiocyanomethylthio) benzothiazole, 2-n-octyl-4-isothiazolin-3-one, 2-chloro-
4,6-bis (ethylamino) -1,3,5-triazine, 2-[(4-chloro-6-ethylamino-1,3,3
Examples include 5-triazin-2-yl) amino] -2-methylpropionitrile and tetrachloroisophthalonitrile. Among these, those represented by the following chemical formula 17 are particularly preferably used.

[Chemical 17]

The algal repellent used in the present invention is particularly preferably a compound having a hydrolyzable silyl group in its molecule. Hydrolyzable silyl group can be used for cement concrete, mortar, block, slate, brick, tile,
It has excellent affinity with inorganic materials such as roof tiles, stone materials, and gypsum, and further, metal elements of these inorganic materials and ≡Si-OM-
Since it can be bonded like (M is a metal element),
Since the algae preventative agent is fixed to the inorganic material, the sustainability of the effect is dramatically improved.

The hydrolyzable silyl group is (A)
Since it is possible to form a copolymerized siloxane polymer by polycondensation with the organosilicon compound as the component or the alkoxysilyl group or silanol group contained in the acryl-silicone copolymer as the component (B), the algae-proof function is insoluble. It will be retained in the polysiloxane. This makes the composition of the present invention further excellent in durability and water resistance.

As such a compound containing a hydrolyzable silyl group in the molecule, a compound represented by the following chemical formula 18 is preferably used.

[Chemical 18] In the formula, R ¹⁰ and R ¹¹ are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, and l is 0, 1 or 2.

The compound having such a hydrolyzable silyl group is known as, for example, a silane coupling agent, and has a hydrolyzable silyl group and an amino group, an epoxy group, an isocyanate group, a methacryl group or a vinyl group in the molecule. Can be synthesized by reacting an organosilicon compound having an organic reactive group represented by a mercapto group with an algae control agent having a functional group that chemically reacts with the organic reactive group.

Specific examples of such a reaction include an isocyanate group-containing alkoxysilane represented by the following chemical formula 19 and active hydrogen such as a hydroxyl group, a primary or secondary amino group, a mercapto group, an amide group or a urea group. The reaction with the anti-algae agent is shown.

[Chemical 19] In the formula, R ¹⁰ , R ¹¹ and l are the same as in the case of
Z is the residue of the algal repellent.

Among the component (C) of the present invention, the antifungal agent can be used without particular limitation as long as it is a substance having an antifungal effect. Examples of the substance exhibiting an antifungal action in a system in which the organic silicon compound as the component (A) and the acrylic-silicone graft copolymer as the component (B) are combined are:
Alcohols such as hexaline, tris (hydroxymethyl) nitromethane, 2-bromo-2-nitropropane-1,3-diol; p-tert-pentylphenol, 6-pentyl-m-cresol, o-benzyl-phenol, Phenols such as o-phenylphenol, p-phenylphenol, dihydroxydiphenyl, resorcin, pterstilbene;

Trichlorophenol, p-chloro-m-
Cresol, 4-chloro-3,5-xylenol, 2,
4-dichloro-3,5-xylenol, chlorothymol, p-chloro-o-cyclopentylphenol, p-
Chlorophenols such as chloro-o-benzylphenol, chloro-p-phenylphenol, and 5,5'-dichloro-2,2'-dihydroxydiphenylmethane; 3-iodo-2-propenyl-2,4,5- Ethers such as trichlorophenyl ether, phenoxyacetic acid, 5-nitrofuran, dehydroacetic acid; aldehydes such as 2,6-dichlorobenzaldehyde;

Ketones such as dibromozalysyl and p-benzoquinone; acetyl-m-cresol, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, p
-Esters such as propyl hydroxybenzoate; 3,
Acid amides such as 4 ', 5-tribromosalicylanilide, 3,4'-dibromo-salicylanilide, N- (florodichloromethylthio) phthalimide; 2-mercaptopyridine-N-oxide, 2,3,5,6 -Pyridines such as tetrachloromethylsulfonyl pyridine; 8
-Quinolines such as hydroxyquinoline, 5-chloro-8-quinolinol, chlorquinaldol;

Methylol dimelhydantoin, 3-
(3 ', 5'-Dichlorophenyl) -1-isopropylcarbamoylimidazolidine-2,4-dione, 2-
Imidazoles such as (methoxycarbonylamino) benzimidazole and triazoylbenzimidazole;
Thiazoles such as benzisothiazolone, 2-mercaptobenzthiazole, 2-dimeramino-6- (β-diaminoethoxy) -benzthiazole-dihydrochloride; methylene-bis-thiocyanate, chloromethyl-bis-thiocyanate, vinylene- Thiocyans such as bis-thiocyanate and chloroethylene-bis-thiocyanate;

Thioureas such as 3,5-dichloro-4'-fluorothiocarbanilide; N, N-dimethyl-N'-
Examples thereof include sulfamides such as phenyl-N '-(fluorodichloromethylthio) -sulfamide. These antifungal agents may be used alone, but it is preferable to use two or more kinds in combination in order to prevent the generation of various kinds of fungi.

The impregnable waterproofing agent composition of the present invention comprises the above components (A), (B) and (C) in a weight ratio of (A) /
(B) / (C) is (50.0-99.4) / (0.5-
It can be obtained by mixing at a ratio of 40.0) / (0.1-10.0). Here, the component (A) is 5
If it is less than 0.0, the water absorption preventing property becomes insufficient.
If the amount of the component (B) is less than 0.5, the durability of water repellency will be insufficient, and if it exceeds 40.0, the appearance of the object to be treated will be a wet color. Further, if the amount of the component (C) is less than 0.1, it is difficult to obtain antialgal and / or antifungal properties, and if it exceeds 10.0, the water repellency is adversely affected.

The impregnating waterproofing agent composition of the present invention has a good impregnating property and workability during construction by adding a solvent to the components (A), (B) and (C) to form a uniform solution. Can be improved. As the solvent used in this case, methanol, ethanol, isopropanol, n-
Alcohols such as butanol and s-butanol, n-
Hexane, cyclohexane, n-octane and other aliphatic hydrocarbons, toluene, xylene and other aromatic hydrocarbons,
Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, propyl acetate, and butyl acetate, organic solvents including multi-component mixed solvents such as kerosene, petroleum ether, ligroin, solvent naphtha, and kerosene. Water etc. are illustrated. In addition, the solvent may use only 1 type and may use a mixed system of 2 or more types.

If desired, colorants, stabilizers, fats and oils, waxes, fillers and the like can be added to the composition of the present invention. Further, the composition of the present invention comprises
A curing catalyst for an alkoxysilyl group or silanol, such as an organic metal salt, a metal alkoxide, a metal chelate, an organic amine, or a quaternary ammonium salt may be added as long as the stability is not impaired. These additives promote hydrolysis, polycondensation in the pores of the object to be treated, and reaction with the surface of the inorganic material.

The impregnable waterproofing agent composition of the present invention is useful for waterproofing inorganic materials such as cement, concrete, mortar, blocks, slate, bricks, tiles, roof tiles, stones and gypsum. When the composition of the present invention is applied to these materials, the composition is brush-coated, roller-coated, flow-coated, dip-coated or spray-coated on the surface of the object to be treated. In this case, the coating amount is 1 m ^{2 of the} object to be treated.
It is preferably from 1 to 1000 g, particularly from 10 to 2
It is preferable to perform impregnation with 00 g.

When treated in this manner, (A) in the composition
Since the component is a monomer of an organic silicon compound or a polymer having a low degree of polymerization and having a low surface tension, it easily penetrates into the pores of the object to be treated, and its SiOR ² group (particularly, alkoxysilyl group) As a result of the hydrolysis polycondensation of (1), an organosiloxane polymer having excellent waterproof performance and durability is obtained. Further, a part of the SiOR ² group is chemically bonded to the M—OH group (M is a metal atom) existing on the surface in the pores, so that the durability is further improved.

Further, the acrylic-silicone graft copolymer as the component (B) is excellent in film forming property, water repellency and weather resistance, so that a durable water repellent film is formed on the surface of the object to be treated. The surface is hard to grow algae and fungi.
Therefore, the durability of the anti-algal property and / or antifungal property imparted by the action of the component (C) is good.

As described above, the impregnable waterproofing agent composition of the present invention contains cement, concrete, mortar, block,
It can be applied to inorganic materials such as PC boards, slate boards, bricks, tiles, roof tiles, stone materials, plaster, and buildings,
Houses, warehouse walls, stairs, balconies, fences, flower beds, sidewalks,
It is effective not only for civil engineering structures such as bridges, dams, and levees, but also for underwater structures such as tetrapots, revetments for coasts and rivers, cooling water inlets and outlets for power plants, piers, and piers.

[0051]

EFFECTS OF THE INVENTION The impregnating waterproofing agent composition of the present invention has a good film-forming property and can stably hold the algae-proofing agent and / or antifungal agent in the film. In addition, since the coating film and the object to be treated have a sufficient affinity, by applying the impregnating waterproofing agent composition of the present invention to the inorganic object to be treated, the object can be easily treated.
It is possible to impart durable anti-algal and / or anti-mold property, anti-water absorption property, and water repellency.

[0052]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Synthetic Example of Acrylic-Silicone Copolymer
1 . To a 1 liter glass flask equipped with a stirrer, a reflux condenser and a thermometer, 300 g of toluene was charged, and while passing nitrogen gas, 90 g of radical-polymerizable silicone macromonomer of the following chemical formula 20 at a temperature of 80 to 90 ° C. and methyl methacrylate. 150 g, butyl methacrylate 60
A mixed solution of 6 g of g and 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. Furthermore, after carrying out a polymerization reaction at a temperature of 80 to 90 ° C. for 5 hours, the solution cooled to room temperature was poured into 3 liters of methanol to precipitate an acryl-silicone copolymer.

When the precipitate was dried under reduced pressure at 120 ° C./5 mmHg, 271 g of a colorless transparent solid was obtained. The polystyrene reduced weight average molecular weight by GPC was about 65,000.

[Chemical 20]

Synthetic Example of Acrylic-Silicone Copolymer
2 . The mixed solution of Synthesis Example 1 was mixed with 45 g of the radical-polymerizable silicone macromonomer represented by the following chemical formula 21, 150 g of methyl methacrylate, 45 g of butyl acrylate, 60 g of 2-ethylhexyl acrylate, and 6 g of 2,2′-azobisisobutyronitrile. Except that it was changed, in the same manner as in Synthesis Example 1, 265 g of a colorless and transparent solid having a polystyrene reduced weight average molecular weight of about 52,000 by GPC was obtained.

[Chemical 21]

Synthesis example of acrylic-silicone copolymer
3 . 105 g of radical-polymerizable silicone macromonomer represented by the following chemical formula 22 and 13
5 g, 30 g of butyl acrylate, 30 g of γ-methacryloxypropyltrimethoxysilane, and 6 g of 2-2′-azobisisobutyronitrile were used in the same manner as in Synthesis Example 1 except that the weight was converted to polystyrene by GPC. A colorless and transparent solid 27 having an average molecular weight of about 68,000.
5 g was obtained.

[Chemical formula 22]

Examples 1-22 and Comparative Examples 1-5 . Impregnable waterproofing agent compositions having the compositions shown in Tables 1 and 2 below were prepared.

[Table 1]

[Table 2]

However, the organosilicon compounds A to E which are the components (A) in the table are compounds represented by the following chemical formula 23.

[Chemical formula 23] In addition, the antifungal agents F and G, which are the components (C) in the table, are compounds shown in the following chemical formula 24, and the antifungal agents H and I are the compounds shown in the following chemical formula 25.

[Chemical formula 24]

[Chemical 25]

The impregnable waterproofing agent composition prepared according to Table 1 was applied to mortar to prepare a sample for evaluation. Tables 3 and 4 show data of water absorption prevention performance, algae prevention performance, mold prevention performance, water repellency performance, and appearance of these samples. For comparison, data on untreated mortar are also shown.

[Table 3]

[Table 4] In addition, water absorption prevention performance, algae prevention performance, mold prevention performance, water repellent performance,
The appearance was evaluated by the following method.

Water Absorption Prevention Performance Water absorption rate: Each composition was brush coated on the entire surface of JIS mortar (50 × 50 × 25 mm) so that the active ingredient was 100 g / m ^2, and the atmosphere was 25 ° C. and 50% RH. After aging for 7 days, the whole surface was immersed in tap water for 28 hours, and the water absorption rate was calculated using the formula shown in the following mathematical formula 1.

[Equation 1]

Alkali resistance: A mortar test piece prepared by the same method as in the water absorption test was entirely immersed in a 5% aqueous solution of sodium hydroxide for 7 days, and the alkali resistance was calculated using the formula shown below. .

[Equation 2]

Durability: A mortar test piece prepared by the same method as the water absorption test was exposed in a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 1000 hours,
Next, the water absorption rate after the entire surface was soaked in tap water for 28 days was calculated using the formula shown in the above mathematical expression 1.

A mortar piece of 40 × 40 × 4 mm algae-proofing performance was added to tap water (running water).
After soaking for one day, it was left to dry in an atmosphere of 25 ° C. and 50% for 2 weeks. On one side of this mortar piece, the active ingredient is 10
Brush the composition so that the amount becomes 0 g / m ^2, and
A sample was prepared by aging for 7 days in an atmosphere of 50% RH. The effect test on the algae of the test body prepared as described above was performed as follows.

Inorganic salt agar medium for algae is put into a sterilized petri dish having a diameter of 9 cm to coagulate, and then the test body is placed at the center. The above-mentioned petri dish is inoculated with a mixed solution of various algae that have been previously cultured in a liquid medium at 25 ° C. under the condition of 10001 × for 2 weeks. The test algae were green algae such as Chlorella vulgarizs, Holmium s. p. (Hor
midium sp) and Anabaena were selected as cyanobacteria.

After culturing for 4 weeks in a sunlight low temperature machine at 25 ° C. and 10001 ×, the degree of algae generation was visually evaluated according to the following criteria. -: No algae was observed on the test body. ±: The presence or absence of algae on the surface of the test body is unclear. +: Generation of algae is recognized on 10% or less of the upper surface of the test body. ++: Generation of algae is recognized on 10 to 50% of the upper surface of the test body. +++: Algae are observed on 50% or more of the upper surface of the test body.

The composition was brush-coated on one side of a mortar piece having a mold resistance of 40 × 40 × 4 mm so that the active ingredient was 100 g / m ^2.
A sample was prepared by aging for 7 days in an atmosphere of 50 ° C and 50% RH. The effect test on the fungi of the test body prepared as described above was carried out according to the mold resistance test method of JIS-Z-2911 and the paint test (page 7). The test bacteria were Aspergillus niger and Penicillium funiculosu.
m, Cladosporium cladosporioides, Aureobasidium pu
Five strains of lluans and Gliocladium virens were selected.

Culturing was carried out under the temperature condition of 28 ± 1 ° C. for 4 weeks,
The degree of mold production was visually evaluated according to the following criteria. -: No mold is found on the test piece. ±: Presence or absence of mold on the upper surface of the test piece is unclear. +: Generation of mold is recognized in one third or less of the upper surface of the test body. ++: Generation of mold is recognized in two thirds or less of the upper surface of the test body. +++: The generation of mildew is recognized on two-thirds or more of the upper surface of the test body.

Water repellent performance Initial water repellency: 5 μl of pure water was dropped on a mortar test piece prepared by the same method as the water absorption test, and a contact angle measuring device (Co
Contact angle was measured using ntact Angle Meter CA-A: trade name manufactured by Kyowa Kagaku Co., Ltd.).

Durability and water repellency: A mortar test piece prepared in the same manner as in the water absorption test was exposed in a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 1000 hours and then in an atmosphere of 25 ° C. and 50% RH. The contact angle of water was measured in the same manner as in the case of the initial water repellency for the one that was left to stand for one day and below and dried.

Appearance The appearance of the mortar test pieces prepared by the same method as in the water absorption test was visually judged to be a wet color. ○: No treatment and no change (no wet color) ×: Wet color The results in Tables 3 and 4 demonstrate the effectiveness of the present invention.

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Claims (4)

[Claims] 1. (A) 50.0 to 99.4% by weight of an organosilicon compound represented by the following chemical formula 1, (B) an organopolysiloxane compound having one radical-polymerizable group in one molecule, and an acrylate. And / or acrylic-silicone-based graft copolymer 40.0 obtained by radical polymerization of a radical-polymerizable monomer mainly containing methacrylate
To 0.5% by weight, and (C) 10.0 to 0.1% by weight of an algae-proofing agent and / or antifungal agent as a main component, an impregnable waterproofing agent composition; In the formula, R ¹ represents the same or different monovalent hydrocarbon group having 1 to 18 carbon atoms, R ² represents the same or different monovalent hydrocarbon group having 1 to 4 carbon atoms, and a is 0.2. ≦ a ≦ 1.5, b is 1 ≦ b ≦ 3, c is 0 ≦ c ≦ 1, and 1 <a + b + c ≦ 4. 2. An acrylic-silicone graft copolymer comprising an organopolysiloxane compound having one radical-polymerizable group in one molecule, an alkoxysilane compound having a radical-polymerizable group, and an acrylate and / or a methacrylate. The impregnable waterproofing agent composition according to claim 1, which is obtained by radically polymerizing a radically polymerizable monomer as a main component. 3. The impregnable waterproofing agent composition according to claim 1, wherein the algal repellent has a hydrolyzable silyl group in its structure. 4. The impregnable waterproofing agent composition according to claim 1, wherein two or more antifungal agents are used in combination.