JP2009046575A - Treating agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent composition imparting an excellent surface anti-fouling property onto a porous base material such as a stone material. <P>SOLUTION: This treating agent composition contains (1) a fluoroalkyl group-containing ethylenic unsaturated monomer expressed by formula (I), and (2) an isobornyl group-containing ethylenic unsaturated monomer, and (3) a copolymer prepared by copolymerizing silicon-containing unsaturated monomers. The formula (I): CH<SB>2</SB>=CR<SP>1</SP>-COO-(CH<SB>2</SB>)n<SP>1</SP>-Rf, where Rf represents 1C-6C perfluoroalkyl group, n<SP>1</SP>is an integer of 0-3, and R<SP>1</SP>represents a hydrogen atom or methyl group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a treatment agent composition that imparts antifouling properties to a porous substrate, particularly a porous substrate such as a building stone.

  Conventionally, a polymer comprising a monomer containing a perfluoroalkyl group (hereinafter referred to as Rf group) or a copolymer of this and another monomer is used as an organic solvent solution or aqueous dispersion. It is well known to impart water and oil repellency by treating the material. This water / oil repellency is attributed to the fact that the surface energy of the substrate surface is lowered by the surface orientation of the Rf group. Conventionally, those having 8 or more carbon atoms have been used as the Rf group. However, when the carbon number of the Rf group is 6 or less, the surface energy reduction ability of the substrate surface is inferior, so that the water and oil repellency also decreases. End up. Therefore, when such a polymer composed of a monomer containing an Rf group having a small number of carbon atoms is treated on a porous substrate, the water / oil repellency is not sufficient.

JP 58-118882 A

  An object of the present invention is to provide a surface antifouling property excellent for a porous substrate such as a stone using a copolymer comprising a monomer containing an Rf group having 6 or less carbon atoms and another polymer. It is in providing the processing agent composition which provides.

The present invention includes (1) a fluoroalkyl group-containing ethylenically unsaturated monomer represented by the following formula (I), (2) an isobornyl group-containing ethylenically unsaturated monomer, and (3) silicon-containing unsaturated A treating agent composition containing a copolymer (A) obtained by copolymerizing monomers and a solvent.
^{_{CH 2 = CR 1 -COO- (CH}} 2) n 1 -Rf (I)
However, the symbols in the formulas have the following meanings.
Rf: C1-C6 perfluoroalkyl group.
n ¹ : An integer of 0 to 3.
R ¹ : a hydrogen atom or a methyl group.

In the copolymer (A), the isobornyl group-containing ethylenically unsaturated monomer is preferably represented by the following formula (II).
^{_{CH 2 = C (R 2)}} -COO- (CH 2) n 2 -IB (II)
However, the symbols in the formulas have the following meanings.
R ² : a hydrogen atom or a methyl group.
integer of 0~6: n ^2.
IB: Isobonyl group.

In the copolymer (A), the silicon-containing unsaturated monomer is preferably represented by the following formula (III).
_{^{CH 2 = C (R 3)}} - (COO) n 3 - (CH 2) n 4 -SiR 4 R 5 R 6 (III)
However, the symbols in the formulas have the following meanings.
R ³ : a hydrogen atom or a methyl group.
R ⁴ , R ⁵ , R ⁶ : each independently an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group, or a phenyl group.
n ³ : An integer of 0 or 1.
integer of 0~6: n ^4.

  In the copolymer (A), an organic solvent is preferably used as the solvent.

  The treatment agent composition of the present invention is preferably used for antifouling of a porous substrate.

  The porous substrate is preferably a stone material.

  By treating with the treating agent composition of the present invention, excellent antifouling property can be imparted to the porous substrate.

The treatment agent composition of the present invention contains a copolymer (A). The copolymer (A) comprises (1) a fluoroalkyl group-containing ethylenically unsaturated monomer represented by formula (I), (2) an isobornyl group-containing ethylenically unsaturated monomer, and (3) It is obtained by copolymerizing a silicon unsaturated monomer.
^{_{CH 2 = CR 1 -COO- (CH}} 2) n 1 -Rf (I)
However, the symbols in the formulas have the following meanings.
Rf: C1-C6 perfluoroalkyl group.
n ¹ : An integer of 0 to 3.
R ¹ : a hydrogen atom or a methyl group.

  Rf of the fluoroalkyl group-containing ethylenically unsaturated monomer represented by formula (I) (hereinafter referred to as compound (I); the same applies to other formulas) has 1 to 6 carbon atoms. Perfluoroalkyl group. The perfluoroalkyl group may be linear or branched. In some cases, an etheric oxygen atom may be contained between carbon-carbon atoms in the group.

Specific examples of compound (I) include the following.
_{CH 2 = CH-COO- (CH} 2) 2 -CF 3
_{CH 2 = CH-COO- (CH} 2) 2 -C 2 F 5
_{CH 2 = CH-COO- (CH} 2) 2 -C 4 F 9
_{CH 2 = CH-COO- (CH} 2) 2 -C 6 F 13
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -CF 3
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -C 2 F 5
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -C 4 F 9
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -C 6 F 13

  30-90 mass% is preferable, and, as for the ratio of compound (I) in a copolymer (A), 40-80 mass% is more preferable. When the ratio of the compound (I) is less than 30% by mass, sufficient water / oil repellency cannot be exhibited. On the other hand, when it exceeds 90% by mass, the solubility in a fluorine-based organic solvent is improved, but the solubility in a cheaper hydrocarbon-based solvent is lowered. Compound (I) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount is contained in the said range.

In the present invention, the isobornyl group-containing ethylenically unsaturated monomer includes compound (II).
^{_{CH 2 = C (R 2)}} -COO- (CH 2) n 2 -IB (II)
However, the symbols in the formulas have the following meanings.
R ² : a hydrogen atom or a methyl group.
integer of 0~6: n ^2.
IB: Isobonyl group.

Specific examples of compound (II) include the following.
CH ₂ = CH-COO-IB
_{CH 2 = CH-COO- (CH} 2) 2 -IB
_{CH 2 = C (CH 3)} -COO-IB
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -IB

  5-60 mass% is preferable and, as for the ratio of compound (II) in a copolymer (A), 20-45 mass% is more preferable. If it is less than 5% by mass, the solubility in a hydrocarbon-based organic solvent is low, and if it exceeds 60% by mass, sufficient water / oil repellency cannot be exhibited. Compound (II) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount is contained in the said range.

In the present invention, examples of the silicon-containing unsaturated monomer include compound (III).
^{_{CH 2 = C (R 3)}} - (COO) n 3 - (CH 2) n 4 -SiR 4 R 5 R 6 (III)
However, the symbols in the formulas have the following meanings.
R ³ : a hydrogen atom or a methyl group.
R ⁴ , R ⁵ , R ⁶ : each independently an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group, or a phenyl group.
n ^3: 0~1 integer.
integer of 0~6: n ^4.

  Specific examples of the compound (III) include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meta ) Acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meta ) Acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropyltrisilanol, γ- (meth) acryloxypropylmethyldihydroxysilane, γ- (meth) acryl Roxypropylphenyl dihydro Sisilane, γ- (meth) acryloxypropyldimethylhydroxysilane, γ- (meth) acryloxypropylphenylmethylhydroxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyldimethyl Examples include methoxysilane and vinyldimethylethoxysilane.

  0.1-10 mass% is preferable and, as for the ratio of compound (III) in a copolymer (A), 1.0-8.0 mass% is more preferable. If it is less than 0.1% by mass, the durability is low, and if it exceeds 10% by mass, the oil repellency is adversely affected. Only one type of compound (III) may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount is contained in the said range.

  In the copolymer (A) of the present invention, (1) a fluoroalkyl group-containing ethylenically unsaturated monomer represented by the formula (I), (2) an isobornyl group-containing ethylenically unsaturated monomer, and ( 3) In addition to the silicon-containing unsaturated monomer, other unsaturated monomers can be used. 0-50 mass% is preferable and, as for the ratio of the other monomer in a copolymer (A), 0-30 mass% is more preferable.

  Examples of other unsaturated monomers include (meth) acrylic acid esters having 1 to 18 carbon atoms and monomers containing reactive functional groups such as maleic acid, itaconic anhydride, succinic anhydride, and the like. Amide compounds such as ethylenically unsaturated carboxylic acids, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxy (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth ) Hydroxyl group-containing monomers such as hydroxypropyl acrylate, epoxy group-containing monomers such as glycidyl (meth) acrylate, aldehyde group-containing monomers such as acrolein, caprolactone-modified hydroxy (meth) acrylate, and the like.

  0.5-15 mass% is preferable and, as for the density | concentration of the copolymer (A) in the processing agent composition of this invention, 1.0-5.0 mass% is more preferable.

In this invention, it is also possible to form a water absorption prevention layer inside a stone material by adding the alkyl alkoxysilane represented by the following Formula (IV) in addition to the said processing agent composition.
^{R 7 n 4 -Si-X4-} n 4 (IV)
However, the symbols in the formulas have the following meanings.
R ⁷ : an alkyl group having 1 to 18 carbon atoms.
X: Hydrolyzable group.
n ^4: 1~3 of integer.

  Examples of the alkyl alkoxysilane represented by the formula (IV) include methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, and nonyl. Triethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, Octadecyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimeth Sisilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane Hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane and the like.

  0.1-20 mass% is preferable and, as for the density | concentration of the alkyl alkoxysilane in the processing agent composition of this invention, 1.0-10 mass% is more preferable.

In addition to the alkylalkoxysilane represented by the formula (IV), the water absorption preventing layer can be formed inside the stone material even when the alkylsilicate represented by the formula (V) and these oligomers are used in combination.
Si- (OR ⁸ ) ₄ (V)
However, ^{R 8} in the formula represents an alkyl group having 1 to 18 carbon atoms.

  Examples of the alkyl silicate represented by the formula (V) include methyl silicate, ethyl silicate, propyl silicate, butyl silicate, and oligomers thereof.

  0.1-20 mass% is preferable and, as for the density | concentration of the alkyl silicate and these oligomers in the processing agent composition of this invention, 1.0-10 mass% is more preferable.

  Examples of the catalyst for promoting hydrolysis of the silane component include organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and butyltin tri-2-ethylhexoate, tetrabutyl titanate, and tetra-2-ethylhexyl titanate. Organic catalysts such as organosiloxane titanium, inorganic catalysts such as hydrochloric acid, phosphoric acid and sulfuric acid, acidic catalysts such as organic acids such as formic acid, acetic acid and chloroacetic acid, quaternary ammonium salts of these inorganic acids and organic acids And amine salts are used alone or in combination.

  The concentration of the catalyst in the treatment agent composition of the present invention is preferably 0.01 to 5.0 mass%, more preferably 0.1 to 1.0 mass%.

In the present invention, the treating agent composition contains a solvent, and can be used by dissolving it in an appropriate solvent at an arbitrary ratio. The solvent that can be used is not particularly limited, but a solvent that can stably dissolve these treatment agent compositions is desirable. As such a solvent, a hydrocarbon solvent, an alcohol solvent, an ester solvent, an ether solvent, a silicone solvent, a fluorine solvent, or the like can be used. Specific examples include 2,2,4-trimethylpentane (hereinafter referred to as isooctane). Moreover, a mixed solvent with those compatible with these solvents can also be used.
The coating method of the present invention is not particularly limited, and for example, spraying, brush coating, coating with a roller coater, a dipping method, or the like can be appropriately employed. The film thickness of the composition of this invention in a process base material is not specifically limited.

  In preparing the composition of the present invention, an additive can be further contained in addition to the above. Such additives are not particularly limited, and examples thereof include pigments, preservatives, antibacterial agents, flame retardants, surface modifiers, curing catalysts, viscosity modifiers, leveling agents, ultraviolet absorbers, antifoaming agents, and the like. Known additives and the like that are usually used can be mentioned, and the addition amount thereof is not particularly limited, and the usual addition amount can be adopted.

  The treating agent composition of the present invention is preferably used for a porous substrate. In particular, it is preferably used as an antifouling treatment agent.

  Examples of the porous substrate to which the composition of the present invention can be applied include stone, concrete, and wood. Of these, stones are preferable, and natural stones such as granite, granite, and marble are particularly preferable.

  The copolymer (A) of the present invention may be any production method as long as it is a normal polymerization method such as bulk polymerization or solution polymerization. The reaction conditions can be arbitrarily selected. As the polymerization method, solution polymerization is preferred.

  Next, the present invention will be described with reference to specific examples, but this is not intended to limit the present invention.

(Reference Example 1)
Production of copolymer (A) 124.01 g of CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₂ —C ₆ F ₁₃ as perfluoro group-containing ethylenically unsaturated monomer, isobonyl group-containing ethylenic 72.27 g of isobornyl methacrylate (“Eye ester” IB-X manufactured by Kyoeisha Chemical Co., Ltd.) as the unsaturated monomer, and γ-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical) as the silicon-containing unsaturated monomer ) 13.69 g, isooctane (manufactured by Wako Pure Chemical Industries, Ltd.) 387.999 g, 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.10 g, and 1 L autoclave. The mixture was stirred under a nitrogen atmosphere and polymerized at 65 ° C. for 15 hours. According to gas chromatography, the reaction rate was 90% or more. The obtained copolymer (A) solution had a solid content concentration of 35% by mass.

Example 1
The copolymer (A) solution obtained in Reference Example 1 was diluted with isooctane so that the solid content concentration was 2.5% by mass to obtain a treatment liquid. Subsequently, the treatment liquid was treated with natural stone (mocha cream), allowed to stand at room temperature for 24 hours or more, and then the surface was wiped with a cloth to conduct an antifouling test. The treatment was carried out by a method in which the treatment solution was soaked in a sponge and spread on the surface of a stone material.

(Comparative Reference Example 1)
Production method of polymer 10.51 g of perfluoro group-containing ethylenically unsaturated monomer CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₂ —C ₆ F ₁₃ , stearyl methacrylate (Kyoeisha Chemical “Light” 6.12 g of ester “S), 0.87 g of γ-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical), 32.35 g of isooctane (manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2 , 4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 100 ml ampoule, stirred in a nitrogen atmosphere, and polymerized at 65 ° C. for 15 hours. According to gas chromatography, the reaction rate was 90% or more. The obtained copolymer solution had a solid content concentration of 34% by mass.

(Comparative Example 1)
The copolymer solution obtained in Comparative Reference Example 1 was diluted with isooctane so that the solid content concentration was 2.5% by mass to obtain a treatment liquid. Subsequently, the treatment liquid was treated with natural stone (mocha cream) in the same manner as in Example 1, and allowed to stand at room temperature for 24 hours or more, and then the surface was wiped with a cloth to conduct an antifouling test.

(Anti-fouling test)
1 ml of tap water, soy sauce, sauce, orange juice, olive oil, and coffee was dropped on the treated stone surface, and the state after 24 hours was visually confirmed and evaluated by the following methods. The evaluation results are shown in Table 1.
0 = Dense and large 1 = Dense and small 2 = Light stain 3 = No stain

Claims (6)

(1) a fluoroalkyl group-containing ethylenically unsaturated monomer represented by the following formula (I), (2) an isobornyl group-containing ethylenically unsaturated monomer, and (3) a silicon-containing unsaturated monomer. A treating agent composition comprising a copolymer (A) obtained by copolymerization and a solvent.
^{_{CH 2 = CR 1 -COO- (CH}} 2) n 1 -Rf (I)
However, the symbols in the formulas have the following meanings.
Rf: C1-C6 perfluoroalkyl group.
n ¹ : An integer of 0 to 3.
R ¹ : a hydrogen atom or a methyl group. The treating agent composition according to claim 1, wherein the isobornyl group-containing ethylenically unsaturated monomer is represented by the following formula (II).
^{_{CH 2 = C (R 2)}} -COO- (CH 2) n 2 -IB (II)
However, the symbols in the formulas have the following meanings.
R ² : a hydrogen atom or a methyl group.
integer of 0~6: n ^2.
IB: Isobonyl group. The treatment agent composition according to claim 1 or 2, wherein the silicon-containing unsaturated monomer is represented by the following formula (III).
^{_{CH 2 = C (R 3)}} - (COO) n 3 - (CH 2) n 4 -SiR 4 R 5 R 6 (III)
However, the symbols in the formulas have the following meanings.
R ³ : a hydrogen atom or a methyl group.
R ⁴ , R ⁵ , R ⁶ : each independently an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group, or a phenyl group.
n ³ : An integer of 0 or 1.
an integer of 0~6: n ^4.   The processing agent composition according to claim 1, 2 or 3, wherein an organic solvent is used as the solvent.   The processing agent composition of Claim 1, 2, 3 or 4 used for antifouling of a porous substrate.   The processing agent composition according to claim 5, wherein the porous substrate is a stone.