JP2877616B2 - Hydrophilic oil repellent treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a treating agent for imparting hydrophilic oil repellency to various substrate surfaces.

[0002]

2. Description of the Related Art In the case of various substrates such as glass, ceramics, metals, plastics, wood, and fibers, moisture is condensed on the surface due to the influence of humidity and temperature in the atmosphere, or the surface is wetted by water. In such a case, the components in the base material are eluted or deteriorated by the moisture. In order to prevent this, the surface of these substrates is provided with water repellency. Further, in order to prevent the adhesion of oily dirt to the surface of the substrate, it has been practiced to impart oil repellency to the surface of the substrate.

[0003] Conventionally, water- and oil-repellents having both water repellency and oil repellency as described above are effective for stain resistance.
Used for surface treatment of various substrates. Many such water and oil repellents are known, such as fluorine,
Silicone type, zirconia type, metal soap type and the like are available. For example, JP-A-60-40254 discloses a water / oil repellent comprising a compound having a polyfluorinated organic group.

[0004]

However, when the surface treatment of the substrate is carried out using a conventional water- and oil-repellent agent, fine water droplets remain on the surface and dry to form stains called watermarks. However, there was still a problem with respect to stain resistance. In addition, when fibers are treated using these water and oil repellents, the water repellency reduces the permeability of water during washing, making it difficult to remove dirt. there were.

Accordingly, it is an object of the present invention to provide various types of substrates with good stain resistance, excellent water permeability, and easy removal of stains from the substrates. It is to provide a possible treating agent. Another object of the present invention is to provide a hydrophilic oil repellent having hydrophilicity and oil repellency.

[0006]

According to the present invention, (A) the following general formula (1): (Rf¹Q¹)_aSi (Z¹)_4-abY¹ _b (1) and the following general formula (2): Y¹ _b(Z¹)_3-bSi (Q¹Rf²Q¹) Si (Z¹)_3-bY¹ _b  (2) where Rf¹Is a perfluoroalkyl group or perfluoro
R alkyl ether group, Rf²Is a perfluoroalkylene group or perful
O-alkylene ether group, Q¹Is a divalent organic group, Z¹Is a monovalent organic group, Y¹Is a halogen atom or a hydrolyzable group; a is an integer of 1 to 3; b is an integer of 1 to 3; a + b is 4 or less; (B) the following general formula (3): (Hy-A)_aSi (Z²)_4-abY² _b (3) where Hy isThe following equation (14):

Embedded image Wherein R is a hydrogen atom or an atom having 22 or less carbon atoms.
The alkyl group, s and t are each an integer of 0 to 50.
And s and t do not become 0 at the same time.]
An ether group represented by the following formula (15): -N ⁺ R ¹ R ² R ³ .X ^1- (15) wherein R ¹ , R ² and R ³ are each a hydrogen atom or
Are organic groups having 1 to 20 carbon atoms, which are
X ¹ , which may combine to form a ring, is
An ammonium group represented by the formula:
(16):

Embedded image [Wherein, R is a hydrogen atom or a carbon atom number as described above.
An organic group of 20 or less, c is an integer of 1 to 3, X ² is CO
₂ ^- or SO ₃ ^- it is, represented by] Karubokishibe
A hydrophilic organic group selected from a tine group or a sulfobetaine group, A is an alkylene group, Z ² is a monovalent organic group, Y ² is a halogen atom or a hydrolyzable group, a is 1 to 3 And b is an integer of 1 to 3, and a + b is 4 or less. A hydrophilic silane compound represented by the following formula:

(A) Fluorine-Containing Silane Compound In the hydrophilic oil repellent treating agent of the present invention, the fluorine-containing silane compound as the component (A) imparts oil repellency, and is represented by the general formula (1). And a fluorine-containing silane compound represented by the general formula (2).

In the general formula (1), Rf ¹ is a monovalent fluorine-containing organic group, and is a perfluoroalkyl group or a perfluoroalkyl ether group. Here, as the perfluoroalkyl group, those represented by the following formula (4): C _p F _{2p + 1-} (4) [where p is an integer of 4 to 30] are preferable.

Further, as the perfluoroalkyl ether group, the following formula (5) or (6):

Embedded image

Embedded image [Wherein, n is an integer of 1 or more], and those having 5 to 30 carbon atoms are preferred.

[0010] In the general formula (1), examples of the divalent organic group Q ¹ which is interposed between the fluorine-containing organic group Rf ¹ and a silicon atom, for example, can be exemplified by the following . -CH ₂ CH ₂ - polyalkylene group such _{as, -CONH- (CH 2) 3 -} , -CONH- (CH 2) 2 -NH- (CH 2) 3 -, -SO 2 N (CH 3) - ( _{CH 2) 2 -NH- (CH 2} ) 3 -, - (CH 2) 2 -OCO- (CH 2) 2 -S- (CH 2) 3 -, - (CH 2) 2 -OCONH- (CH 2 ) ₃ -,-(CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -and the following formula (7):

Embedded image Group represented by

Further, in the general formula (1), Z ¹ is a monovalent organic group, particularly a methyl group, an ethyl group, a propyl group,
A lower alkyl group having 6 or less carbon atoms such as a butyl group,
It is preferably an aryl group such as a phenyl group. Y ¹ is a halogen atom or a hydrolyzable group,
Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group,
Examples include an aminoxy group and an amide group.

The fluorine-containing silane compound represented by the general formula (1) preferably has a fluorine content of at least 20% by weight, and for example, the following compounds are suitable.

Embedded image In the above formula, Rf ¹ has the above-mentioned meaning. These fluorinated silane compounds are, for example, a olefin having a corresponding fluorinated organic group and a corresponding alkoxysilane, a hydrosilylation reaction with a halogenated silane, or a carboxylic acid or a sulfonic acid having a corresponding fluorinated organic group. And a condensation reaction with a corresponding amino group-containing alkoxysilane or the like.

In the general formula (2), Rf ² is a divalent fluorine-containing organic group, and is a perfluoroalkylene group or a perfluoroalkylene ether group. For example, examples of the perfluoroalkylene group include those represented by the following formula (8):-(CF ₂ ) _m- (8), wherein m is an integer of 4 to 30. Further, as the perfluoroalkylene ether group, the following formula (9):

Embedded image [Wherein, p and q are each 0 or 1 or more, and p + q is in the range of 0 to 10].

In the general formula (2), other groups, Q ¹ ,
As Z ¹ and Y ^{1, the same} as those exemplified in the aforementioned general formula (1) can be mentioned.

The fluorine-containing silane compound of the general formula (2) preferably has a fluorine content of 20% by weight or more.
0) to (13).

Embedded image

Embedded image

Embedded image

Embedded image Wherein p and q are the same as above, and m is 4 to 30.
And n is an integer of 1 to 3.] These fluorine-containing silane compounds include olefins having vinyl groups bonded to both ends of a corresponding fluorine-containing organic group, and corresponding alkoxysilanes, halogenated silanes and the like. Can be produced by a hydrosilylation reaction with

(B) Hydrophilic silane compound The hydrophilic silane compound of the component (B) imparts hydrophilicity to the substrate, and is a silane compound represented by the general formula (3). In the general formula (3), the organic group Hy having hydrophilicity is represented by the following formula (14):

Embedded image Wherein R is a hydrogen atom or an alkyl group having 22 or less carbon atoms, s and t are each an integer of 0 to 50, and s and t are not simultaneously 0.
An ether group represented by the following formula (15): -N ⁺ R ¹ R ² R ³ .X ^1- (15) wherein R ¹ , R ² and R ³ each represent a hydrogen atom or a carbon atom number; 20 is an organic group, they may be bonded to each other to form a ring, X ¹ is an ammonium group represented by a monovalent anion,], and the following formula (16) :

Embedded image [Wherein, R is a hydrogen atom or an organic group having 20 or less carbon atoms, c is an integer of 1 to 3, X ² is CO
₂ ^- or SO ₃ ^- in which, selected from carboxy betaine groups or sulfobetaine a group represented by. Y ² is a halogen atom or a hydrolyzable group,
As the hydrolyzable group can be exemplified the same groups as those listed above Y ^1, it is preferably an alkoxy group.

In the present invention, typical examples of the hydrophilic silane compound represented by the general formula (3) include the following.

Embedded image And other polyether-based silane compounds.

Embedded image And other ammonium-based silane compounds.

Embedded image And other betaine-based silane compounds. These hydrophilic silane compound, such as the corresponding olefin and an alkoxysilane having an ether group, a hydrosilylation reaction with a halogenated silane such as, addition of a hydrocarbon-substituted by the corresponding tertiary amino group-containing silane and X ¹ It can be produced by a reaction or a ring-opening addition reaction of the corresponding tertiary amino group-containing silane with lactone, sultone or the like.

Hydrophilic oil repellent treating agent The hydrophilic oil repellent treating agent of the present invention comprises at least one kind of the above-mentioned fluorine-containing silane compound (A) and at least one kind of the hydrophilic silane compound (B). It is prepared by mixing in an organic solvent. In this case, the fluorine-containing silane compound of (A) and the hydrophilic silane compound of (B) are, on a weight basis,
It is desirable to use A / B at a ratio of 0.05 to 10, particularly 0.1 to 5. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, t-butanol, 2,2,2-trifluoroethanol, ethers such as diethyl ether and tetrahydrofuran, and ketones such as acetone and methyl ethyl ketone. , Methylene chloride, chloroform, trichlorotrifluoroethane, halogenated hydrocarbons such as meta-xylene hexafluoride, and a mixed solvent thereof are suitable.
Among them, methanol, n-butanol, methyl ethyl ketone, and meta-xylene hexafluoride are preferred. In such an organic solvent solution, the silane compounds (A) and (B) are preferably contained in a total amount of 1 to 15% by weight, particularly 3 to 10% by weight.

It is preferable that a curing catalyst be added to the organic solvent solution. Such a curing catalyst promotes polycondensation of the component (A) and the component (B) when the surface treatment of the substrate is performed using the treating agent, and forms a cured film on the substrate surface promptly. Act on. Examples of the curing catalyst include hydrochloric acid, inorganic acids such as sulfuric acid, organic acids such as methanesulfonic acid, and organic metal compounds such as tetra-n-butyl titanate and dibutyl tin dilaurate. Tetra-n-butyl titanate, dibutyl tin dilaurate and the like are preferably used. The amount of the curing catalyst to be added varies depending on the type of the component (A) and the component (B) and the type of the catalyst, but is generally 0.05% based on 100 parts by weight of the total amount of the components (A) and (B). Used in amounts of up to 10 parts by weight.

Further, the hydrophilic oil-repellent treating agent comprising the organic solvent solution may be used as long as its properties are not impaired.
If necessary, additives such as an inorganic filler, an antistatic agent and a cross-linking agent can be blended. Such a hydrophilic oil repellent is generally used in the form of an organic solvent solution, but is not necessarily limited thereto. In some cases, a solvent dispersion,
It can be used in any form such as an emulsion or an aerosol. In use, a condensation catalyst, silica sol, a silane coupling agent and the like may be added to the organic solvent solution, and the silane compound of the component (A) or (B) may be co-condensed before use. Furthermore, the ingredients
As the silane compound (A) or (B), a compound in which Y ¹ and Y ² are halogen may be used in a form in which a silazane bond is formed by reacting with ammonia or the like in an organic solvent solution. it can.

Surface treatment The treatment of a substrate with the hydrophilic oil repellent treatment agent of the present invention is performed by applying the composition to the surface of the substrate and then heating as necessary to form a cured film on the surface of the substrate. This is done by letting
The application to the substrate can be performed by spraying, brushing, dipping, or the like. The heating performed as needed is hot air,
It can be performed using infrared rays or the like. The heating temperature varies depending on the type of the silane compound (A) and (B) used, the substrate to be treated, etc.
A range of 160 ° C. is suitable, and a heating time of 20 minutes or more is suitable. If this heating temperature is set higher than necessary,
The silane compounds of the components (A) and (B) may be decomposed to form an appropriate coating, or the substrate to be treated may be inconveniently deformed. Further, the thickness of the treatment film formed on the surface of the base material can be adjusted by changing the concentration of the effective component (the silane compound of A and B) in the treatment agent, the application conditions, and the like. For example, in the treatment method by immersion, a film having an appropriate thickness can be formed by adjusting the concentration of the active ingredient in the treatment agent or adjusting the pulling speed of the substrate. The treating agent of the present invention is extremely effective as a surface treating agent for glass, ceramics, metal, various plastics, wood, fibers and the like. In particular,
Since both hydrophilicity and oil repellency are imparted at the same time, even when used in the treatment of textile products, the permeability of water during washing is not hindered, and the stain removability is not impaired.

[0022]

Examples 1 to 7 The fluorine-containing silane compound and the hydrophilic silane compound shown in Table 1 were diluted together with 0.06 g of tetra-n-butyl titanate in a mixed solvent of methanol / methyl ethyl ketone (weight ratio: 3/1). To prepare a 40 g solution. Separately, washed and washed with acetone and dried glass plate (2.6 × 7.6cm)
Was prepared and immersed in the solution prepared above. After pulling up at a pulling rate of 15 cm / min, the coating was cured at 120 ° C. for 2 hours to form a hydrophilic oil-repellent coating on the glass surface. The contact angle of water and n-hexadecane was measured on the surface on which the coating film was formed, and the hydrophilic oil repellency was evaluated. The results are shown in Table 1.

[0023]

[Table 1]

In the above table, Me represents a methyl group;
f is the following formula:

Embedded image Represents a group represented by In Examples 2 to 4, the contact angle was too small, and accurate measurement was difficult.

Comparative Examples 1 to 5 Fluorine-containing silane compounds shown in Table 2 as silane compounds
Using only 1.2 g, a solution was prepared in the same manner as in the example, and a hydrophilic oil-repellent coating film was formed on the glass surface in the same manner. The contact angle of water and n-hexadecane was measured on the surface on which the coating film was formed, and the hydrophilic oil repellency was evaluated. The results are shown in Table 2.

[0026]

[Table 2]

In the above table, Rf represents the same group as described above.

[0028]

The hydrophilic oil repellent treating agent of the present invention can impart the same oil repellency as when only a silane compound having a fluorinated organic group such as a perfluoroalkyl group is used, and at the same time, has a hydrophilic property. Can also be given. Therefore, this treatment agent can permanently impart hydrophilic oil repellency to various substrates, can improve the antifouling property of the substrate, and can improve the antifogging property. There is no loss in stain removal.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazutoshi Sozawa 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Yasushi Yasushi, Gunma Prefecture Matsuida Town, Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (56) References JP-A-58-172243 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C09K 3/18 D06M 15/657 CA (STN) WPI / L (QUESTEL)

Claims (1)

(57) [Claims] (A) The following general formula (1): (Rf¹Q¹)_aSi (Z¹)_4-abY¹ _b (1) and the following general formula (2): Y¹ _b(Z¹)_3-bSi (Q¹Rf²Q¹) Si (Z¹)_3-bY¹ _b  (2) where Rf¹Is a perfluoroalkyl group or perfluoro
R alkyl ether group, Rf²Is a perfluoroalkylene group or perful
O-alkylene ether group, Q¹Is a divalent organic group, Z¹Is a monovalent organic group, Y¹Is a halogen atom or a hydrolyzable group; a is an integer of 1 to 3; b is an integer of 1 to 3; a + b is 4 or less; (B) the following general formula (3): (Hy-A)_aSi (Z²)_4-abY² _b (3) where Hy isThe following equation (14): Embedded image  Wherein R is a hydrogen atom or an atom having 22 or less carbon atoms.
The alkyl group, s and t are each an integer of 0 to 50.
And s and t do not become 0 at the same time.]
An ether group represented by the following formula (15): -N ⁺ R ¹ R ² R ³ ・ X ^1- (15) [Wherein, R ¹ , R ² And R ³ Is a hydrogen atom or
Are organic groups having 1 to 20 carbon atoms, which are
X which may combine with each other to form a ring, ¹ Is a monovalent shade
An ammonium group represented by the formula:
(16): Embedded image  [Wherein, R is a hydrogen atom or a carbon atom number as described above.
An organic group of 20 or less, c is an integer of 1 to 3, X ² Is CO
₂ ⁻ Or SO ₃ ⁻ Is a carboxybe represented by
Selected from Tyne or SulfobetaineHydrophilic
A is an alkylene group, Z is²Is a monovalent organic group, Y²Is a halogen atom or a hydrolyzable group, a is an integer of 1 to 3, b is an integer of 1 to 3, and a + b is 4 or less. A hydrophilic oil-repellent treating agent.