JPH1129585A - Perfluoropolyether modified aminosilane and finishing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound excellent in water and oil repellency, chemical resistance, and lubricity, etc., and capable of being used as a finishing agent when applied to various substrate surfaces. SOLUTION: This compound is a perfluoropolyether modified aminosilane of formula I (X is a hydrolyzable group; R1 is a lower alkyl or phenyl; R2 is H, a lower alkyl, phenyl; Q is CH2 CH2 CH2 or CH2 CH2 NHCH2 CH2 CH2 ; (m) is an integer of 6 to 50; (n) is 2 or 3; (x) and (y) are each an integer of 1 to 3), e.g. a compound of formula II. A compound of formula I is obtained e.g. by carrying a condensation reaction between a perfluoropolyether carboxylic acid derivative of formula III (R is H or a lower alkyl) and animoalkylsilane of formula IV having a hydrolyzable group. The obtained compound is applied to a substrate surface so as to form a rigid coating film thereon and the effect produced by the film lasts for a long time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel perfluoropolyether-modified aminosilane capable of forming a cured film having excellent water and oil repellency, releasability and the like, and a surface treating agent containing the same as a main component. .

[0002]

2. Description of the Related Art Generally, a compound containing a perfluoropolyether group has a very small surface energy, so that it has poor water repellency, oil repellency, chemical resistance, lubricity and mold release properties. Has properties. Utilizing its properties, it is industrially widely used for water and oil repellents such as paper and fiber, lubricants for magnetic recording media, oil preventives for precision equipment, mold release agents, cosmetics, and protective films.

However, its properties indicate that it has non-adhesiveness and non-adhesion to other substrates at the same time, and although it can be applied to the surface of a substrate, it forms a film and adheres to the substrate. I couldn't let it.

On the other hand, a silane coupling agent is well known as a method for bonding the surface of a substrate such as glass or cloth with an organic compound. The silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group undergoes a self-condensation reaction due to moisture in the air and the like to form a siloxane, forming a film. At the same time, by chemically and physically bonding to surfaces such as glass and metal,
It becomes a strong film having durability. Utilizing this property, silane coupling agents are widely used as coating agents for various substrate surfaces.

[0005] JP-A-58-167597 discloses a fluoroaminosilane compound represented by the following formula (2), taking advantage of these characteristics.

[0006]

Embedded image (Wherein R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms, and Q is C
H ₂ CH ₂ CH ₂ group or CH ₂ CH ₂ NHCH ₂ CH ₂ CH
_Two groups, m is an integer of 1 to 4, and n is 2 or 3. )

However, in this compound, the perfluoropolyether group portion is as short as a dimer to pentamer of hexafluoropropylene oxide (HFPO), so that the characteristics of the perfluoropolyether group cannot be sufficiently exhibited. Was.

Further, Japanese Patent Application Laid-Open No. 58-122797 discloses a compound represented by the following formula (3) as a water / oil repellent on a glass surface. The number is as small as 1 to 20, and a sufficient effect has not been obtained.

[0009]

Embedded image (Wherein, Rf is a polyfluoroalkyl group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ¹
Is a hydrogen atom or a lower alkyl group, A is an alkylene group, X
Is -CON (R ²⁾ -Q- group or -SO ^₂ N (R ₂₎ -Q
Group (where R ² represents a lower alkyl group, Q represents a divalent organic group), Y represents a lower alkyl group, Z represents a halogen, an alkoxy group, or an R ³ COO— group (where R ³ represents a hydrogen atom or Represents a lower alkyl group), n is 0 or 1, a is 1-3
And b represents 0, 1 or 2. )

[0010] In recent years, with the increase in the height of buildings, the demand for technologies for "reducing dirt" and "removing dirt" has been increasing year by year. The development of materials that can be used has been desired.

[0011]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a perfluoropolyether carboxylic acid derivative and an aminoalkyl having a hydrolyzable group By the condensation reaction with silane, a novel perfluoropolyether-modified aminosilane represented by the following general formula (1) is obtained, and the perfluoropolyether-modified aminosilane of the formula (1) has water- and oil-repellency, chemical resistance Excellent in lubricity, release properties, etc.
It has been found that it can be used as a surface treatment agent, and that the treated film is firmly adhered to the substrate, so that the effect can be maintained for a long time. in this case,
The perfluoropolyether-modified aminosilane of the formula (1), which is the main component of this surface treatment agent, contains an amide bond, but the amide bond is effective for efficiently orienting the fluorine-modified group on the substrate surface. Is known to be
Also from this point, the surface treating agent shown in the present invention is superior to the conventional ones.

[0012]

Embedded image (In the formula, X is a hydrolyzable group, R ¹ is a lower alkyl group or a phenyl group, R ² is a hydrogen atom or a lower alkyl group or a phenyl group, Q is CH ₂ CH ₂ CH ₂ group or CH ₂ CH ₂
NHCH ₂ CH ₂ CH ₂ group, m is an integer of 6 to 50, n is 2
Or 3, x and y each show an integer of 1-3. )

Accordingly, the present invention provides a perfluoropolyether-modified aminosilane represented by the above formula (1) and a surface treating agent containing the aminosilane or a partially hydrolyzed condensate thereof as a main component.

Hereinafter, the present invention will be described in more detail.
The perfluoropolyether-modified aminosilane of the present invention is represented by the following general formula (1).

[0015]

Embedded image (In the formula, X is a hydrolyzable group, R ¹ is a lower alkyl group or a phenyl group, R ² is a hydrogen atom or a lower alkyl group or a phenyl group, Q is CH ₂ CH ₂ CH ₂ group or CH ₂ CH ₂
NHCH ₂ CH ₂ CH ₂ group, m is an integer of 6 to 50, n is 2
Or 3, x and y each show an integer of 1-3. )

Here, X represents a hydrolyzable group, and specific examples thereof include an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. An oxyalkoxy group having 2 to 6 carbon atoms, particularly 2 to 4 carbon atoms, such as a methoxyethoxy group;
Examples include acyloxy groups such as acetoxy groups, alkenyloxy groups such as isopropenoxy groups, and halogen groups such as chloro groups, bromo groups, and iodo groups. Among them, a methoxy group, an ethoxy group, an isopropenoxy group and a chloro group are preferred.

R ¹ is a lower alkyl group or a phenyl group,
Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, etc.
Among them, a methyl group is preferred.

R ² is a hydrogen atom, a lower alkyl group or a phenyl group. Specific examples of the lower alkyl group include R ¹
Is the same as Among them, a hydrogen atom and a methyl group are preferred.

Q is a CH ₂ CH ₂ CH ₂ group or CH ₂ CH ₂
Any of NHCH ₂ CH ₂ CH ₂ groups may be used, and these may be mixed.

M is an integer of 6 to 50. If it is smaller than this range, the characteristics of the perfluoropolyether group will not be sufficiently exhibited, and if it is larger than this range, the proportion of the alkoxysilyl group in the entire molecule will be extremely small, so that the condensation reaction of the alkoxysilyl group will not occur. It ’s hard to go,
It is not preferable in forming a film. The value of m is 15
The range of ~ 35 is particularly desirable on the balance between the expression of function and reactivity.

N may be either 2 or 3, and n =
2 and n = 3 may be used in combination.

X and y are each an integer of 1 to 3;
_x F _2x, as the C _y F _2y, can be mentioned as follows.

[0023]

Embedded image

The above F (C _x F _2x O) _m C _y F _2y is
Particularly, the following are preferable.

[0025]

Embedded image (M is the same as above.)

The above-mentioned perfluoropolyether-modified aminosilane is, for example, a condensation reaction of a perfluoropolyethercarboxylic acid derivative represented by the following formula (i) with an aminoalkylsilane having a hydrolyzable group represented by the following formula (ii) Can be manufactured by

[0027]

Embedded image (R represents a hydrogen atom or a lower alkyl group, and X, R ¹ ,
R ² , Q, m, n, x, and y have the same meanings as described above. )

The above condensation reaction can be carried out in the presence of a solvent such as meta-xylene hexafluoride at 20 to 100 ° C. in an atmosphere of an inert gas such as nitrogen.

The perfluoropolyether-modified aminosilane of the present invention is excellent in water / oil repellency, chemical resistance, lubricity, releasability, etc., and can be used for the following applications. Water and oil repellents… Paper, wood, fiber, leather, metal, glass, stone, ceramic, plastic, powder, etc. Lubricant… Paper, wood, fiber, metal, glass, stone, ceramic, plastic, etc. Release agent… Adhesive tape, molding die, roll, glass,
Plastics, fibers, etc. Coating agents for electronic components, semiconductor elements, etc. Protective coating agents for paints, wax additives Paint additives, resin modifiers, fluidity / dispersibility improvers for inorganic fillers, etc.

The perfluoropolyether-modified aminosilane of the present invention is suitably used as a surface treating agent for various substrates as described above, and the surface treating agent of the present invention is a perfluoropolyether of the formula (1) of the present invention. A polyether-modified aminosilane and / or a partially hydrolyzed condensate thereof are used as a main component. In this case, a hydrolytic condensation catalyst may be added to the surface treatment agent as needed. Such catalysts include:
Organic tin compounds (such as dibutyltin dimethoxide and dibutyltin dilaurate); organic titanium compounds (such as tetra-n-butyl titanate); organic acids (such as acetic acid and methanesulfonic acid); and inorganic acids (such as hydrochloric acid and sulfuric acid). Particularly, acetic acid, tetra-n-butyl titanate, dibutyl tin dilaurate and the like are desirable.

The surface treating agent can be used after being diluted with a solvent. As the solvent, those which uniformly dissolve the surface treating agent are preferable. For example, fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane) and fluorine-modified aromatic hydrocarbon solvents (m-xylenehexa) Fluoride, benzotrifluoride, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.),
Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) are mentioned, and a fluorine-modified solvent is desirable in terms of solubility and the like (particularly, m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), etc.) ). These solvents may be used alone or in combination of two or more.

The above-mentioned surface treating agent can be treated by a known method such as brushing, dipping, spraying or vapor deposition as it is or dissolved in the above-mentioned solvent. The processing temperature is appropriately selected, but the processing humidity is preferably performed under humidification in order to promote the reaction.

[0033]

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

Synthesis Example 1 A 500 ml four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with HFPO oligomer methyl ester 2 represented by the following formula (4).
54.8 g, 3-aminopropyltrimethoxysilane 1
1.8 g, metaxylene hexafluoride 127.4 g
And heated at 70 ° C. for 6 hours under a nitrogen stream.

[0035]

Embedded image

After confirming that the absorption of the raw material ester had ceased from the IR spectrum, the solvent and the like were distilled off under reduced pressure to obtain 260.3 g of a yellow viscous liquid. The data of ¹ H-NMR spectrum and IR spectrum of the obtained compound are shown.

[0037] ¹ H-NMR (TMS standard, ppm) 0.7-1.0 (m, 2H , -C H 2 Si≡) 1.8-2.0 (m, 2H, -CH 2 C H 2 _{CH 2 -) 3.4-3.6 (m,} 2H, -CONHC H 2 -) 3.7 (s, 9H, -Si (OC H 3) 3) 7.3 (s, 1H, -CON H −) IR (KBr plate, liquid film method, cm ⁻¹ , FIG. 1) 2950-2850 (CH) 1710 (CONH) 1315-1110 (CF)

From the above results, it was found that the structural formula of the obtained compound was as shown below.

[0039]

Embedded image

[Synthesis Example 2] HFPO oligomer methyl ester 1 represented by the following formula (5) was placed in a 300 ml four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer.
24.3 g, 3-aminopropyltriethoxysilane 1
2.2 g and 62.2 g of meta-xylene hexafluoride were added and heated at 70 ° C. for 6 hours under a nitrogen stream.

[0041]

Embedded image

After confirming that the absorption of the raw material ester had ceased from the IR spectrum, the solvent and the like were distilled off under reduced pressure to obtain 131.8 g of a yellow viscous liquid. The data of ¹ H-NMR spectrum and IR spectrum of the obtained compound are shown.

¹ H-NMR (TMS standard, ppm) 0.7-0.9 (m, 2H, -CH ₂ Si≡) 1.1-1.3 (t, 9H, -Si (OCH ₂ C)
_{H 3) 3) 1.9-2.1 (m} , 2H, -CH 2 C H 2 CH 2 -) 3.4-3.6 (m, 2H, -CONHC H 2 -) 3.8 (q , 6H, -Si (OC H ₂ C
_{H 3) 3) 7.1 (s} , 1H, -CON H -) IR (KBr plate, Ekimakuho, cm ^-1, Fig. 2) 2945-2860 (C-H) 1710 (CONH) 1320-1100 ( CF)

From the above results, it was found that the structural formula of the obtained compound was as shown below.

[0045]

Embedded image

Synthesis Example 3 HFPO oligomer methyl ester 1 represented by the following formula (6) was placed in a 300 ml four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer.
79.2 g, 5.9 g of 3-aminopropyltrimethoxysilane, and 89.6 g of meta-xylene hexafluoride were added, and heated at 70 ° C. for 7 hours under a nitrogen stream.

[0047]

Embedded image

After confirming from the IR spectrum that the absorption of the raw material ester had ceased, the solvent and the like were distilled off under reduced pressure to obtain 181.5 g of a yellow viscous liquid. The data of ¹ H-NMR spectrum and IR spectrum of the obtained compound are shown.

[0049] ¹ H-NMR (TMS standard, ppm) 0.8-1.0 (m, 2H , -C H 2 Si≡) 2.0-2.1 (m, 2H, -CH 2 C H 2 CH _2- ) 3.4-3.6 (m, 2H, -CONCH _2- ) 3.8 (q, 6H, -Si (OCH ₃ ) ₃ ) 7.3 (s, 1H, -CON H −) IR (KBr plate, liquid film method, cm ⁻¹ , FIG. 3) 2950-2840 (CH) 1710 (CONH) 1320-1100 (CF)

From the above results, it was found that the structural formula of the obtained compound was as shown below.

[0051]

Embedded image

Synthesis Example 4 HFPO oligomer methyl ester 1 represented by the following formula (7) was placed in a 300 ml four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer.
62.0 g, 3-aminopropyltrimethoxysilane 3
5.9 g and 81.0 g of meta-xylene hexafluoride were added and heated at 70 ° C. for 4 hours under a nitrogen stream.

[0053]

Embedded image

After confirming from the IR spectrum that the absorption of the raw material ester had ceased, the solvent and the like were distilled off under reduced pressure to obtain 170.8 g of a yellow viscous liquid. The data of ¹ H-NMR spectrum and IR spectrum of the obtained compound are shown.

[0055] ¹ H-NMR (TMS standard, ppm) 0.9-1.1 (m, 2H , -C H 2 Si≡) 2.0-2.2 (m, 2H, -CH 2 C H 2 _{CH 2 -) 3.3-3.5 (m,} 2H, -CONHC H 2 -) 3.7 (q, 6H, -Si (OC H 3) 3) 7.0 (s, 1H, -CON H −) IR (KBr plate, liquid film method, cm ⁻¹ , FIG. 4) 2950-2846 (CH) 1709 (CONH) 1309-1105 (CF)

From the above results, it was found that the structural formula of the obtained compound was as shown below.

[0057]

Embedded image

[Examples 1 to 3] 3.0 g of perfluoropolyether-modified aminosilane synthesized in Synthesis Examples 1 to 3
To perfluoro (2-butyltetrahydrofuran) 9
7.0 g, and melted on a glass plate (2.5 × 10 × 0.5
cm) with a brush. It was left for 1 hour in an atmosphere of 25 ° C. and 70% humidity to form a cured film. The following evaluation was performed using this sample piece.

(1) Evaluation of Water and Oil Repellency The contact angle of the cured film to water and n-hexadecane was measured using a contact angle meter (A3 type manufactured by Kyowa Interface Science Co., Ltd.).
The water and oil repellency was evaluated. (2) Evaluation of releasability A cellophane adhesive tape (25 mm width) was adhered to the surface of the cured film, and the peeling force was measured to evaluate the releasability. Measurement was performed at a 180 ° angle using a tensile tester at a peeling speed of 300 m.
m / min. I went in. (3) Evaluation of Durability of Coating After wiping the cured coating surface with a cellulose nonwoven fabric 30 times with a constant load, the contact angle with water was measured by the method shown in Evaluation (1) to evaluate the durability. . Table 1 shows the evaluation results of (1) to (3).

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the fluoroaminosilane synthesized in Synthesis Example 4 was used instead of the fluoroaminosilane used in Examples 1 to 3. Table 1 shows the evaluation results.

Comparative Example 2 Instead of the fluoroaminosilane used in Examples 1 to 3, C ₈ H ₁₇ CH ₂ CH ₂ Si
Evaluation was made in the same manner as in the example except that (OCH ₃ ) ₃ was used. Table 1 shows the evaluation results.

[0062]

[Table 1]

From the results in Table 1, the following points were confirmed. Water / oil repellency: Examples are more excellent in water / oil repellency than comparative examples. Releasability: All of the examples are practically sufficiently low, but the comparative examples cannot be put to practical use. Endurance: The examples are more durable than the comparative examples.

[0064]

The perfluoropolyether-modified aminosilane shown in the present invention forms a strong film on the surface of the substrate,
It can be applied as a surface treatment agent excellent in water repellency, oil repellency, release property and the like.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of Synthesis Example 1.

FIG. 2 is an infrared absorption spectrum of Synthesis Example 2.

FIG. 3 is an infrared absorption spectrum of Synthesis Example 3.

FIG. 4 is an infrared absorption spectrum of Synthesis Example 4.

Claims (4)

[Claims] [Claim 1] The following general formula (1) (In the formula, X is a hydrolyzable group, R ¹ is a lower alkyl group or a phenyl group, R ² is a hydrogen atom or a lower alkyl group or a phenyl group, Q is CH ₂ CH ₂ CH ₂ group or CH ₂ CH ₂
NHCH ₂ CH ₂ CH ₂ group, m is an integer of 6 to 50, n is 2
Or 3, x and y each show an integer of 1-3. A) a perfluoropolyether-modified aminosilane. 2. F (C _x F _2x O) _m C _y F _2y is represented by the following formula: The perfluoropolyether-modified aminosilane according to claim 1, wherein m is an integer of 6 to 50. 3. The aminosilane modified with perfluoropolyether according to claim 1, wherein the hydrolyzable group X is an alkoxy group. 4. A surface treating agent comprising the perfluoropolyether-modified aminosilane according to claim 1, 2 or 3 and / or a partially hydrolyzed condensate thereof as a main component.