KR101335042B1 - Perfluoropolyether-modified silane, surface treating agent using the same as main component, and article having cured coating film formed therefrom - Google Patents

Abstract

The present invention is a novel perfluoropolyether-modified silane which is excellent in water / oil repellency, mold release property, chemical resistance, lubricity, antifouling property, fingerprint removal property, especially scratch resistance, which can maintain long-term performance, and a main component thereof. It is an object of the present invention to provide an antireflection filter and a polarizing plate having a surface treating agent having a polyfunctional hydrolyzable group, and an antifouling layer having excellent antifouling properties and fingerprint removal properties and particularly excellent scratch resistance.

The present invention also provides a perfluoropolyether modified silane represented by the following formula (1).

Wherein Rf is a monovalent or divalent perfluoropolyether group, Q is a divalent group connecting Rf group to Z, Z is a trivalent or higher organopolysiloxane group having three or more siloxane bonds, and R is carbon number 1 An alkyl group or a phenyl group of 4 to 4, X is a hydrolyzable group, a is 2 or 3, b is 2 to 10, α is 1 or 2, and c is an integer of 1 to 5.

Perfluoropolyether modified silane, surface treatment agent, antireflection filter, polarizing plate

Description

PERFLUOROPOLYETHER-MODIFIED SILANE, SURFACE TREATING AGENT USING THE SAME AS MAIN COMPONENT, AND ARTICLE HAVING CURED COATING FILM FORMED THEREFROM}

1 is an IR chart of compound 1. FIG.

2 is an NMR chart of compound 1. FIG.

3 is an IR chart of compound 2.

4 is an NMR chart of compound 2. FIG.

5 is an IR chart of compound 3.

6 is an NMR chart of compound 3. FIG.

7 is an IR chart of compound 4. FIG.

8 is an NMR chart of compound 4. FIG.

9 is an IR chart of compound 5.

10 is an NMR chart of compound 5. FIG.

[Patent Document 1] Japanese Unexamined Patent Publication No. 58-167597

[Patent Document 2] Japanese Unexamined Patent Publication No. 58-122979

[Patent Document 3] Japanese Unexamined Patent Publication No. 9-258003

[Patent Document 4] Japanese Patent Application Laid-Open No. 6-5324

[Patent Document 5] Japanese Patent Application Laid-Open No. 11-29585

[Patent Document 6] Japanese Patent Application Laid-Open No. 2001-188102

[Patent Document 7] Japanese Unexamined Patent Publication No. 2002-348370

[Patent Document 8] Japanese Unexamined Patent Publication No. 2003-113244

[Patent Document 9] Japanese Unexamined Patent Publication No. 2003-238577

The present invention provides a novel perfluoropolyether-modified silane having excellent water / oil repellency, mold release property, antifouling property, fingerprint removal property, and the like, and in particular, adhesion to a substrate, and a surface treating agent having a polyfunctional hydrolyzable group containing the same as a main component, and The present invention relates to an antireflection filter and a polarizing plate having an antifouling layer excellent in antifouling property and fingerprint removal property and particularly excellent in scratch resistance.

Generally, the perfluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, mold release property, antifouling property and the like because its surface free energy is very small. These properties are widely used in water and oil repellent antifouling agents such as paper and fibers, lubricants for magnetic recording media, oil repellents for precision instruments, mold release agents, cosmetics, and protective films.

However, the above properties indicate that they are non-adhesive and non-adhesive to other substrates at the same time, and even though it is possible to apply them to the surface of the substrate, it was difficult to form a film and bring it into close contact.

On the other hand, a silane coupling agent is well known as what couple | bonds the surface of base materials, such as glass and 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 causes a self-condensation reaction by moisture in the air or the like to form a siloxane to form a film. At the same time, by bonding chemically and physically to the surface of glass, metal, etc., it becomes a durable durable film. Silane coupling agents are widely used as coating agents for various substrate surfaces by utilizing these properties.

Taking advantage of these features, Japanese Patent Laid-Open No. 58-167597 discloses a fluoroaminosilane compound represented by the following formula (8). However, this compound could not fully utilize the characteristics possessed by the perfluoropolyether group because the portion of the perfluoropolyether group was short with 2 to 5 mers of hexafluoropropylene oxide (HFPO).

Wherein, R ^1, R ² is an alkyl group having 1 to 4, Q ¹ is CH ₂ CH ₂ CH ₂ or CH ₂ CH ₂ NHCH ₂ CH ₂ CH _2, h is an integer of 1 to 4, i is 2 or 3 to be.

In addition, Japanese Patent Laid-Open No. 58-122979 discloses a compound represented by the following formula (9) as a water / oil repellent agent on the glass surface. No effect could be obtained.

Wherein Rf ¹ is a polyfluoroalkyl group having 1 to 20 carbon atoms, and may contain one or more ether bonds, R ³ is a hydrogen atom or a lower alkyl group, A is an alkylene group, X ¹ is -CON (R ⁴ ) -Q- or SO ₂ N (R ⁴ ) -Q- (where R ⁴ is a lower alkyl group and Q represents a divalent organic group), Z is a lower alkyl group, Y is a halogen, alkoxy group or R ⁵ COO- (Wherein R ⁵ represents a hydrogen atom or a lower alkyl group), s represents an integer of 0 or 1, t represents an integer of 1 to 3, and u represents 0 or an integer of 1 to 2.

In particular, recently, due to the high-rise building, the maintenance of window glass is not performed, and the technology to prevent dirt from being stained with fingerprints on the display surface to improve appearance and visibility. The demand for technology that easily removes "is increasing year by year, and the development of the material which can respond to these requirements is calculated | required.

Taking advantage of the properties of the perfluoropolyether group-containing compound and the silane coupling agent to form a solid coating on the surface of the substrate, and to prevent the fluorine-containing silane compound as a surface treatment agent excellent in water and oil repellency, antifouling properties, chemical resistance, lubricity, mold release properties, etc. Although a lens used for a five-layer is known (Japanese Patent Laid-Open No. 9-258003), the fluorine-containing silane compound has a relatively high content of hydrolyzable groups in one molecule, but is present only at one end thereof, and thus is particularly useful as a substrate. Inadequate adhesiveness has problems in terms of durability, and when used as a surface treatment agent for a lens, it is not appropriate because the desired performance can not be sustained over a long period of time.

In addition, in an anti-reflection film that is generally installed on the surface of a visual device, contaminants such as hand, fingerprint, sweat, saliva, and cosmetic material are easily adhered, and the surface reflectance is changed or the attachment floats white due to the adhesion. As there is a difficulty that contaminants are more noticeable than simple transparent plates such as unclear contents, it is excellent in preventing adhesion of these contaminants and removal of attached contaminants and maintaining antifouling performance in the long term. Providing an antireflection film has long been a problem.

Conventionally, as an anti-reflection film for the purpose of improvement of fouling resistance, an organic polysiloxane-based polymer is formed on the surface of an anti-reflection layer comprising a single layer or a multilayer inorganic material layer having a surface layer mainly composed of silicon dioxide formed by PVD method. Or it is known to have a hardened layer containing a perfluoroalkyl group containing polymer (Japanese Patent Laid-Open No. 6-5324).

However, in case of attaching human contaminants such as hand or fingerprint, it is difficult to wipe with tissue paper, etc., and the antireflection film is damaged when the contaminants spread through a thin film and rubbed strongly, so that satisfactory removal cannot be achieved. .

Generally, the perfluoropolyether group-containing compound has the above-mentioned characteristics, and the perfluoropolyether-modified aminosilane represented by the following general formula (10) in Japanese Patent Laid-Open No. Hei 11-29585 is utilized. The anti-reflection film which used this for the antifouling layer is disclosed. However, the anti-reflection film is excellent in water / oil repellency, antifouling property, chemical resistance, lubricity, mold release property, and the like, but has high affinity with water in the perfluoropolyether-modified aminosilane molecule used in the antifouling layer. Since it contains a polar group and the ratio (weight%) of the hydrolyzable group in one molecule is small, it requires time until hardening, has a problem, such as adhesive surface to a base material, and has sufficient performance in using as a surface treating agent. It was required to provide.

Wherein X ³ is a hydrolyzable group, R ⁵ is a lower alkyl group, R ⁶ is a hydrogen atom or a lower alkyl group, Q ² is CH ₂ CH ₂ CH ₂ or CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ , e is 6 to An integer of 50, f is 2 or 3, c and d are each an integer of 1 to 3.

In addition, Japanese Patent Laid-Open No. 2001-188102 discloses an antireflection film using a perfluoropolyether group-containing silane coupling agent represented by the following formula (11) for an antifouling layer, and a perfluoro used for the antifouling layer. The ropolyether group-containing silane coupling agent does not contain a polar group, but the ratio of hydrolyzable groups in one molecule is not sufficient, so it takes time to cure or is used as a surface treatment agent such as poor adhesion to a substrate. It did not say that it had enough performance.

Wherein, Rf ² is a constant, j is 0, a C 1 -C 16 linear or branched alkyl group with ground perfluoroalkyl, R ⁷ is an alkyl group having 1 to 10, k is from 1 to 50 integer, r is 0 to 6 An integer of 3 to 1, where l is an integer of 0 to 3, where 0 <j + l ≦ 6.

In Japanese Patent Laid-Open Nos. 2002-348370 and 2003-113244, a perfluoropolyether group-containing silane coupling agent having a large number of hydrolyzable groups at one end is said to be a good surface treatment agent.

Further, Japanese Laid-Open Patent Publication No. 2003-238577 discloses that the perfluoropolyether group-containing silane coupling agent represented by the following general formula (12) has two or three hydrolyzable groups at both ends, and is excellent in adhesion to the substrate. It does not get dirty, is easy to remove contaminants, has good surface slipping properties, is not damaged, sustains their performance, etc., but still does not perform long-term performance, especially scratch resistance It is a reality.

In the formula, Rf is a divalent linear perfluoropolyether group, R is an alkyl or phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, p is 0 to 2, q is an integer of 1 to 5, a is 2 Or three.

Therefore, even if the contaminants do not adhere, even if the contaminants are attached, the contaminants are not visible, and at the same time, the attached contaminants, including human contaminants such as hand or fingerprints, can be easily wiped off with tissue paper, and the like. The adhesion of water droplets and the like can be easily dropped without being damaged by the removal operation, and further, development of an antireflection filter and a polarizing plate which last long-term performances such as contamination resistance, ease of removal, scratch resistance and water repellency are required. .

Therefore, the present invention is a novel perfluoro that can maintain long-term performance excellent in water and oil repellency, mold releasability, chemical resistance, lubricity, etc., and excellent in antifouling property, fingerprint removal property, especially scratch resistance, in order to meet the above demands. An object of the present invention is to provide an antireflection filter and a polarizing plate having a polyether-modified silane and a surface treating agent having a polyfunctional hydrolyzable group having the main component thereof, and an antifouling layer having excellent antifouling property and fingerprint removal property and particularly excellent scratch resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to respond to the said request | requirement, the novel perfluoro polyether modified silane represented by the following formula is excellent in water-oil repellency, antifouling property, chemical resistance, lubricity, mold release property, etc. The present invention can be used as a surface treatment agent by coating on the surface, and since the treatment film is firmly adhered to the substrate, it has been found that the effect can be sustained for a long time, and the present invention has been completed.

Accordingly, the present invention provides a surface treating agent based on a perfluoropolyether-modified silane of the above formula, the silane and / or its partially hydrolyzed condensate, and the silane and / or its partially hydrolyzed condensate as a main component. An article having a cured coating on its surface is provided. In particular, an antireflection filter and a polarizing plate having an antifouling layer having excellent scratch resistance are provided.

Accordingly, the present invention is a perfluoropolyether modified silane represented by the following formula (1).

&Lt; Formula 1 >

Wherein Rf is a monovalent or divalent perfluoropolyether group, Q is a divalent group connecting Rf group and Z, Z is a trivalent or higher organopolysiloxane group having three or more siloxane bonds, and R Is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, a is 2 or 3, b is 2 to 10, α is 1 or 2, and c is an integer of 1 to 5;

BEST MODE FOR CARRYING OUT THE INVENTION [

Perfluoropolyether-modified silanes of the general formula (1), which are the main components of the surface treatment agent of the present invention, have a large number of hydrolyzable silyl groups at one or both ends of the molecule, and one end or both ends are firmly adhered to the substrate, and thus This is an improvement in the compatibility. In addition, although perfluoropolyether modified silane of (1) contains a silicon functional group, in order to efficiently orient an fluorine-modified group on the surface of a base material, introduction of the silicon functional group of a suitable size is effective, and from this point, The surface treatment agent shown can be said to be superior to that of the past, and is excellent in both adhesion and antifouling performance.

Hereinafter, the present invention will be described in more detail.

The perfluoropolyether modified silane shown by this invention is represented by following General formula (1).

&Lt; Formula 1 >

Wherein Rf is a monovalent or divalent perfluoropolyether group, Q is a divalent group connecting Rf group and Z, Z is a trivalent or higher organopolysiloxane group having three or more siloxane bonds, and R Is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, a is 2 or 3, b is 2 to 10, α is 1 or 2, and c is an integer of 1 to 5;

Here, Rf is a monovalent or divalent perfluoroether group and may be linear or branched. The perfluoroether structure includes a plurality of repeating units of -C _g F _2g O- (wherein each unit is independently an integer of 1 to 6), for example, a chemical formula (C _g F _2g O) _h etc. are mentioned. Here, h is an integer of 1-500, Preferably it is 2-400, More preferably, it is 10-200.

Roneun recurring units -C _g F _2g O- represented by the above formula, for example, and the like to units of g. In addition, the said perfluoroalkyl ether structure may be comprised individually by 1 type of these repeating units, and may be a combination of 2 or more types.

In the case of a perfluoropolyether group, perfluoropolyether groups of various chain lengths are included, among which perfluoro having a perfluoropolyether group having 1 to 4 carbon atoms represented by the following units as a repeating unit Polyether.

In the formula (1), the monovalent perfluoroether group is preferably a perfluorooxyalkyl group selected from the group represented by the following formulas (2), (3) and (4).

In the formula, m is 2 to 200, d is an integer of 1 to 3, and Y is an F or CF ₃ group.

In formula, m is 2-200 and d is an integer of 1-3.

In the formulas, e and f are each an integer of 0 to 200, and e + f is 2 to 200, and the arrangement of the repeating units (CF ₂ O) and (C ₂ F ₄ O) in the formula is random.

In the formula (1), as the divalent perfluoroether group, a perfluorooxyalkyl group selected from the group represented by the following formulas (5), (6) and (7) is preferable.

In the formulas, each Y is independently an F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, and m + n is 2 To 200, s is an integer of 0 to 6, and the arrangement of repeating units in the formula is random.

In formula, l is an integer of 1-200 and d is an integer of 1-3.

Wherein Y is an F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, m + n is 2 to 200, and the arrangement of repeating units in the formula Is random.

In the case of the above-mentioned perfluoropolyether group, perfluoropolyether groups of various chain lengths are included, and preferably perfluoropolyethers having a perfluoropolyether group having about 1 to 4 carbon atoms as a repeating unit. The sum total of the repeating units in the said chemical formula is 1-60, More preferably, it is the range of 10-50. In addition, the molecular structure of a perfluoropolyether is not limited to these things.

In formula, Q is a coupling group of Rf group and Z group, The group containing an amide, ether, ester, a vinyl bond, etc. are mentioned.

Specific examples include the following chemical formulas.

In formula, Z may contain 1 type, or 2 or more types chosen from an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom, Preferably it is a silicon functional group, It is more preferable to have 3 or more of siloxane bonds.

Specifically, the following are mentioned.

In formula, X represents a hydrolysable group and has three or more in the terminal, respectively, and may be same or different. Specific examples thereof include an oxyalkoxy group having 2 to 10 carbon atoms, such as an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a methoxymethoxy group and a methoxyethoxy group, and acetok. C1-C10 alkenyloxy groups, such as a C1-C10 acyloxy group and an isopropenoxy group, halogen groups, such as a chloro group, a bromo group, and an iodine group, etc. are mentioned. Especially, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.

R is a C1-C4 lower alkyl group or a phenyl group, Specifically, they are a methyl group, an ethyl group, a phenyl group, etc. Especially, a methyl group is preferable. a is 2 or 3, and 3 is preferable from a viewpoint of reactivity and adhesiveness to a base material. b is 2 or more, but 2-5 are preferable for compatibility with adhesiveness to a base material, and antifouling performance, but it is not limited to this.

The present invention provides a surface treating agent based on the perfluoropolyether modified silane and / or its partially hydrolyzed condensate.

In this case, a hydrolytic condensation catalyst, for example, an organic tin compound (dibutyltin dimethoxide, dibutyl dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate etc.) is contained in this surface treating agent as needed. ), An organic acid (acetic acid, methanesulfonic acid, etc.), and an inorganic acid (hydrochloric acid, sulfuric acid, etc.) can also be added. Among them, acetic acid, tetra n-butyl titanate, dibutyl tin dilaurate and the like are particularly preferable. The addition amount is catalytic amount and is usually 0.01 to 5 parts by weight, in particular 0.1 to 1 part by weight, based on 100 parts by weight of silane and / or its partial hydrolysis condensate.

In addition, the surface treating agent of this invention can also be diluted and used with a suitable solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), fluorine-modified ether solvents ( Methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc., fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, minerals) Spirits, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be illustrated. Among these, solvents modified with fluorine are preferable in view of solubility and wettability, and m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, and the like are particularly preferable.

Although the said solvent may be used individually by 1 type, and 2 or more types may be mixed, It is preferable to dissolve the said component uniformly. In addition, the concentration of the silane represented by the formula (1) and / or partial hydrolysis condensate thereof dissolved in the solvent is different from the optimum concentration depending on the treatment method, but is preferably from 0.01 to 50% by weight, in particular from 0.05 to 20% by weight.

Thus, as a treatment method of the surface treating agent diluted with the solvent, it can process by well-known methods, such as a hair-coating, dipping, spraying, and a vapor deposition process. In addition, although the optimum temperature differs depending on a treatment method, the treatment temperature is preferably in the range from room temperature to 120 ° C. in the case of hair-coating and immersion, for example. As treatment humidity, it is preferable to carry out under humidification in order to accelerate the reaction.

Moreover, since processing conditions differ according to the silane compound and other additives to be used, it is preferable to optimize every time.

Although the base material treated with the said surface treating agent is not specifically limited, As a base material, the thing of various materials, such as paper, cloth, a metal, its oxide, glass, a plastic, ceramics, and a ceramic, can be used. Specifically, the following are mentioned.

Water and oil repellents: paper, cloth, metal, glass, plastic, ceramics, etc.

Release agent: Adhesive tape, resin molding mold, roll, etc.

Antifouling agents: paper, cloth, metal, glass, plastic, ceramics, etc.

Although the film thickness of the cured film formed on the said various base material-the surface of an article is suitably selected according to the kind of base material, it is usually 0.1 nm-5 micrometers, especially 1 nm-100 nm.

The surface treating agent of this invention is applicable to the following, for example.

Fingerprints and sebum-proof coatings of optical members such as spectacle lenses and antireflection filters;

Water-repellent, antifouling coatings of hygiene products such as bathtubs and sinks;

Antifouling coatings such as window glass and headlamp covers of automobiles, trams and aircrafts;

Water repellent and antifouling coating for exterior wall construction materials;

Grease resistant coatings for kitchen building materials;

Water repellent, antifouling and anti-stick coating of telephone box;

Coating for imparting water and oil repellency and anti-fingerprint adhesion to art works;

Anti-fingerprint coatings such as compact discs and DVDs;

In addition, the fluidity and dispersibility of paint additives, resin modifiers and inorganic fillers are modified, and the lubricity of tapes and films is improved.

<Examples>

Hereinafter, although an Example and a comparative example are given and this invention is concretely demonstrated, this invention is not limited by this. In addition, in the following example, the physical property in a table is measured by the following test method.

[Evaluation method of water and oil repellency]

The water and oil repellency was evaluated by measuring the contact angle of water of the cured film and the receding contact angle with respect to oleic acid by using a contact angle meter (type A3 manufactured by Kyowa Chemical Co., Ltd.).

[Evaluation of scratch resistance of the film]

Using a rubbing tester, a rubbing test was performed under the following conditions to evaluate scratch resistance with cloth.

Evaluation environmental conditions: 25 degrees C, humidity 40%

Rubbing material: 8 nonwoven fabrics were wrapped in the tip (1.5 cm x 1.5 cm) of the tester in contact with the sample, and fixed with a rubber band.

Travel Distance (One Way): Travel Speed: Load: Tip Contact Area: Number of Rubs: 1000

After the rubbing test, the treated surface was coated with magic and evaluated by magic resilience. The scratch resistance evaluation was evaluated as ΔΔ ×.

○: good repulsion of magic

(Triangle | delta): There exists a part which repels magic and a part which is not

×: No magic at all

&Lt; Synthesis Example 1 &

로 표시되는 한쪽 말단에 α-불포화 결합을 갖는 퍼플루오로폴리에테르 50 g, m-크실렌헥사플루오라이드 70.3 g, 염화백금산/비닐실록산 착체의 톨루엔 용액 0.0442 g(Pt 단체로서 1.1×10^{- 6}몰을 함유)을 넣어 90 ℃로 가열 교반하였다. 하기에 나타낸 H4Q 21.93 g을 적하하여 90 ℃에서 3 시간 숙성하고, ¹H-NMR로 원료의 알릴기가 소실된 것을 확인한 후, 용제나 과잉의 H4Q를 감압 증류 제거한 후, 활성탄 처리를 행한 후 무색 투명한 액체 퍼플루오로폴리에테르 77.5 g을 얻었다. The

As one perfluoroalkyl having α- unsaturated bond at the terminal polyether 50 g, m- xylene hexafluoride 70.3 g, 0.0442 g of a toluene solution (Pt groups of chloroplatinic acid / vinyl siloxane complex represented by 1.1 × 10 ^{- 6} moles Was added), and the mixture was heated and stirred at 90 ° C. 21.93 g of H4Q shown below was added dropwise and aged at 90 ° C. for 3 hours, and after confirming that allyl groups of the raw material were lost by ¹ H-NMR, the solvent and excess H4Q were distilled off under reduced pressure, and then treated with activated carbon and then colorless and transparent. 77.5 g of liquid perfluoropolyether were obtained.

Further, the perfluoro polyether obtained above 25 g, m- xylene hexafluoride 30 g, 0.0225 g of a toluene solution of a chloroplatinic acid / vinyl siloxane ^complex-put (2.2 × 10 Pt as group containing ⁶ mol) 90 ℃ Stirred with heating. 4.63 g of trimethoxysilane was added dropwise, aged at 80 ° C. for 3 hours, and the solvent was distilled off under reduced pressure to obtain 26.8 g of a colorless transparent liquid (Compound 1). Its specific gravity was 1.55 and the refractive index was 1.336.

IR and NMR charts of Compound 1 are shown in FIGS. 1 and 2. In addition, ¹ H-NMR data of the obtained compound is shown below.

¹ H-NMR (in TMS, ppm)

From the above results, the structural formula of the obtained compound is

Was found to be.

&Lt; Synthesis Example 2 &

Among the compounds used in Synthesis Example 1, Compound 2 shown below was obtained in the same manner as in Synthesis Example 1, except that cyclic siloxane H4 (tetramethylcyclotetrasiloxane) was used instead of H4Q. Its specific gravity was 1.55 and its refractive index was 1.343.

IR, NMR charts of Compound 2 are shown in FIGS. 3 and 4. In addition, ¹ H-NMR data of the obtained compound is shown below.

¹ H-NMR (in TMS, ppm)

From the above results, the structural formula of the obtained compound is

Was found to be.

&Lt; Synthesis Example 3 &

Among the compounds used in Synthesis Example 1, Compound 3 shown below was obtained in the same manner as in Synthesis Example 1, except that a branched methylhydrogenpolysiloxane containing a silethylene group was used instead of H4Q. Its specific gravity was 1.71 and its refractive index was 1.330.

IR, NMR charts of Compound 3 are shown in FIGS. 5 and 6. In addition, ¹ H-NMR data of the obtained compound is shown below.

¹ H-NMR (in TMS, ppm)

From the above results, the structural formula of the obtained compound is

Was found to be.

&Lt; Synthesis Example 4 &

(여기서, p/q=0.9, p+q≒45)로 표시되는 양쪽 말단에 α-불포화 결합을 갖는 퍼플루오로폴리에테르 50 g, m-크실렌헥사플루오라이드 70 g, 염화백금산/비닐실록산 착체의 톨루엔 용액 0.0442 g(Pt 단체로서 1.1×10^-7몰을 함유)을 넣어 90 ℃로 가열 교반하였다. 하기에 나타낸 H4Q 49.3 g을 적하하여 90 ℃에서 3 시간 숙성하고, ¹H-NMR로 원료의 알릴기가 소실된 것을 확인한 후, 용제나 과잉의 H4Q를 감압 증류 제거한 후, 활성탄 처리를 행하여 무색 투명한 액체 퍼플루오로폴리에테르 46.4 g을 얻었다. The

50 g of perfluoropolyethers having α-unsaturated bonds at both ends represented by (wherein p / q = 0.9, p + q ≒ 45), m-xylenehexafluoride, platinum chloride / vinylsiloxane complex 0.0442 g of toluene solution (containing 1.1 × 10 ⁻⁷ mol as Pt alone) was added thereto, and the mixture was heated and stirred at 90 ° C. 49.3 g of H4Q shown below was added dropwise and aged at 90 ° C. for 3 hours. After confirming that the allyl group of the raw material was lost by ¹ H-NMR, the solvent and excess H4Q were distilled off under reduced pressure, and then activated carbon was treated to give a colorless transparent liquid. 46.4 g of perfluoropolyether was obtained.

Further, 30 g of the perfluoropolyether, 30 g of m-xylene hexafluoride, and 0.0223 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 5.6 × 10 ⁻⁸ moles as Pt alone) were heated to 90 ° C. Stirred. 5.76 g of trimethoxysilane was added dropwise, aged at 80 ° C. for 3 hours, and the solvent was distilled off under reduced pressure to obtain 33.7 g of a colorless transparent liquid (Compound 4). Its specific gravity was 1.71 and its refractive index was 1.327.

IR, NMR charts of Compound 3 are shown in FIGS. 7 and 8. In addition, ¹ H-NMR data of the obtained compound is shown below.

¹ H-NMR (in TMS, ppm)

From the above results, the structural formula of the obtained compound is

(Wherein p / q = 0.9, Mw ≒ 4000 to 6000).

&Lt; Synthesis Example 5 &

에 나타낸 한쪽 말단 퍼플루오로폴리에테르 대신에 합성예 4에서 사용한 양쪽 말단 퍼플루 오로폴리에테르를 사용한 것 이외에는, 합성예 1과 동일한 방법으로 하기에 나타낸 화합물 5를 얻었다. 이것의 비중은 1.72, 굴절률은 1.330이었다.In the compound used by the synthesis example 2,

Compound 5 shown below was obtained in the same manner as in Synthesis Example 1, except that both terminal perfluoropolyethers used in Synthesis Example 4 were used instead of one terminal perfluoropolyether shown in. Its specific gravity was 1.72 and the refractive index was 1.330.

IR, NMR charts of Compound 5 are shown in FIGS. 9 and 10. In addition, ¹ H-NMR data of the obtained compound is shown below.

¹ H-NMR (in TMS, ppm)

From the above results, the structural formula of the obtained compound is

Was found to be.

<Reference Examples 1 to 3 and Examples 1 and 2>

The perfluoropolyether modified silanes synthesized in Synthesis Examples 1 to 5 were dissolved in HFE7200, and 0.1 wt% solution was prepared and used as a treatment agent. After the antireflection film (8 x 15 x 0.2 cm) was immersed in the treatment agent for 10 seconds, the resultant was pulled up at a speed of 150 mm / min and left for 24 hours in an atmosphere of 25 ° C and 40% humidity to form a cured film. The following (1) (2) evaluation was performed using this sample piece.

&Lt; Comparative Examples 1 and 2 >

Instead of the perfluoro modified silanes of the compounds 4 and 5 used in the examples, the same evaluation as in the examples was carried out except that the following compounds 6 and 7 were used.

Compound 6

Compound 7

Where p / q = 0.9 and Mw M4000 to 6000

The evaluation results are shown in Table 1 below.

All the Examples were very excellent in scratch resistance compared with Comparative Examples 1 and 2. In addition, compounds 1, 4 and 5 had equivalent or more water / oil repellency.

From the above, the perfluoropolyether modified silane shown in this invention forms a firm film on the surface of a base material, and can be applied as a surface treating agent excellent in water / oil repellency, mold release property, etc.

According to the silane of the present invention, a cured film excellent in water / oil repellency and antifouling property can be provided, and can be effectively used for various coating applications over a long period of time.

Claims (9)

The perfluoropolyether modified silane represented by following formula (1). &Lt; Formula 1 >

Wherein Rf is a divalent perfluoropolyether group, Q is an Rf group and Z, which may or may not include one or more bonds selected from the group consisting of amide bonds, ether bonds, ester bonds, and vinyl bonds. Is a hydrocarbon group of 2 to 12 carbon atoms connecting Z, Z is a linear, cyclic or branched organopolysiloxane having 3 or more siloxane bonds and containing or without a -CH ₂ CH ₂ -group. R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, each X is independently a hydrolyzable group selected from the group consisting of an alkoxy group, an oxyalkoxy group, an acyloxy group, an alkenyloxy group, and a halogen group. 2 or 3, b is 2-10, (alpha) is 2 and c is an integer of 1-5. The compound of claim 1, wherein Rf in formula (I) is a repeating unit of a linear or branched perfluoroether group of -C _g F _2g O-, wherein each unit of g is independently an integer of 1 to 6. A perfluoropolyether modified silane, consisting of a divalent group comprising a perfluoroether structure represented by the formula (C _g F _2g O) _{h wherein} h is an integer from 1 to 500. delete The perfluoropolyether-modified silane according to claim 1, wherein Rf in the formula (1) is a perfluorooxyalkylene group selected from the group represented by the following formulas (5), (6) and (7). &Lt; Formula 5 >

(Wherein each Y is independently an F or CF ₃ group, r is an integer from 2 to 6, d is an integer from 1 to 3, m, n are each an integer from 0 to 200, and m + n is 2 to 200, s is an integer of 0 to 6, the arrangement of repeating units in the formula is random.) (6)

(Wherein l is an integer of 1 to 200 and d is an integer of 1 to 3). &Lt; Formula 7 >

(Wherein Y is an F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, m + n is 2 to 200, and the arrangement of repeating units in the formula Is random.) The perfluorine according to any one of claims 1, 2, and 4, wherein in the formula (1), Q is a linking group of the Rf group and the Z group, and is a group containing amide, ether, ester, and vinyl bonds. Ropolyether modified silanes. The perfluoropolyether-modified silane according to any one of claims 1, 2, and 4, wherein the hydrolyzable group X is an alkoxy group. The perfluoropolyether modified silane according to any one of claims 1, 2 and 4, wherein the alkoxy equivalent is in the range of 7 to 30. The surface treating agent containing the perfluoroether modified silane and / or its partial hydrolysis-condensate as described in any one of Claims 1, 2, and 4 as a main component. An article having a cured coating on the surface of the perfluoroether-modified silane according to any one of claims 1, 2, and 4 and / or its partially hydrolyzed condensate as a main component.

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