JP2023080075A - Curable composition and cured film thereof - Google Patents

Abstract

To provide a thermosetting composition capable of forming a protective layer that exhibits excellent wear resistance especially even when used outdoors.SOLUTION: The present invention relates to a thermosetting composition including the following components of (1) a perfluoropolyether group-containing alkoxysilane and (2) an alkoxysilane containing two or more trialkoxysilyl groups (excluding the alkoxysilane of (1)).SELECTED DRAWING: None

Description

The present invention relates to a novel curable composition and its cured film.

Optical products such as various lightings, lenses, displays, indicators, and accessories such as their covers must have a surface that is imparted with antifouling, water repellency, abrasion resistance, etc., so that their optical characteristics can be maintained over a long period of time. has been processed.

Various chemical and physical means have been employed for surface treatment, but a method of applying a coating agent to a base material (object to be coated) is widely used from the viewpoint of its simplicity and the like. Recently, various coating agents using perfluoropolyether group-containing materials have been proposed. For example, surface treatment agents containing perfluoropolyether group-containing silane compounds represented by specific chemical formulas are known (Patent Documents 1 to 3).

JP 2020-90652 A JP 2018-172655 A International publication WO2018/79743

However, although these conventional surface treatment agents exhibit good properties in terms of water repellency, antifouling properties, abrasion resistance, etc., further improvements are required. In other words, perfluoropolyether group-containing materials are designed mainly for the purpose of protecting touch panels of smartphones, tablet terminals, etc., and are capable of obtaining sufficient properties under such conditions of use. There is no guarantee that water repellency, stain resistance, abrasion resistance, etc. can be obtained under other usage conditions (especially outdoors where it is exposed to dust, dust, etc.).

For example, outdoor security cameras, weather observation cameras, river surveillance cameras, cameras mounted on vehicles and ships, outdoor lighting (street lights, parking lots, stadiums, etc.), or covers for these, etc., may be exposed to dust, dust, etc. for a long period of time. It is necessary to be able to withstand these because it will be exposed to For such applications, even if a protective layer is formed by applying a surface treatment agent containing a conventional perfluoropolyether group-containing silane compound, collisions with particles such as dust and dust (such as sand grains) are repeated. As a result, the protective layer is worn out, and as a result, there is a possibility that the original optical characteristics of the illumination, lenses, etc. are degraded. Therefore, there is a demand for the development of a protective layer that can be effectively protected even in such an environment.

SUMMARY OF THE INVENTION Accordingly, it is a primary object of the present invention to provide a thermosetting composition capable of forming a protective layer exhibiting excellent abrasion resistance even when used outdoors.

As a result of intensive research in view of the problems of the prior art, the present inventors have found that the above objects can be achieved by adopting a composition having a specific composition, and have completed the present invention.

That is, the present invention relates to the following thermosetting composition and its cured film.
1. Ingredients:
(1) a perfluoropolyether group-containing alkoxysilane, and (2) an alkoxysilane containing two or more trialkoxysilyl groups (excluding the alkoxysilane of (1) above).
A thermosetting composition comprising:
2. 2. The thermosetting composition according to item 1, wherein the alkoxysilane (1) has a number average molecular weight of 3000 or more.
3. wherein the trialkoxysilyl groups in the alkoxysilane (2) are the same or different and are represented by the general formula —Si(OC _n H _2n+1 ) ₃ (where n is an integer of 1 to 3); 3. The thermosetting composition according to Item 1 or 2.
4. In the alkoxysilane of (2) above, two or more trialkoxysilyl groups are bonded to each other through an organic group containing an alkylene group in which some or all of the hydrogen atoms may be substituted with fluorine atoms. , the thermosetting composition according to any one of the above items 1 to 3.
5. 5. The thermosetting composition according to claim 4, wherein said organic group has an isocyanuric ring skeleton.
6. 6. The thermosetting composition according to any one of Items 1 to 5, which contains 50 to 300 parts by mass of the alkoxysilane of (2) with respect to 100 parts by mass of the perfluoropolyether group-containing alkoxysilane.
7. 7. The thermosetting composition according to any one of items 1 to 6, further comprising (3) an alkoxysilane containing one trialkoxysilyl group (excluding the alkoxysilane of (1) above).
8. 8. The thermosetting composition according to any one of items 1 to 7, further comprising (4) a tetraalkoxysilane hydrolyzed condensate.
9. 9. The thermosetting composition according to any one of Items 1 to 8, which further contains an organic solvent and is liquid.
10. A cured film obtained by curing the thermosetting composition according to any one of items 1 to 9 above.
11. 11. A laminate obtained by laminating the cured film according to item 10 on a substrate.
12. 11. An article in which the cured film according to item 10 is laminated on a substrate.
13. 11. An optical product in which the cured film according to item 10 is laminated on a substrate.
14. 14. The optical product according to item 13, which is used outdoors.

According to the present invention, it is possible to provide a thermosetting composition capable of forming a protective layer that can withstand outdoor use. The thermosetting composition of the present invention exhibits high resistance to wear due to collision with particles (sand grains, etc.) that constitute sand dust, dust, etc., due to the combination of two or three types of alkoxysilanes. , it is possible to maintain the abrasion resistance over a long period of time and, in turn, the water repellency, transparency, etc. of the cured film.

Conventional hardened films are designed mainly with increasing hardness in mind, but the higher the hardness, the greater the brittleness. , and cannot withstand collisions with particles such as dust. In particular, the cured film formed from an alkoxysilane compound contains silicon atoms as a constituent element, and dust and dust generally contain silicon atoms as the main component. The membrane is easily destroyed.

On the other hand, the cured film of the present invention is considered to have a certain degree of softness and suppleness, and is therefore expected to have a certain degree of durability against collisions with particles such as dust and dust. guessed. In particular, when an alkyl group or an alkylene group is introduced, higher wear resistance can be exhibited. Although the mechanism of action is not clear, the C—C bond enhances the flexibility and the like, thereby further reducing the brittleness. It is considered that higher wear resistance (collision resistance) is exhibited.

The thermosetting composition or its cured film of the present invention having such characteristics can not only be used as a protective film for optical products used indoors (indoors), but also is resistant to collisions with particles such as dust and dust. It can be suitably used as a protective film for optical products and the like that are likely to be used outdoors.

1. Thermosetting Composition The curable composition of the present invention (the composition of the present invention) comprises the following components:
(1) a perfluoropolyether group-containing alkoxysilane (first component), and (2) an alkoxysilane containing two or more trialkoxysilyl groups (excluding the alkoxysilane of (1) above) (second component)
characterized by comprising

A. Constituent Components of the Composition of the Present Invention First Component The first component, the perfluoropolyether group-containing alkoxysilane, mainly functions to impart good water and oil repellency, water slideability, abrasion resistance, etc. to the cured film. Fulfill.

In the present invention, the type of perfluoropolyether group-containing alkoxysilane is not particularly limited, but for example, the general formula A-PFPE-B (where PFPE represents a perfluoropolyether group, one or both of A and B , is an organic group having an alkoxysilyl group at the terminal, and if the terminal is not the organic group, it is an alkyl group in which some or all of the hydrogen atoms may be substituted with fluorine atoms.). can be used for In particular, in the present invention, from the viewpoint of film-forming properties, etc., it is desirable that A and B are the same or different organic groups having terminal alkoxysilyl groups.

The organic group having an alkoxysilyl group may be an alkoxysilyl group alone or may contain an alkoxysilyl group and another organic group. The alkoxysilyl group is not particularly limited, but usually a trialkoxysilyl group represented by the general formula —Si(OC _n H _2n+1 ) ₃ (where n is an integer of 1 to 3) is preferred. For example, a trimethoxysilane group, a triethoxysilane group, and the like can be mentioned.

When A or B is a single alkoxysilyl group, the structure is such that the alkoxysilyl group is directly linked to PFPE.

When A or B contains an alkoxysilyl group and another organic group, the structure is such that the alkoxysilyl group is bonded to PFPE via the other organic group. When an alkoxysilyl group and another organic group are included, the organic group having the alkoxysilyl group is particularly represented by the general formula —R ¹ —(OCONH) _m —R ² —R ³ (provided that R ¹ and R ² are the same as each other). or differently, a divalent hydrocarbon group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine, such as —(CH ₂ ) _n — (where n is 1 Integer of ~10), -(CF ₂ ) _n - (where n is an integer of 1 to 10), -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF(CF ₃ )-, - CF(CF ₃ )CH ₂ —, etc., R ³ represents an alkoxysilyl group, and m represents 0 or 1.) (specific organic group) can be preferably employed.

Here, the number of carbon atoms in R ¹ and R ² may be the same or different, preferably in the range of about 1 to 10, more preferably 1 to 6.

The above m is 0 or 1. That is, the specific organic group may or may not contain a urethane bond —OCONH—.

The alkoxysilyl group R ³ is not particularly limited, but usually a trialkoxysilyl group represented by the general formula —Si(OC _n H _2n+1 ) ₃ (where n is an integer of 1 to 3) is preferred. . For example, a trimethoxysilane group, a triethoxysilane group, and the like can be mentioned.

In the above A-PFPE-B, when A or B is not an organic group having an alkoxysilyl group at the end, an alkyl having 10 or less carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms It is preferably a group. Examples include organic groups such as CF ₃ —, CF ₃ CF ₂ —, CF ₃ CH ₂ —, CH ₃ —, CF ₃ CF ₂ CF ₂ —.

A perfluoropolyether group (PFPE) has a structure in which a plurality of -(C _x F _2x O) _m - (x and m are integers other than 0) are linked as a basic unit (unit). have. When m is 2 or more, each (C _x F _2x O) may be the same as or different from each other. In other words, the PFPE may have a structure consisting of repetitions of one type of unit alone, or may have a structure consisting of a combination of two or more different types of units. In addition, (C _x F _2x O) may have either a linear or branched carbon chain.

Examples of -(C _x F _2x O) - _which is a unit include CF ₂ O, CF ₂ CF ₂ O, CF 2 CF 2 CF ₂ O, CF ₂ CF ₂ CF _{2 CF 2 CF 2} O, CF (CF ₃ ) CF ₂ O and the like, but are not limited thereto. In particular, in the present invention, -(CF ₂ CF ₂ O) _m -(CF ₂ O) _n - (where m and n are integers other than 0) or the like can be suitably employed as PFPE. . In this case, m and n can be within the ranges of, for example, about 10 ≤ m ≤ 40 and 10 ≤ n ≤ 40. Not limited.

The number average molecular weight of the perfluoropolyether group-containing alkoxysilane, which is the first component, is not particularly limited, but is usually preferably 3000 or more, particularly more preferably 3000 to 8000, especially 3500 to 7000. is most preferred. By having such a molecular weight, more excellent effects can be obtained in terms of water and oil repellency, water slideability, wear resistance, and the like.

The method for measuring the number average molecular weight in the present invention is not particularly limited, and may be carried out by measurement by polymethyl methacrylate conversion using gel permeation chromatography, or by structural analysis using nuclear magnetic resonance. can be done.

As such a first component, a known or commercially available product can be used, and a compound synthesized by a known production method can also be used. As a commercially available product, for example, the product name "OPTOOL DSX" (manufactured by Daikin Industries, Ltd.) can be used.

When synthesizing the first component, for example, a method of bonding trialkoxysilyl groups to both ends or one end of a perfluoropolyether group can be employed. More specifically, a compound (starting compound) having a perfluoropolyether group as a main chain and an OH group as both terminal groups or one terminal group (starting compound) is reacted with an isocyanate group-containing alkoxysilane compound. , the first component can be suitably prepared. More specifically, the above-mentioned starting compound is represented by the general formula X-PFPE-Y (where PFPE represents a perfluoropolyether group, one or both of X and Y are hydroxyl groups, and X or Y is a hydroxyl group If not, it represents an alkyl group having 10 or less carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms.) can be preferably used.

Known or commercially available compounds can be used as the starting compounds. That is, a compound in which both terminal groups of a perfluoropolyether group are hydroxyl groups, a compound in which only one terminal group of a perfluoropolyether group is a hydroxyl group, or the like can be used either publicly known or commercially available.

Examples of commercially available products of compounds having hydroxyl groups at both ends of a perfluoropolyether group include product names "FLUOROLINK D-4000" and "FLUOROLINK D-6000" (both manufactured by Solvay Co., Ltd.). The "FLUOROLINK D-4000" and the "FLUOROLINK D-6000" have a basic structure represented by the following general formula (1).

Commercially available compounds in which only one terminal group of the perfluoropolyether group is a hydroxyl group include, for example, the product names "DOL-3000" and "DOL-4000" (both manufactured by Sinochem) and "PFPE KFE240AL" (Chemers Co., Ltd.) and the like can be used.

In the above starting compound, when one terminal group is a hydroxyl group, the terminal group at the other terminal may be an alkyl group having 10 or less carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms. Good luck. Examples include CF ₃ —, CH ₃ —, CF ₃ CH ₂ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ — and the like.

The isocyanate group-containing alkoxysilane compound may be any compound having an isocyanate group and an alkoxysilyl group, and known or commercially available compounds can also be used. As a commercially available product, for example, "KBE-9007N" (3-isocyanatopropyltriethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.) can be preferably used.

The production conditions are not particularly limited, but for example, a step of reacting a starting compound and an isocyanate group-containing alkoxysilane compound in a solvent at a temperature of 20 to 70 ° C. (reaction step) and a first component (object) from the reaction product liquid. can be carried out by a method including a step of recovering (recovery step).

In the reaction step, the charging ratio of the starting compound and the isocyanate group-containing alkoxysilane compound is not particularly limited, but can be appropriately set, for example, within the range of about 1:1 to 1:4 in terms of molar ratio.

Moreover, in the reaction step, a liquid phase reaction using a solvent may be carried out, and it is preferable to use a fluorinated solvent as the solvent. Hydrofluoroether-based solvents, for example, can be suitably used as fluorine-based solvents. Known or commercially available solvents can also be used as such solvents. For example, 1,3-bis(trifluoromethyl)benzene or the like can be used. Commercially available products such as "Novec HFE-7200" and "Novec HFE-7300" (both of which are products of 3M) can be preferably used.

The reaction step can also be carried out in the presence of a catalyst, if desired. As the catalyst, an alkaline catalyst can be preferably used, and among them, an organic alkaline catalyst of at least one of triethylamine, tributylamine, pyridine and 1,4-diazabicyclo[2.2.2]octane is particularly preferable.

In the recovery step, the method is not particularly limited as long as the first component, which is the target product, can be recovered (isolated). For example, a method of adding an alcohol (methanol, ethanol, etc.) to the reaction product liquid, separating the layers, and then removing the supernatant liquid (the upper layer of the reaction product liquid) can be employed. That is, since the first component generally settles in the reaction product liquid, it can be purified and separated by removing the supernatant liquid. The first component can be obtained with a higher yield by repeating a series of steps of adding the alcohol and removing the supernatant liquid a plurality of times. In this case, if necessary, the first component can be recovered as a solid content by performing decompression, drying, or the like.

The solid content of the first component in the composition of the present invention is not limited, but is usually 10 to 60% by mass, preferably 10 to 50% by mass, particularly 15 to 30% by mass. is more preferred. Thereby, excellent abrasion resistance and the like can be formed more reliably.

Second component Alkoxysilane containing two or more trialkoxysilyl groups, which is the second component, mainly reduces the brittleness of the cured film and absorbs the impact of collisions with particles such as dust and dust (such as grains of sand). It is used to provide high wear resistance by

The number of trialkylsilyl groups may be 2 or more, and may be, for example, 2, 3, or 4. Moreover, when using multiple types of second components, the number of the components may be the same as each other or may be different from each other. For example, a second component having two trialkylsilyl groups and a second component having three trialkylsilyl groups can be used together.

The trialkoxysilyl group in the second component is not limited, but is usually a trialkoxysilyl represented by the general formula —Si(OC _n H _2n+1 ) ₃ (where n is an integer of 1 to 3). groups can be preferably used. For example, a trimethoxysilane group, a triethoxysilane group, and the like can be mentioned.

In the second component, two or more trialkylsilyl groups are preferably bonded to each other via an organic group containing an alkylene group in which some or all of the hydrogen atoms may be substituted with fluorine atoms. .

Examples of the alkylene group include those having about 1 to 10 carbon atoms. _{For example , -CH2- , -CH2CH2- , CF2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2CH2CH2- , -CH2CH2CH _ _ 2CH 2} CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CF ₂ CF ₂ CF ₂ - and the like. A carbon atom of the alkylene group is preferably directly bonded to a silicon atom of the trialkylsilyl group.

Examples of the organic group include an organic group composed only of the above alkylene group, and an organic group in which the above alkylene group is bonded to a cyclic skeleton. Examples of the cyclic group include an isocyanuric ring skeleton, a cyclohexyl ring skeleton, a benzene ring skeleton and the like.

Specific examples of the second component include 1,6 bis-(trimethoxysilyl)hexane, bis(trimethoxysilyl)ethylene, tris(trimethoxysilylpropyl)isocyanurate and the like.

The bistrimethoxysilylethylene is represented by the following general formula (2). The 1,6 bis(trimethoxysilyl)hexane is represented by the following general formula (3). The above tris(trimethoxysilylpropyl)isocyanurate is represented by the following general formula (4). In addition, each Me in the following formula represents a methyl group.

Known or commercially available compounds can be used for these compounds. As commercially available products, for example, product names such as “KBM-3066” and “KBM-9659” (both manufactured by Shin-Etsu Silicone Co., Ltd.) can be used.

The solid content of the second component in the composition of the present invention is not particularly limited. It is preferably 40% by mass.

The second component excludes the perfluoropolyether group-containing alkoxysilane, which is the first component. That is, the second component is composed of a compound containing no perfluoropolyether group.

Third Component In the present invention, an alkoxysilane containing one trialkoxysilyl group may be included as a third component, if necessary. The alkoxysilane containing one trialkoxysilyl group, which is the third component, mainly has the function of imparting good film-forming properties, curability, and the like.

The alkoxysilane _is not particularly ^limited as long ^as it has one trialkoxysilyl group ^. represents an alkyl group which may be partially or wholly substituted with fluorine atoms, and R ⁵ represents an alkyl group having 1 to 3 carbon atoms.) can be preferably used. More specifically, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, 3,3,3-trifluoropropyltrisilane. methoxysilane and the like.

Known or commercially available products can also be used for these. Commercial products include, for example, product names "KBE-3083", "KBE-13", "KBM-3033", "KBE-3033", "KBE-3083", and "KBM-7103" (all manufactured by Shin-Etsu Silicone Co., Ltd. ) etc. can be mentioned.

The solid content of the third component in the composition of the present invention is not particularly limited, but is usually about 0 to 60% by mass, preferably 25 to 60% by mass, and preferably 30 to 60% by mass. More preferably, it is most preferably 40 to 50% by mass. This makes it possible to obtain excellent scratch resistance and the like more reliably.

The third component excludes the perfluoropolyether group-containing alkoxysilane, which is the first component. That is, the third component is composed of a compound containing no perfluoropolyether group.

In addition, the ratio of the first component to the third component is not limited, but in particular, the second component is 50 to 300 parts by mass and the third component is 0 to 300 parts by mass with respect to 100 parts by mass of the first component. is preferable, more preferably 50 to 300 parts by mass of the second component and 100 to 300 parts by mass of the third component, particularly 100 to 200 parts by mass of the second component and 200 parts by mass of the third component with respect to 100 parts by mass of the first component It is most preferably ∼250 parts by mass.

Fourth Component In the present invention, a tetraalkoxysilane hydrolysis condensate (silicate oligomer) can be contained as a fourth component, if necessary. By blending the tetraalkoxysilane hydrolyzed condensate, film-forming properties, curability, hardness, etc. can be enhanced.

The hydrolytic condensate of tetraalkoxysilane is not particularly limited, and examples thereof include compounds produced by hydrolysis and polycondensation reaction of two or more molecules of tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane. Depending on the number of molecules to be polycondensed, there are, for example, dimers, trimers, tetramers, etc. In the present invention, 2 to 10 mers (average value) can be preferably used.

Such compounds can be known or commercially available, and can also be synthesized by known production methods. Examples of commercially available products include product names "Methyl Silicate 51" and "Methyl Silicate 53A" (both manufactured by Colcoat Co., Ltd.).

The solid content of the fourth component in the composition of the present invention is not particularly limited. It is preferably 15% by mass.

Other Components In addition to the first component to the fourth component, the composition of the present invention may optionally contain other components as long as the effects of the present invention are not impaired. Examples thereof include solvents described later, inorganic fine particles (fine oxide particles such as silica, alumina, titania, and zirconia), colorants, and the like.

B. Properties, etc. of the Composition of the Present Invention Although the form of the composition of the present invention is not particularly limited, it is usually a liquid. In order to make it liquid, a solvent may be added, but either a solution or a dispersion may be used.

The solvent can be appropriately set according to the type of the first component and the like. For example, at least one of fluorine-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, and amide-based solvents can be used.

Examples of fluorine-based solvents include trifluorotoluene, perfluorobutylmethylether, perfluorobutylethylether, and meta-xylene hexafluoride.

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.

Examples of ester solvents include ethyl acetate, butyl acetate, methoxybutyl acetate, methoxypropyl acetate and the like.

Examples of alcohol solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol) and the like.

The amount of the organic solvent used is, for example, such that the solid content of the composition of the present invention is in the range of about 0.1 to 10% by weight (preferably about 0.1 to 5% by weight). type, desired viscosity, etc., but is not limited to this.

C. Manufacture of the composition of the present invention The composition of the present invention can be prepared by uniformly mixing the components as described above. There are no particular restrictions on the mixing order and the like when mixing, and any order can be adopted. In particular, when preparing a liquid composition, a solvent may be mixed with the first component and the like. Mixing can be carried out using known or commercially available devices such as mixers and kneaders. In addition, the atmosphere for mixing is not limited to this, although each component may be mixed under normal temperature and normal pressure.

D. Use of the Composition of the Present Invention A desired cured film can be formed by curing the coating film of the composition of the present invention. That is, from the composition of the present invention, it is possible to more reliably obtain a protective layer that is resistant to scratches and the like even outdoors.

The cured film may be transparent, translucent or opaque. In particular, when used as a protective layer for lighting, lenses, or covers for these, the cured film is desirably transparent or translucent. Although the transparency in this case is not limited, it is usually desirable to have a haze value of about 0.1 to 5%.

The thickness of the cured film can be appropriately set according to the application, the site of use, etc., but it is usually about 0.05 to 2 μm, preferably 0.1 to 0.5 μm.

The method for forming the cured layer is not particularly limited. For example, it is preferably carried out by a method comprising the steps of a) forming a coating film of the composition of the present invention on a substrate and b) curing the coating film. can.

The substrate that serves as the base (lower layer) of the cured layer is not particularly limited, and may be, for example, synthetic resin, rubber, ceramics, glass, metal, or the like. In particular, transparent substrates such as glass and synthetic resins (polyester-based resins, acrylic-based resins, etc.) can be preferably used. Also, the base material may be, for example, a raw material, a semi-finished product, a finished product, or the like.

The method of forming the coating film of the composition of the present invention can be appropriately carried out by known coating methods such as doctor blade method, bar coating method, dipping method, air spray method, roller brush method, roller coater method, and vapor deposition method. can be done.

The amount of the coating film to be formed may be, for example, an amount that provides the desired thickness of the cured film. range) can be set as appropriate.

Prior to curing, the obtained coating film may be subjected to a drying step, if necessary. The drying method may be natural drying or heating at a temperature of about 60 to 120°C.

Then, the coating film is cured. In the present invention, the coating film is cured by heating (thermosetting). The conditions for heat curing may be appropriately set according to the type of the first component, etc., but it is usually preferable to set them at about 50 to 200° C. (especially 120 to 180° C.) in the atmosphere. The heating time may be a time sufficient to cure the coating film, and can be set, for example, within the range of 0.1 to 2 hours, but is not limited thereto.

Furthermore, in the present invention, a laminate in which a cured film is laminated on a substrate can be obtained by a method comprising a step of forming a coating film of the composition of the present invention on a substrate and a step of curing the coating film. . Such laminates can also be used, for example, as materials for various products.

2. Goods (optical products)
The present invention includes articles (particularly optical products) in which the cured film of the present invention is laminated on a substrate. In particular, the cured film of the present invention has durability not only against rubbing between substances, but also against abrasion caused by collisions with particles such as dust and dust (scattered grains of sand, etc.). It can be applied as a protective layer. In particular, it can be suitably used as a protective layer for substrates (products) that are exposed to dust, dust and the like.

Therefore, the cured film of the present invention can be applied as a protective layer (outermost layer) for illumination, lenses, or covers used indoors, as well as for illumination, lenses, or covers used outdoors. . For example, a) outdoor security cameras, weather observation cameras, river surveillance cameras, cameras mounted on vehicles and ships, outdoor lighting (street lights, parking lots, stadiums, etc.), or b) lenses used for these (lighting lenses for cameras or lenses for cameras), c) covers for illumination or lenses, etc. In addition, it can also be used as a protective layer for smartphone screens, tablet screens, etc.

The method of applying the cured film of the present invention to these articles (especially optical products) includes, for example, the step of forming a coating film of the composition of the present invention on the surface of a substrate to be protected as described above, followed by curing. Examples include, but are not limited to, a method of forming a predetermined cured film (protective layer) by a method.

EXAMPLES Examples and comparative examples are shown below to describe the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples.

Example 1
As shown in Table 1, in a 200 mL beaker, 0.20 g of perfluoropolyether group-containing alkoxysilane (Production Example 1), alkoxysilane containing one trialkoxysilyl group (product name "KBM-7103", Shin-Etsu Chemical Co., Ltd. 0.5 g of bistrimethoxysilylethylene, 0.2 g of bistrimethoxysilylethylene, 0.1 g of hydrolyzed condensate of tetramethoxysilane (product name: "Methyl Silicate 51" manufactured by Colcoat, average tetramer), 0.1 g of fluorine-based solvent (product name: "Novec HFE-7200" (manufactured by 3M) 99.0 g was weighed and stirred at room temperature for 1 hour to obtain a liquid composition. The liquid composition was applied to a washed glass plate and placed in an oven at 170°C. The composition was heat-cured for 30 minutes to prepare a cured film having a thickness of about 0.2 μm.

Examples 2-12 and Comparative Examples 1-4
A liquid composition was prepared in the same manner as in Example 1, except that the composition was changed to that shown in Table 1. A cured film was prepared in the same manner as in Example 1 using the above liquid composition.

The abbreviations in Table 1 have the following meanings.
(1) First component: Perfluoropolyether group-containing alkoxysilane "Production example 1": Perfluoropolyether group-containing alkoxysilane 1 synthesized in <Production example 1> below
<Production Example 1>
In a 30 mL eggplant flask containing a stirrer, 18.0 g (3.0 mmoL) of a perfluoropolyether compound containing a hydroxyl group (product name “FLUOROLINK D-6000” (manufactured by Solvay Corporation, average molecular weight 6000) and 3-isocyanatopropyltri 1.48 g (7.2 mmoL) of methoxysilane (manufactured by Kanto Chemical Co., Ltd.), 0.015 g (0.15 mmoL) of triethylamine (manufactured by Kanto Chemical Co., Ltd.), and 18.0 g of meta-xylene hexafluoride were weighed. The liquid was stirred for 6 hours at 50° C. Methanol was added to the reaction liquid after the reaction, and the reaction liquid was separated into layers.Since the lower layer was the target product, the solvent in the upper layer was removed.Using methanol, three washing steps were performed. The product was placed in an eggplant flask and dried under reduced pressure to remove the solvent and synthesize the target perfluoropolyether group-containing alkoxysilane 1 (yield 90%, 17.3 g). .
・ “Production Example 2”: Perfluoropolyether group-containing alkoxysilane 2 synthesized in <Production Example 2> below
<Production Example 2>
In a 30 mL eggplant flask containing a stirrer, 12.0 g (3.0 mmoL) of a perfluoropolyether compound containing a hydroxyl group (product name “FLUOROLINK D-4000” (manufactured by Solvay Corporation, average molecular weight 4000) and 3-isocyanatopropyltri 1.48 g (7.2 mmoL) of methoxysilane (manufactured by Kanto Chemical Co., Ltd.), 0.015 g (0.15 mmoL) of triethylamine (manufactured by Kanto Chemical Co., Ltd.), and 12.0 g of meta-xylene hexafluoride were weighed. The liquid was stirred for 6 hours at 50° C. Methanol was added to the reaction liquid after the reaction, and the reaction liquid was separated into layers.Since the lower layer was the target product, the solvent in the upper layer was removed.Using methanol, three washing steps were performed. The product was placed in an eggplant flask and dried under reduced pressure to remove the solvent and synthesize the target perfluoropolyether group-containing alkoxysilane 2 (yield 87%, 10.2 g). .
・ “Production Example 3”: Perfluoropolyether group-containing alkoxysilane 3 synthesized in <Production Example 3> below
<Production Example 3>
A hydroxy-containing perfluoropolyether compound (product name “DOL-3000” manufactured by Sinochem, average molecular weight 3000) (4.0 mmol, 12 g), 3-isocyanatopropyltrimethoxysilane (4. 8 mmol, 0.99 g), triethylamine (0.20 mmol, 0.020 g), and 12.0 g of meta-xylene hexafluoride were weighed. The reaction was stirred at 50° C. for 6 hours. Methanol was added to the reaction solution after the reaction to separate the layers of the reaction. Since the lower layer was the target product, the solvent in the upper layer was removed. The washing step with methanol was repeated three times. The product was placed in an eggplant flask and dried under reduced pressure to remove the solvent, thereby synthesizing the target perfluoropolyether-containing alkoxysilane 3 (yield 90%, 11.5 g).
(2) Second component: Alkoxysilane containing two or more trialkoxysilyl groups "Raw material A": bis(trimethoxysilyl)ethylene "Raw material B": 1,6-bis(trimethoxysilyl)hexane "Raw material C": Shin-Etsu Silicone Co., Ltd. "KBM-9659" (tris (trimethoxysilylpropyl) isocyanurate)
(3) Third component: Alkoxysilane containing one trialkoxysilyl group "KBM-7103": Shin-Etsu Silicone Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane)
・n-Pro-Si(OMe) ₃ : CH ₃ CH ₂ CH ₂ —Si(OMe) ₃ (Me is a methyl group)
・_{C6F13Si : CF3CF2CF2CF2CF2CF2 -} Si(OMe) ₃ (Me is _{a methyl} group)
(4) Fourth component: tetraalkoxysilane hydrolysis condensate "MS-51": "Methylsilicate 51" manufactured by Colcoat (tetramethoxysilane hydrolysis condensate (average tetramer))
(5) Solvent "Novec HFE-7200" (manufactured by 3M) (fluorine-based solvent)

Test example 1
The water repellency of the cured films prepared in Examples and Comparative Examples was examined. More specifically, the contact angle (initial) of the cured film to water was measured at 25°C. The water contact angle was measured using a contact angle measuring device (product name “DropMaster 700” manufactured by Kyowa Interface Chemical Co., Ltd.) (the same applies to the following tests). Table 2 shows the results.

Test example 2
For the cured films produced in Examples and Comparative Examples, water repellency against water was measured after carrying out a predetermined abrasion test.
The wear test was carried out using an ultrasonic cleaner as follows. A dispersion in which 10% by mass of Kanto loam (JIS test powder 1, eight types) was dispersed in water was used, and the dispersion was placed in a stainless steel container (SUS container). Then, the test piece (hardened film-attached glass plate) was placed in the SUS container. The SUS container was placed in a commercially available ultrasonic cleaner, the ultrasonic cleaner was operated, and the dispersion was irradiated with ultrasonic waves to treat the test piece. By treating the test piece in this way, the Kanto loam rocks violently due to the shock wave generated by the bursting of vacuum bubbles generated in the dispersion liquid by ultrasonic waves, and the Kanto loam collides with the test piece. It can damage the specimen. The ultrasonic conditions were a frequency of 28 kHz and an output of 600W. After 8 hours of irradiation, the test piece was collected, washed with pure water, and dried naturally. The contact angle of water with respect to the cured film thus obtained after the test was measured. Table 2 shows the results.

Test example 3
A steel wool resistance test was performed on each specimen. The water contact angle was measured after rubbing the cured film surface of the test piece with steel wool (#0000) 300 times (load: 1000 g). Table 2 shows the results.

From the comparison between Example 1 and Comparative Example 1 in Table 2, it can be seen that when the first component and the second component are not contained, the drop in liquid repellency in the abrasion test is greater. In particular, from the comparison between Examples 1 to 5 and Comparative Examples 2 to 4, it can be seen that when the second component is not contained, the drop in liquid repellency in the abrasion resistance test becomes greater.

As described above, in the present invention, a film having a film thickness of at least about 0.2 μm and containing a certain amount of polysubstituted alkoxysilane having an alkyl chain, in addition to Si—O—Si bonds, particularly C—C bonds are formed. By introducing it, the brittleness of the cured film is reduced, and it becomes possible to increase the durability against wear accompanying impact with particles.

Example 13
As shown in Table 3, a 200 mL beaker was charged with 0.60 g of perfluoropolyether group-containing alkoxysilane (manufacturing example 4), 0.3 g of bistrimethoxysilylethylene, and a tetramethoxysilane hydrolysis condensate (product name: "methylsilicate 51"). Colcoat Co., Ltd., average tetramer) 0.1 g and 99.0 g of a fluorine-based solvent (product name "Novec HFE-7200" (manufactured by 3M) were weighed and stirred for 1 hour at room temperature to obtain a liquid composition. The liquid composition was applied to a washed glass plate and cured by heating in an oven at 170° C. for 30 minutes to prepare a cured film having a thickness of about 0.2 μm.

Examples 14-16 and Comparative Example 5
A liquid composition was prepared in the same manner as in Example 13, except that the composition was changed to that shown in Table 3. A cured film was prepared in the same manner as in Example 1 using the liquid composition.

The abbreviations in Table 3 have the following meanings.
(1) First component: Perfluoropolyether group-containing alkoxysilane "Production example 4": Perfluoropolyether group-containing alkoxysilane 1 synthesized in <Production example 4> below
<Production Example 4>
A hydroxy-containing perfluoropolyether compound (product name “DOL-3000” manufactured by Sinochem, average molecular weight 3000 (6.0 mmol, 18.0 g), 3-isocyanatopropyltrimethoxysilane (7 .2 mmol, 1.48 g), triethylamine (0.30 mmol, 0.030 g), and 18.0 g of meta-xylene hexafluoride were weighed in. The reaction solution was stirred for 6 hours at 50° C. Methanol was added to the reaction solution after the reaction. The reaction was separated into layers.Since the lower layer was the target product, the solvent in the upper layer was removed.The washing process using methanol was repeated three times.The product was placed in an eggplant flask and dried under reduced pressure. The solvent was removed to synthesize the target perfluoropolyether-containing alkoxysilane 4 (yield 90%, 17.3 g).
・ “Production Example 5”: Perfluoropolyether group-containing alkoxysilane 2 synthesized in <Production Example 5> below
<Production Example 5>
A hydroxy-containing perfluoropolyether compound (product name “DOL-4000” manufactured by Sinochem, average molecular weight 4000 (3.0 mmol, 12.0 g), 3-isocyanatopropyltrimethoxysilane (3 .6 mmol, 0.74 g), triethylamine (0.15 mmol, 0.015 g), and 12.0 g of meta-xylene hexafluoride were weighed in. The reaction solution was stirred for 6 hours at 50° C. Methanol was added to the reaction solution after the reaction. The reaction was separated into layers.Since the lower layer was the target product, the solvent in the upper layer was removed.The washing process using methanol was repeated three times.The product was placed in an eggplant flask and dried under reduced pressure. The solvent was removed to synthesize the target perfluoropolyether-containing alkoxysilane 5 (yield 87%, 10.2 g).
(2) Second component: Alkoxysilane containing two or more trialkoxysilyl groups "Raw material A": bis(trimethoxysilyl)ethylene "Raw material B": 1,6-bis(trimethoxysilyl)hexane "Raw material C": Shin-Etsu Silicone Co., Ltd. "KBM-9659" (tris (trimethoxysilylpropyl) isocyanurate)
(3) Third component: Alkoxysilane containing one trialkoxysilyl group "KBM-7103": Shin-Etsu Silicone Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane)
(4) Fourth component: tetraalkoxysilane hydrolysis condensate "MS-51": "Methylsilicate 51" manufactured by Colcoat (tetramethoxysilane hydrolysis condensate (average tetramer))
(5) Solvent "Novec HFE-7200" (manufactured by 3M) (fluorine-based solvent)

Test example 4
In the same manner as in Test Example 1, the water repellency of the cured films prepared in Examples and Comparative Examples was examined. Table 4 shows the results.

Test example 5
In the same manner as in Test Example 2, the water repellency of the cured films prepared in Examples and Comparative Examples was measured after a predetermined abrasion test. Table 4 shows the results.

Test example 6
In the same manner as in Test Example 3, each test piece was subjected to a steel wool resistance test. Table 4 shows the results.

From the comparison between Example 16 and Comparative Example 5, it can be seen that the ultrasonic abrasion resistance is lowered when the polysubstituted alkyl chain-containing alkoxysilane is not contained.
In addition, the film thickness is about 0.2 μm, and by containing a certain amount of polysubstituted alkoxysilane having an alkyl chain, an alkyl chain bond can be introduced in addition to the Si—O—Si bond. , the brittleness of the cured film is reduced, and the wear resistance in the Kanto loam is improved.

Claims (14)

Ingredients:
(1) a perfluoropolyether group-containing alkoxysilane, and (2) an alkoxysilane containing two or more trialkoxysilyl groups (excluding the alkoxysilane of (1) above).
A thermosetting composition comprising: 2. The thermosetting composition according to claim 1, wherein the alkoxysilane (1) has a number average molecular weight of 3,000 or more. The trialkoxysilyl groups in the alkoxysilane (2) are the same or different and are represented by the general formula —Si(OC _n H _2n+1 ) ₃ (where n is an integer of 1 to 3). 3. The thermosetting composition according to Item 1 or 2. In the alkoxysilane of (2) above, two or more trialkoxysilyl groups are bonded to each other through an organic group containing an alkylene group in which some or all of the hydrogen atoms may be substituted with fluorine atoms. , The thermosetting composition according to any one of claims 1 to 3. 5. The thermosetting composition according to claim 4, wherein said organic group has an isocyanuric ring skeleton. The thermosetting composition according to any one of claims 1 to 5, comprising 50 to 300 parts by mass of the alkoxysilane of (2) with respect to 100 parts by mass of the perfluoropolyether group-containing alkoxysilane. The thermosetting composition according to any one of claims 1 to 6, further comprising (3) an alkoxysilane containing one trialkoxysilyl group (excluding the alkoxysilane of (1) above). The thermosetting composition according to any one of claims 1 to 7, further comprising (4) a tetraalkoxysilane hydrolysis condensate. The thermosetting composition according to any one of claims 1 to 8, which further contains an organic solvent and is liquid. A cured film obtained by curing the thermosetting composition according to any one of claims 1 to 9. A laminate obtained by laminating the cured film according to claim 10 on a substrate. An article obtained by laminating the cured film according to claim 10 on a substrate. An optical product obtained by laminating the cured film according to claim 10 on a substrate. 14. The optical product according to claim 13, which is used outdoors.