Sclerotic composition and its sclerotic film

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

Technical Field

[0001] The present invention relates to a novel curable composition and a cured film thereof.

Background Art

[0002] For optical products such as various lighting devices, lenses, displays, indicators, etc., or accessory parts such as covers thereof, surface treatments are applied to impart antifouling properties, water repellency, abrasion resistance, etc. so that their optical properties can be maintained over a long period.

[0003] For surface treatments, various chemical and physical means are employed, but from the viewpoint of simplicity, etc., a method of applying a coating agent to a substrate (coated object) is widely used. Recently, in particular, coating agents using materials containing perfluoropolyether groups have been variously proposed. For example, a surface treatment agent containing a perfluoropolyether group-containing silane compound represented by a specific chemical formula is known (Patent Documents 1 to 3).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, although these conventional surface treatment agents exhibit good properties in terms of water repellency, stain resistance, abrasion resistance, etc., further improvement is necessary. That is, the perfluoropolyether group-containing material is mainly designed for the protection of touch panels of smartphones, tablet terminals, etc., and sufficient properties can be obtained under such usage conditions. However, 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, powder, etc.).

[0006] For example, in outdoor security cameras, weather observation cameras, river monitoring cameras, cameras mounted on vehicles and ships, outdoor lighting (streetlights, parking lots, stadiums, etc.), or their covers, etc., they will be exposed to dust, powder, etc. over a long period of time, so it is necessary to withstand these. For such applications, even if a surface treatment agent containing a conventional perfluoropolyether group-containing silane compound is applied to form a protective layer, the protective layer will wear out due to repeated collisions with particles (such as sand grains) of dust, powder, etc., resulting in the deterioration of the original optical properties of lighting, lenses, etc. Therefore, the development of a protective layer that can effectively protect even in such an environment is required.

[0007] Therefore, the main object of the present invention is to provide a thermosetting composition capable of forming a protective layer that exhibits excellent abrasion resistance especially for outdoor use.

Means for Solving the Problems

[0008] As a result of intensive research in view of the problems of the prior art, the present inventor has found that the above object can be achieved by adopting a composition having a specific composition, and has completed the present invention.

[0009] That is, the present invention relates to the following thermosetting composition and its cured film. 1. The following components: (1) A perfluoropolyether group-containing alkoxysilane, and (2) An alkoxysilane containing two or more trialkoxysilyl groups (however, excluding the alkoxysilane of (1) above). A thermosetting composition characterized by containing the same. 2. The thermosetting composition according to item 1 above, wherein the number average molecular weight of the alkoxysilane of (1) above is 3000 or more. 3. In the alkoxysilane of (2) above, the trialkoxysilyl groups are the same as or different from each other and are represented by the general formula -Si(OC n H 2n+1 )3 (however, n represents an integer from 1 to 3). The thermosetting composition according to item 1 or 2 above. 4. In the alkoxysilane of (2) above, two or more trialkoxysilyl groups are bonded to each other via an organic group containing an alkylene group in which part or all of the hydrogen atoms may be substituted with fluorine atoms. The thermosetting composition according to any one of items 1 to 3 above. 5. The thermosetting composition according to claim 4, wherein the organic group has an isocyanuric ring skeleton. 6. The thermosetting composition according to any one of items 1 to 5 above, containing 50 to 300 parts by mass of the alkoxysilane of (2) above with respect to 100 parts by mass of the perfluoropolyether group-containing alkoxysilane. 7. The thermosetting composition according to any one of items 1 to 6 above, further containing (3) an alkoxysilane containing one trialkoxysilyl group (however, excluding the alkoxysilane of (1) above). 8. The thermosetting composition according to any one of items 1 to 7 above, further containing (4) a tetraalkoxysilane hydrolysis condensate. 9. The thermosetting composition according to any one of items 1 to 8 above, further containing an organic solvent and being in a liquid state. 10. A cured film obtained by curing the thermosetting composition according to any one of items 1 to 9 above. 11. A laminate obtained by laminating the cured film according to item 10 above on a substrate. 12. An article obtained by laminating the cured film according to item 10 above on a substrate. 13. An optical product obtained by laminating the cured film according to item 10 above on a substrate. 14. The optical product according to item 13, which is used outdoors.

Advantages of the Invention

[0010] 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 shows high resistance to abrasion caused by collisions with particles (such as sand grains) constituting dust, powder, etc. due to the combination of two or three types of alkoxysilanes. Therefore, it is possible to maintain long-term abrasion resistance, and thus the water repellency, transparency, etc. of the cured film.

[0011] Conventional cured films are mainly designed with the idea of increasing hardness. However, when the hardness is high, the brittleness is amplified accordingly. Therefore, even if they have a certain degree of abrasion resistance, they cannot withstand collisions with particles such as dust and powder. In particular, cured films formed from alkoxysilane compounds contain silicon atoms as constituent elements. Generally, dust, powder, etc. also have silicon atoms as the main component. Therefore, even if the cured film is made hard and thick, it is easily broken by impact.

[0012] On the other hand, the cured film of the present invention is considered to have a certain degree of softness and flexibility. Therefore, it is presumed to have a certain durability against collisions with particles such as dust and powder. In particular, when an alkyl group or an alkylene group is introduced, higher abrasion resistance can be exhibited. The mechanism of action is not clear, but it is thought that the flexibility, etc. is enhanced by the C-C bond, resulting in a further reduction in brittleness. As a result, it becomes possible to absorb impacts caused by dust, sand grains, etc., and exhibit higher abrasion resistance (impact resistance).

[0013] The thermosetting composition of the present invention or its cured film having such characteristics can be used not only as a protective film for optical products used indoors (inside a room), but also can be suitably used as a protective film for optical products used outdoors where collisions with particles such as dust and powder can occur.

Embodiments for Carrying Out the Invention

[0014] 1. Thermosetting composition The curable composition (the composition of the present invention) of the present invention comprises the following components: (1) A perfluoropolyether group-containing alkoxysilane (the first component), and (2) An alkoxysilane containing two or more trialkoxysilyl groups (however, excluding the alkoxysilane of (1) above) (the second component). It is characterized by including these.

[0015] A. Constituent components of the composition of the present invention The first component The perfluoropolyether group-containing alkoxysilane as the first component mainly functions to impart good water repellency, oil repellency, water slipperiness, abrasion resistance, etc. to the cured film.

[0016] In the present invention, the type of the perfluoropolyether group-containing alkoxysilane is not particularly limited. For example, a compound represented by the general formula A-PFPE-B (wherein PFPE represents a perfluoropolyether group, and one or both of A and B are organic groups having an alkoxysilyl group at the terminal, and when the terminal is not the organic group, a part or all of the hydrogen atoms may be substituted with fluorine atoms, and it is an alkyl group) can be preferably used. 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 from each other and are organic groups having an alkoxysilyl group at the terminal.

[0017] As the organic group having an alkoxysilyl group, in addition to the case of the alkoxysilyl group alone, it may also be the case of including an alkoxysilyl group and other organic groups. The alkoxysilyl group is not particularly limited, but usually, a trialkoxysilyl group represented by the general formula -Si(OC n H 2n+1 )3 (wherein n represents an integer of 1 to 3) is preferable. For example, a trimethoxysilane group, a triethoxysilane group, etc. can be mentioned.

[0018] When A or B is a single alkoxysilyl group, the structure is such that the alkoxysilyl group is directly bonded to PFPE.

[0019] When A or B contains an alkoxysilyl group and other organic groups, the structure is such that the alkoxysilyl group is bonded to PFPE via the other organic group. When it contains an alkoxysilyl group and other organic groups, as the organic group having an alkoxysilyl group, in particular, the general formula -R 1 -(OCONH) m -R 2 -R 3 (wherein R 1 and R 2 are the same as or different from each other and represent a divalent hydrocarbon group having 1 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine. For example, -(CH2) n -(where n is an integer from 1 to 10), -(CF2) n -(where n is an integer from 1 to 10), -CH2CF2-, -CF2CH2-, -CH2CF(CF3)-, -CF(CF3)CH2-, etc. may be mentioned. R 3 represents an alkoxysilyl group. m represents 0 or 1.) The organic group (specific organic group) represented by this can be preferably employed.

[0020] Here, the carbon numbers of R 1 and R 2 are preferably in the range of about 1 to 10, the same as or different from each other, and particularly preferably 1 to 6.

[0021] The above m is 0 or 1. That is, the above specific organic group may or may not contain a urethane bond -OCONH-.

[0022] The above 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 represents an integer from 1 to 3) is preferred. For example, a trimethoxysilane group, a triethoxysilane group, etc. can be mentioned.

[0023] In the above A-PFPE-B, when A or B is not an organic group having an alkoxysilyl group at the terminal, it is preferably an alkyl group having 10 or less carbon atoms and in which part or all of the hydrogen atoms may be substituted with fluorine atoms. Examples thereof include organic groups such as CF3-, CF3CF2-, CF3CH2-, CH3-, CF3CF2CF2-.

[0024] The perfluoropolyether group (PFPE) is -(C x F 2x O) m -(where x and m are integers other than 0) as a basic unit (unit), and has a structure in which a plurality of these are linked. When m is 2 or more, each (C x F 2x O) may be the same as each other or different from each other. That is, PFPE may have a structure consisting of a repetition of a single type of unit alone, or may have a structure consisting of a combination of two or more different types of units. Further, (C x F 2x O) may have a linear or branched carbon chain.

[0025] Examples of the unit -(C x F 2x O)- include, but are not limited to, CF2O, CF2CF2O, CF2CF2CF2O, CF2CF2CF2CF2CF2O, CF(CF3)CF2O, etc. In particular, in the present invention, as PFPE, -(CF2CF2O) m -(CF2O) n -(where m and n are integers other than 0), etc. can be preferably adopted. In this case, m and n can be, for example, in the range of about 10 ≤ m ≤ 40 and about 10 ≤ n ≤ 40, but are not limited to the range of m and n as long as they are within the above molecular weight range.

[0026] 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, more preferably particularly 3000 to 8000, and most preferably 3500 to 7000 among them. By having such a molecular weight, more excellent effects can be obtained in terms of water and oil repellency, water slipperiness, abrasion resistance, etc.

[0027] Regarding the method for measuring the number average molecular weight in the present invention, it is not particularly limited, and it can be carried out by measurement in terms of polymethyl methacrylate conversion using gel permeation chromatography, or measurement by structural analysis using nuclear magnetic resonance method, etc.

[0028] As such a first component, known or commercially available ones can be used, and compounds synthesized by known production methods can also be used. As commercially available products, for example, the product name "Optool DSX" (manufactured by Daikin Industries, Ltd.) etc. can be used.

[0029] When synthesizing the first component, for example, a method of bonding a trialkoxysilyl group to both ends or one end of the perfluoropolyether group can be adopted. More specifically, the first component can be suitably prepared by reacting a compound (starting compound) having a perfluoropolyether group as the main chain and having OH groups as both terminal groups or one terminal group with an isocyanate group-containing alkoxysilane compound. As the above-mentioned starting compound, more specifically, a compound represented by the general formula X-PFPE-Y (wherein PFPE represents a perfluoropolyether group, and one or both of X and Y are hydroxyl groups, and when X or Y is not a hydroxyl group, it represents an alkyl group having 10 or less carbon atoms and in which part or all of the hydrogen atoms are substituted with fluorine atoms) can be preferably used.

[0030] As the starting compound described above, known or commercially available ones can be used. That is, any of a compound in which both terminal groups of the perfluoropolyether group are hydroxyl groups, a compound in which only one terminal group of the perfluoropolyether group is a hydroxyl group, etc. can use known or commercially available ones.

[0031] As commercially available products of a compound in which both terminals of the perfluoropolyether group are hydroxyl groups, for example, product names such as "FLUOROLINK D-4000" and "FLUOROLINK D-6000" (both manufactured by Solvay Co., Ltd.) can be used. The above "FLUOROLINK D-4000" and the above "FLUOROLINK D-6000" have a basic structure represented by the following general formula (1).

Chemical formula

[0032] As commercially available products of a compound in which only one terminal group of the perfluoropolyether group is a hydroxyl group, for example, product names such as "DOL-3000" and "DOL-4000" (both manufactured by Sinochem), "PFPE KFE240AL" (manufactured by Kemars Co., Ltd.) can be used.

[0033] In the above starting compound, when one terminal group is a hydroxyl group, as the other terminal group, an alkyl group having 10 or less carbon atoms and in which part or all of the hydrogen atoms may be substituted with fluorine atoms may be used. For example, CF3-, CH3-, CF3CH2-, CF3CF2-, CF3CF2CF2- etc. are mentioned.

[0034] The isocyanate group-containing alkoxysilane compound described above may be a compound having an isocyanate group and an alkoxysilyl group, and known or commercially available ones can also be used. As commercially available products, for example, "KBE-9007N" (3-isocyanatopropyltriethoxysilane) (manufactured by Shin-Etsu Silicone Co., Ltd.) etc. can be preferably used.

[0035] The manufacturing conditions are not particularly limited. For example, it can be carried out by a method including 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 step of recovering the first component (target product) from the reaction product solution (recovery step).

[0036] In the reaction step, the charging ratio of the starting compound and the isocyanate group-containing alkoxysilane compound is not particularly limited. For example, it can be appropriately set within a range of about 1:1 to 1:4 in terms of molar ratio.

[0037] In addition, in the reaction step, a liquid-phase reaction using a solvent may be carried out. As the solvent, it is preferable to use a fluorine-based solvent. As the fluorine-based solvent, for example, a hydrofluoroether-based solvent can be preferably used. As such a solvent, known or commercially available ones can also be used. For example, 1,3-bis(trifluoromethyl)benzene etc. can be used. Also, as commercially available products, for example, product names such as "Novec HFE-7200", "Novec HFE-7300" (both are products of 3M) etc. can be preferably used.

[0038] In the reaction step, it can also be carried out in the presence of a catalyst as necessary. As the catalyst, an alkaline catalyst can be preferably used, and among them, at least one organic-based alkaline catalyst such as triethylamine, tributylamine, pyridine and 1,4-diazabicyclo[2.2.2]octane is particularly preferable.

[0039] In the recovery process, the method is not particularly limited as long as the target first component can be recovered (isolated). For example, alcohols (such as methanol and ethanol) can be added to the reaction product solution, followed by layering, and then the supernatant (the upper layer of the reaction product solution) can be removed. That is, generally, since the first component precipitates in the reaction product solution, it is possible to purify and separate it by removing the supernatant. By repeating a series of steps of adding alcohols and removing the supernatant multiple times, the first component can be obtained in a higher yield. In this case, if necessary, the first component can also be recovered as a solid content by performing reduced pressure, drying, etc.

[0040] 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, and more preferably 15 to 30% by mass. Thereby, excellent scratch resistance and the like can be more reliably formed.

[0041] Second component The alkoxysilane containing two or more trialkoxysilyl groups as the second component is mainly used to reduce the brittleness of the cured film and impart high wear resistance by absorbing the impact during collision with particles (such as sand grains) such as dust and powder.

[0042] Trialkoxysilyl group The number only needs to be two or more, and may be, for example, 2, 3, 4, etc. Also, when using a plurality of types of the second component, the numbers may be the same as each other or different from each other. For example, Trialkoxysilyl group a second component having 2 Trialkoxysilyl group and a second component having 3 can be used in combination.

[0043] The above trialkoxysilyl group in the second component is not limited, but is usually represented by the general formula -Si(OC n H 2n+1)3(Provided that n represents an integer from 1 to 3.) The trialkoxysilyl group represented by can be preferably used. For example, a trimethoxysilane group, a triethoxysilane group, etc. can be mentioned.

[0044] In the second component, two or more Trialkoxysilyl group are preferably bonded to each other via an organic group containing an alkylene group in which part or all of the hydrogen atoms may be substituted with fluorine atoms.

[0045] Examples of the above alkylene group include those having about 1 to 10 carbon atoms. For example, ―CH2―, ―CH2CH2―, CF2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2-, -CF2CF2CF2-, etc. can be mentioned. It is preferable that the carbon atom of the alkylene group is Trialkoxysilyl group directly bonded to the silicon atom of.

[0046] Examples of the organic group include, in addition to the organic group composed only of the above alkylene group, the case where 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, etc.

[0047] Specific examples of the second component include 1,6-bis-(trimethoxysilyl)hexane, bis(trimethoxysilyl)ethylene, tris(trimethoxysilylpropyl)isocyanurate, etc.

[0048] The above bis(trimethoxysilyl)ethylene is represented by the following general formula (2). The above 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 the following formulas, each Me represents a methyl group.

Chemical formula

[0049] For these compounds, known or commercially available ones can be used. 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.

[0050] The solid content of the second component in the composition of the present invention is not particularly limited. However, in order to more surely exhibit the functions of the second component as described above, it is usually about 10 to 50% by mass, and particularly preferably 20 to 40% by mass.

[0051] Note that the second component excludes the perfluoropolyether group-containing alkoxysilane which is the first component. That is, the second component is composed of a compound that does not contain a perfluoropolyether group.

[0052] The third component In the present invention, if necessary, an alkoxysilane containing one trialkoxysilyl group may be included as the third component. The alkoxysilane containing one trialkoxysilyl group as the third component mainly has a function of imparting good film-forming properties, curability, etc.

[0053] The alkoxysilane is not particularly limited as long as it has one trialkoxysilyl group. In particular, R 4 -Si(OR 5 )3 (wherein R 4 represents an alkyl group having 1 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine atoms. R 5represents an alkyl group having 1 to 3 carbon atoms. Compounds represented by ) can be preferably used. More specifically, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. can be mentioned.

[0054] These can also use those that are known or commercially available. Examples of commercially available products include product names "KBE-3083", "KBE-13", "KBM-3033", "KBE-3033", "KBE-3083", "KBM-7103" (all manufactured by Shin-Etsu Silicone Co., Ltd.), etc.

[0055] 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, more preferably 30 to 60% by mass, and particularly most preferably 40 to 50% by mass. Thereby, excellent scratch resistance, etc. can be obtained more reliably.

[0056] Note that the third component excludes the perfluoropolyether group-containing alkoxysilane which is the first component. That is, the third component is composed of a compound that does not contain a perfluoropolyether group.

[0057] Also, the ratio of the first component to the third component is not limited, but particularly preferably, with respect to 100 parts by mass of the first component, the second component is 50 to 300 parts by mass and the third component is 0 to 300 parts by mass, more preferably the second component is 50 to 300 parts by mass and the third component is 100 to 300 parts by mass, and particularly most preferably, with respect to 100 parts by mass of the first component, the second component is 100 to 200 parts by mass and the third component is 200 to 250 parts by mass.

[0058] Fourth component In the present invention, if necessary, a tetraalkoxysilane hydrolysis condensate (silicate oligomer) can be contained as a fourth component. By blending the tetraalkoxysilane hydrolysis condensate, film-forming properties, curability, hardness, etc. can be enhanced.

[0059] The tetraalkoxysilane hydrolysis condensate is not particularly limited, and examples thereof include compounds formed by hydrolysis and polycondensation reactions 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., but in the present invention, dimers to decamers (average value) can be preferably used.

[0060] As such compounds, known or commercially available ones can be used, and they can also be synthesized by known production methods. Examples of commercially available products include product names such as "Methyl Silicate 51" and "Methyl Silicate 53A" (both manufactured by Colcoat Co., Ltd.).

[0061] The solid content of the fourth component in the composition of the present invention is not particularly limited, but in order to more surely exhibit the functions of the fourth component as described above, it is usually about 0 to 20% by mass, and particularly preferably 1 to 15% by mass.

[0062] Other components In the composition of the present invention, in addition to the first to fourth components, other components can be appropriately blended as necessary within a range that does not hinder the effects of the present invention. For example, in addition to the solvents shown below, inorganic fine particles (oxide fine particles such as silica, alumina, titania, zirconia, etc.), colorants, etc. can be mentioned.

[0063] B. Properties, etc. of the composition of the present invention The form of the composition of the present invention is not limited, but it is usually sufficient to be in a liquid state. To make it liquid, a solvent can be blended, and it can be either a solution or a dispersion.

[0064] The solvent can be appropriately set according to the types of the first component and the like. For example, at least one of a fluorinated solvent, a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent can be used.

[0065] Examples of the fluorinated solvent include trifluorotoluene, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, metaxylene hexafluoride, and the like.

[0066] Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.

[0067] Examples of the ester solvent include ethyl acetate, butyl acetate, methoxybutyl acetate, methoxypropyl acetate, and the like.

[0068] Examples of the alcohol solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), and the like.

[0069] The amount of the organic solvent used can be appropriately adjusted according to, for example, the type of the components used, the desired viscosity, etc., so 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), but is not limited thereto.

[0070] C. Production of the Composition of the Present Invention The composition of the present invention can be prepared by uniformly mixing the above-mentioned respective components. The mixing order and the like during mixing are not particularly limited, and any order can be adopted. In particular, when preparing a liquid composition, the solvent may be mixed together with the first component and the like. The mixing can be carried out using a known or commercially available device such as a mixer or a kneader. Also, the atmosphere for mixing is usually such that the respective components are mixed under normal temperature and normal pressure, but is not limited thereto.

[0071] 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, a protective layer that is less likely to be scratched even outdoors can be obtained more reliably.

[0072] The cured film may be transparent, translucent or opaque. In particular, when used as a protective layer for lighting, lenses or their covers, etc., it is desirable that the cured film be transparent or translucent. The transparency in this case is not limited, but usually it is preferably about 0.1 to 5% as the haze value.

[0073] Also, the thickness of the cured film can be appropriately set according to the use, the part to be used, etc., but it is usually about 0.05 to 2 μm, and particularly preferably 0.1 to 0.5 μm.

[0074] The method for forming the cured layer is not particularly limited, and can be preferably carried out by a method including, for example, a) a step of forming a coating film of the composition of the present invention on a substrate and b) a step of curing the coating film.

[0075] The substrate serving as the base (lower layer) of the cured layer is not particularly limited, and may be any of, for example, synthetic resins, rubbers, ceramics, glass, metals, etc. In particular, transparent substrates such as glass and synthetic resins (such as polyester resins and acrylic resins) can be preferably used. Also, the substrate may be any of, for example, raw materials, semi-finished products, products, etc.

[0076] The method for forming the coating film of the composition of the present invention can be appropriately carried out by known coating methods such as, for example, the doctor blade method, the bar coating method, the dipping method, the air spray method, the roller brush method, the roller coater method, the vapor deposition method, etc.

[0077] The coating amount of the coating film may be, for example, an amount such that the thickness of the desired cured film is obtained, and can usually be appropriately set within a range where the thickness of the obtained cured film is within about 2 μm (preferably within the range of 0.1 to 0.5 μm).

[0078] Further, before curing, the obtained coating film may be subjected to a drying process as necessary. The drying method may be natural drying or heating at a temperature of about 60 to 120°C.

[0079] Next, the coating film is cured. In the present invention, the method of curing the coating film is to perform curing by heating (thermal curing). The conditions for thermal curing may be appropriately set according to the type of the first component and the like, but usually it is preferably about 50 to 200°C (particularly 120 to 180°C) in the air. The heating time may be a time sufficient for the coating film to cure, and for example, it can be set within the range of 0.1 to 2 hours, but it is not limited thereto.

[0080] Furthermore, in the present invention, a laminate in which a cured film is laminated on a substrate can be obtained by a method including a step of forming a coating film of the composition of the present invention on the substrate and a step of curing the coating film. Such a laminate can be used, for example, as a material for various products.

[0081] 2. Articles (Optical Products) The present invention includes an article (particularly an optical product) 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 against abrasion accompanied by collision with particles (such as scattered sand grains) such as dust and powder as well as simple rubbing between substances, and thus can be applied as a protective layer for the substrate (product). Especially, it can be preferably used as a protective layer for a substrate (product) exposed to dust, powder, etc.

[0082] Therefore, in addition to lighting, lenses, or their covers used indoors, the cured film of the present invention can be applied as a protective layer (the outermost surface layer) for lighting, lenses, or their covers used outdoors. For example, a) security cameras, weather observation cameras, river monitoring cameras, cameras mounted on vehicles and ships, outdoor lighting (streetlights, parking lots, stadiums, etc.) installed outdoors, or b) lenses (lighting lenses or camera lenses) used for these, c) surface protection of covers for lighting or lenses, etc. are suitable. In addition, it can also be used as a protective layer for the screens of smartphones, tablet screens, etc.

[0083] The method of applying the cured film of the present invention to these articles (especially optical products) includes, for example, a method of forming a predetermined cured film (protective layer) by a method including a 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 and then curing it, but is not limited thereto.

Examples

[0084] Examples and comparative examples are shown below to more specifically explain the features of the present invention. However, the scope of the present invention is not limited to the examples.

[0085] Example 1 As shown in Table 1, 0.20 g of a perfluoropolyether group-containing alkoxysilane (Production Example 1), 0.5 g of an alkoxysilane containing one trialkoxysilyl group (product name "KBM-7103", manufactured by Shin-Etsu Chemical Co., Ltd.), 0.2 g of bistrimethoxysilylethylene, 0.1 g of a tetramethoxysilane hydrolysis condensate (product name "methyl silicate 51", manufactured by Colcoat Co., Ltd., average tetramer), and 99.0 g of a fluorine-based solvent (product name "Novec HFE-7200" (manufactured by 3M)) were weighed into a 200 mL beaker and stirred at room temperature for 1 hour to obtain a liquid composition. The liquid composition was applied to a washed glass plate and heat-cured in an oven at 170°C for 30 minutes to produce a cured film. The film thickness at this time was about 0.2 μm.

[0086] Examples 2 to 12 and Comparative Examples 1 to 4 A liquid composition was prepared in the same manner as in Example 1, except that the composition shown in Table 1 was changed. A cured film was produced using the above liquid composition in the same manner as in Example 1.

[0087]

Table 1

[0088] The meanings of the abbreviations in Table 1 are as follows. (1) First component: perfluoropolyether group-containing alkoxysilane · "Production Example 1": Perfluoropolyether group-containing alkoxysilane 1 synthesized in the following <Production Example 1> <Production Example 1> 18.0 g (3.0 mmol) of a hydroxyl group-containing perfluoropolyether compound (product name "FLUOROLINK D-6000" (manufactured by Solvay Co., Ltd., average molecular weight 6000), 1.48 g (7.2 mmol) of 3-isocyanatopropyltrimethoxysilane (manufactured by Kanto Chemical Co., Inc.), 0.015 g (0.15 mmol) of triethylamine (manufactured by Kanto Chemical Co., Inc.), and 18.0 g of metaxylene hexafluoride were weighed into a 30 mL eggplant flask equipped with a stirrer. The reaction solution was stirred at 50 °C for 6 hours. Methanol was added to the reaction solution after the reaction to layer the reaction solution. Since the lower layer was the target product, the solvent in the upper layer was removed. The washing process was repeated 3 times using methanol. The product was placed in an eggplant flask and dried under reduced pressure to remove the solvent, and perfluoropolyether group-containing alkoxysilane 1 (yield 90%, 17.3 g) as the target product was synthesized. · "Production Example 2": Perfluoropolyether group-containing alkoxysilane 2 synthesized in the following <Production Example 2> <Production Example 2> 12.0 g (3.0 mmol) of a hydroxyl group-containing perfluoropolyether-based compound (product name: "FLUOROLINK D-4000", manufactured by Solvay Co., Ltd., average molecular weight 4000), 1.48 g (7.2 mmol) of 3-isocyanatopropyltrimethoxysilane (manufactured by Kanto Chemical Co., Inc.), 0.015 g (0.15 mmol) of triethylamine (manufactured by Kanto Chemical Co., Inc.), and 12.0 g of metaxylene hexafluoride were weighed into a 30 mL eggplant flask equipped with a stirrer. The reaction solution was stirred at 50 °C for 6 hours. Methanol was added to the reaction solution after the reaction to separate the reaction solution into layers. Since the lower layer was the target product, the solvent in the upper layer was removed. The washing process was repeated 3 times using methanol. The product was placed in an eggplant flask and dried under reduced pressure to remove the solvent, thereby synthesizing the target perfluoropolyether group-containing alkoxysilane 2 (yield 87%, 10.2 g). · "Production Example 3": Perfluoropolyether group-containing alkoxysilane 3 synthesized in the following <Production Example 3> <Production Example 3> 12 g (4.0 mmol) of a hydroxyl group-containing perfluoropolyether-based compound (product name: "DOL-3000", manufactured by Sinochem Co., Ltd., average molecular weight 3000), 0.99 g (4.8 mmol) of 3-isocyanatopropyltrimethoxysilane, 0.020 g (0.20 mmol) of triethylamine, and 12.0 g of metaxylene hexafluoride were weighed into a 30 mL eggplant flask equipped with a stirrer. The reaction solution was stirred at 50 °C for 6 hours. Methanol was added to the reaction solution after the reaction to separate the reaction 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 3 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: An alkoxysilane containing two or more trialkoxysilyl groups · "Raw material A": Bis(trimethoxysilyl)ethylene · "Raw material B": 1,6-Bis(trimethoxysilyl)hexane · "Raw material C": "KBM-9659" manufactured by Shin-Etsu Silicone Co., Ltd. (tris(trimethoxysilylpropyl) isocyanurate) (3) Third component: an alkoxysilane containing one trialkoxysilyl group · "KBM-7103": "KBM-7103" manufactured by Shin-Etsu Silicone (3,3,3-trifluoropropyltrimethoxysilane) · n-Pro-Si(OMe)3: CH3CH2CH2-Si(OMe)3 (Me is a methyl group) · C6F13Si: CF3CF2CF2CF2CF2CF2-Si(OMe)3 (Me is a methyl group) (4) Fourth component: a tetraalkoxysilane hydrolysis condensate · "MS-51": "Methyl Silicate 51" manufactured by Colcoat Co., Ltd. (tetramethoxysilane hydrolysis condensate (average tetramer)) (5) Solvent · "Novec HFE-7200" (manufactured by 3M) (fluorine-based solvent)

[0089] Test Example 1 The water repellency of the cured films prepared in the examples and comparative examples was examined. More specifically, the contact angle (initial) of the cured films with respect to water was measured at 25°C. The measurement of the water contact angle was performed using a contact angle measuring device (product name "DropMaster700" manufactured by Kyowa Interface Science) (the same applies to each of the following tests). The results are shown in Table 2.

[0090] Test Example 2 For the cured films prepared in the examples and comparative examples, the water repellency after a predetermined abrasion test was measured. The abrasion test was carried out as follows using an ultrasonic cleaner. A dispersion in which 10% by mass of Kanto Loam (8 types of JIS test powder 1) was dispersed in water was used, and the dispersion was placed in a stainless-steel container (SUS container). Next, a test piece (glass plate with a cured film) was placed in the SUS container. The SUS container was placed in a commercially available ultrasonic cleaner, the ultrasonic cleaner was operated, and the test piece was treated by irradiating the dispersion with ultrasonic waves. By treating the test piece in this way, the Kanto Loam is violently shaken by the shock wave generated by the rupture of the vacuum bubbles generated in the dispersion by the ultrasonic waves, and the Kanto Loam collides with the test piece to damage the test piece. The conditions of the ultrasonic waves were a frequency of 28 kHz and an output of 600 W. After 8 hours of irradiation, the test piece was recovered, washed with pure water, and air-dried. The contact angle of water with respect to the cured film after the test thus obtained was measured. The results are shown in Table 2.

[0091] Test Example 3 The steel wool resistance test was carried out for each test piece. The water contact angle was measured after rubbing the cured film surface of the test piece 300 times back and forth (load 1000 g) with steel wool (#0000). The results are shown in Table 2.

[0092]

Table 2

[0093] From the comparison between Example 1 and Comparative Example 1 in Table 2, it can be seen that when the first component to the second component are not included, the decrease in liquid repellency due to the abrasion test becomes large. In particular, from the comparison between Examples 1 to 5 and Comparative Examples 2 to 4, it can also be seen that when the second component is not included, the decrease in liquid repellency in the abrasion resistance test becomes large.

[0094] Thus, in the present invention, by having a film thickness of at least about 0.2 μm and containing a certain amount of a polysubstituted alkoxysilane having an alkyl chain, in addition to the Si-O-Si bond, particularly by introducing a C-C bond, the brittleness of the cured film is reduced, and it becomes possible to enhance the durability against abrasion accompanied by impact with particles.

[0095] Example 13 As shown in Table 3, 0.60 g of a perfluoropolyether group-containing alkoxysilane (Production Example 4), 0.3 g of bistrimethoxysilylethylene, 0.1 g of a hydrolysis condensate of tetramethoxysilane (product name "Methyl Silicate 51", manufactured by Colcoat Co., average tetramer), and 99.0 g of a fluorine-based solvent (product name "Novec HFE-7200" (manufactured by 3M)) were weighed into a 200 mL beaker and stirred at room temperature for 1 hour to obtain a liquid composition. The liquid composition was applied to a washed glass plate and heat-cured in an oven at 170 °C for 30 minutes to produce a cured film. The film thickness at this time was about 0.2 μm.

[0096] Examples 14 to 16 and Comparative Example 5 A liquid composition was prepared in the same manner as in Example 13, except that the composition shown in Table 3 was changed. A cured film was produced using the liquid composition in the same manner as in Example 1.

[0097]

Table 3

[0098] The meanings of the abbreviations in Table 3 are as follows. (1) First component: perfluoropolyether group-containing alkoxysilane · "Production Example 4": perfluoropolyether group-containing alkoxysilane synthesized in the following <Production Example 4> 4 <Production Example 4> Into a 30 mL eggplant flask equipped with a stirrer, a hydroxyl group-containing perfluoropolyether-based compound (product name: "DOL-3000", manufactured by Shinochem Co., Ltd., 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 metaxylene hexafluoride were weighed. The reaction solution was stirred at 50 °C for 6 hours. After the reaction, methanol was added to the reaction solution to separate the reaction. Since the lower layer was the target product, the solvent in the upper layer was removed. The washing step using methanol was repeated 3 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 4 (yield 90%, 17.3 g). · "Production Example 5": The perfluoropolyether group-containing alkoxysilane synthesized in the following <Production Example 5> 5 <Production Example 5> Into a 30 mL eggplant flask equipped with a stirrer, a hydroxyl group-containing perfluoropolyether-based compound (product name: "DOL-4000", manufactured by Shinochem Co., Ltd., 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 metaxylene hexafluoride were weighed. The reaction solution was stirred at 50 °C for 6 hours. After the reaction, methanol was added to the reaction solution to separate the reaction. Since the lower layer was the target product, the solvent in the upper layer was removed. The washing step using methanol was repeated 3 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 5 (yield 87%, 10.2 g). (2) Second component: An alkoxysilane containing two or more trialkoxysilyl groups · "Raw material A": Bis(trimethoxysilyl)ethylene · "Raw material B": 1,6-Bis(trimethoxysilyl)hexane · "Raw material C": "KBM-9659" (tris(trimethoxysilylpropyl)isocyanurate) manufactured by Shin-Etsu Silicone Co., Ltd. (3) Component 3: An alkoxysilane containing one trialkoxysilyl group · "KBM-7103": "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Silicone (4) Component 4: A hydrolytic condensate of tetraalkoxysilane · "MS-51": "Methyl Silicate 51" (hydrolytic condensate of tetramethoxysilane (average tetramer)) manufactured by Colcoat (5) Solvent · "Novec HFE-7200" (manufactured by 3M) (fluorinated solvent)

[0099] Test Example 4 In the same manner as in Test Example 1, the water repellency of the cured films prepared in each Example and Comparative Example was examined. The results are shown in Table 4.

[0100] Test Example 5 In the same manner as in Test Example 2, for the cured films prepared in the Examples and Comparative Examples, the water repellency against water after conducting a predetermined abrasion test was measured. The results are shown in Table 4.

[0101] Test Example 6 In the same manner as in Test Example 3, a steel wool resistance test was conducted on each test piece. The results are shown in Table 4.

[0102]

Table 4

[0103] From the comparison between Example 16 and Comparative Example 5, it can be seen that when the alkoxysilane containing a multi-substituted alkyl chain is not contained, the ultrasonic abrasion resistance decreases. Also, the film thickness is about 0.2 μm. By containing a certain amount of multi-substituted alkoxysilane having an alkyl chain, in addition to the Si-O-Si bond, the alkyl chain bond is introduced, and it can be seen that the brittleness of the cured film is reduced and the abrasion resistance in the Kanto region is improved.

Claims

1. The following components: (1) Perfluoropolyether group-containing alkoxysilane: 10 to 60% by mass, (2) 1,6-bis-(trimethoxysilyl)hexane or bis(trimethoxysilyl)ethylene: 10 to 50% by mass, (3) Alkoxysilane containing one trialkoxysilyl group (excluding the alkoxysilane of (1) above): 0% by mass, and (4) Tetraalkoxysilane hydrolysis condensate: 1 to 15% by mass A thermosetting composition characterized by containing the same.

2. The thermosetting composition according to Claim 1, wherein the number average molecular weight of the alkoxysilane of (1) above is 3000 or more.

3. The thermosetting composition according to Claim 1, containing 50 to 200 parts by mass of the alkoxysilane of (2) with respect to 100 parts by mass of the perfluoropolyether group-containing alkoxysilane.

4. The thermosetting composition according to Claim 1, further containing an organic solvent and being in a liquid state.

5. The thermosetting composition according to Claim 1, used for forming a protective layer for a substrate exposed to dust or powder.

6. A cured film formed by curing the thermosetting composition according to any one of Claims 1 to 5.

7. A laminate formed by laminating the cured film according to Claim 6 on a substrate.

8. An article formed by laminating the cured film according to Claim 6 on a substrate.

9. An optical product formed by laminating the cured film according to Claim 6 on a substrate.

10. The optical product according to Claim 9, used for outdoor use.

11. The optical product according to Claim 10, wherein the substrate is lighting, a lens used outdoors, or a cover thereof.

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