JP6996897B2 - Laminate - Google Patents

Description

The present invention relates to a novel laminate, and more particularly to a laminate having adhesion prevention properties (water repellency and oil repellency).

In recent years, materials exhibiting water repellency or oil repellency have been attracting attention from the viewpoints of antifouling property and reduction of frictional resistance at the solid-liquid interface. For example, Patent Document 1 discloses a coating film comprising metal oxide composite particles having a resin layer containing a polyfluoroalkyl metaacryllate resin on the surface.

Japanese Unexamined Patent Publication No. 2014-80465

However, although high water repellency and oil repellency can be obtained with respect to water or most oils with conventional techniques such as the technique of Patent Document 1, satisfactory oil repellency can be obtained with some oils such as oleic acid. It cannot be obtained, and there is room for further improvement in that respect.

Therefore, an object of the present invention is to provide a laminate capable of exhibiting higher water repellency and oil repellency than conventional ones.

As a result of diligent 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 specific layer structure, and has completed the present invention.

That is, the present invention relates to the following laminated body.
1. 1. A laminate containing a base material and an adhesion prevention layer,
(1) The adhesion prevention layer contains fluorine-containing composite particles, and the adhesion prevention layer contains fluorine-containing composite particles.
(2) Fluorine-containing composite particles are composite particles in which the surface of the silica-based fine particles is coated with at least one of 1) a fluorine-containing compound and 2) a fluorine-containing group formed by siloxane bonding with silicon of the silica-based fine particles. And,
The fluorine-containing compound is [-Si (OR) ₃ ] on the terminal side of at least one of the main chains made of perfluoropolyether (however, the three Rs are the same or different from each other and have hydrogen or 1 to 10 carbon atoms. It is a compound containing a functional group represented by () and is a compound containing an alkyl group.
(3) The laminated weight of the silica-based fine particles coated with the fluorine compound per unit area of the surface of the base material is 0.7 to 5.0 g / m ² .
A laminated body characterized by that.
2. 2. Item 2. The laminate according to Item 1, which has a primer layer between the base material and the adhesion prevention layer.
3. 3. Item 2. The laminate according to Item 2, further comprising packed particles having an average particle size of 10 to 60 μm in the primer layer.
4. Item 2. The laminate according to any one of Items 1 to 3, wherein the silica-based fine particles have an average primary particle diameter of 3 to 500 nm.
5. Item 2. The laminate according to any one of Items 1 to 4, wherein the base material is at least one of a resin, a rubber, a metal material, an inorganic material, and a composite material containing the same.
6. The fluorine-containing compound is (RO) ₃ Si- (CH ₂ ) _k -NHC (= O) -CF ₂ -O- (Cn F _2n ) _m -C (= O) NH- (CH ₂ ) _{k -} Si. (OR) ₃ (where R is an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 7, m is an integer of 7 or more, and k is an integer of 1 to 5). Item 2. The laminate according to any one of Items 1 to 5, which comprises.

According to the present invention, it is possible to provide a laminate capable of exhibiting higher water repellency and oil repellency than before. In particular, the fluorine-containing composite particles of the present invention can exhibit high oil repellency against specific oils such as oleic acid.

Therefore, the laminate of the present invention can be suitably used as a product, a member, a component, or the like capable of exhibiting an adhesion preventing effect (water repellency / oil repellency).

FIG. 1A is a schematic view of a laminate in which an adhesion prevention layer made of fluorine-containing composite particles is formed on the surface of a base material. FIG. 1B shows a schematic diagram of the structure of the fluorine-containing composite particles of the present invention. FIG. 2 is a schematic view of the device used for measuring the sliding angle in the test example. FIG. 2A shows a state before jacking up an aluminum plate. FIG. 2B shows a state in which an aluminum plate is jacked up.

1. 1. Laminated body The laminated body of the present invention is a laminated body including a base material and an adhesion prevention layer.
(1) The adhesion prevention layer contains fluorine-containing composite particles, and the adhesion prevention layer contains fluorine-containing composite particles.
(2) Fluorine-containing composite particles are composite particles in which the surface of the silica-based fine particles is coated with at least one of 1) a fluorine-containing compound and 2) a fluorine-containing group formed by siloxane bonding with silicon of the silica-based fine particles. And,
The fluorine-containing compound is [-Si (OR) ₃ ] on the terminal side of at least one of the main chains made of perfluoropolyether (however, the three Rs are the same or different from each other and have hydrogen or 1 to 10 carbon atoms. It is a compound containing a functional group represented by () and is a compound containing an alkyl group.
(3) The laminated weight of the silica-based fine particles coated with the fluorine compound per unit area of the surface of the base material is 0.7 to 5.0 g / m ² .
It is characterized by that.

FIG. 1A shows a schematic diagram of a layer structure according to an embodiment of the laminated body of the present invention. As shown in FIG. 1A, in the laminated body 1, the adhesion prevention layer 26 is laminated on the surface of the base material 10 via the primer layer 20. That is, the primer layer 20 is laminated so as to be in direct contact with the base material 10, and the adhesion prevention layer 26 is further laminated so as to be in direct contact with the primer layer 20. Although the primer layer 20 is not essential in the present invention, it is desirable that the primer layer 20 is laminated via the primer layer from the viewpoint of adhesion between the base material 10 and the adhesion prevention layer 26.

As shown in FIG. 1A, the primer layer 20 preferably contains the primer component 22 and the packed particles 24. By including the packed particles 24, unevenness can be formed on the surface of the primer layer 20, and as a result, a higher adhesion prevention effect can be realized. In particular, since the adhesion prevention layer 26 of the recess formed by the filled particles is not easily affected by friction or the like, it can exist for a long period of time, and thus can contribute to the realization of a highly durable adhesion prevention effect.

The adhesion prevention layer 26 contains fluorine-containing composite particles 26a. In particular, it is preferable that the adhesion prevention layer 26 is substantially formed of fluorine-containing composite particles 26a. Further, as shown in FIG. 1A, the adhesion prevention layer 26 is preferably a porous layer having a three-dimensional network structure formed by adhering a plurality of fluorine-containing composite particles to each other. Thereby, a higher adhesion prevention effect can be obtained.

A schematic cross-sectional view of the fluorine-containing composite particles 26a is shown in FIG. 1 (b). As shown in FIG. 1 (b), in the fluorine-containing composite particles 26a, the surface of the silica-based fine particles 27 is coated with the fluorine-containing compound 28.

Hereinafter, each configuration of the laminated body of the present invention will be described. In addition, in FIGS. 1A and 1B, each structure is schematically shown in an easy-to-understand manner, and the size, number, etc. of each configuration do not necessarily reproduce the actual laminated body.

(1) Base material The base material serves as a support portion for laminating silica-based fine particles. That is, it is a target for imparting an adhesion prevention effect.

The material of the base material is not particularly limited, and examples thereof include at least one of a resin, a rubber, a metal material (including an alloy), an inorganic material, and a composite material containing these. The form is not limited, and may be any of, for example, a sheet, a film, a molded body, fibers (including woven fabric, non-woven fabric, paper, etc.), powder particles, and the like. Therefore, it can be applied to various materials such as resin film, resin sheet, paper, non-woven fabric, synthetic paper, metal foil, metal plate, resin film, metal film, rubber, glass, ceramics, and plastic molded products.

Further, in the present invention, a product (final product or semi-finished product) or a component thereof can also be used as a base material. That is, the form in which such a final product or a component thereof is used as a base material is also included in the laminate of the present invention. These products or parts include, for example, packaging materials, daily necessities (glasses, rain gear, bags, etc.), building materials (roofs, wallpaper, flooring materials, ceiling materials, tiles, window glass, etc.), paving materials (asphalt pavement, concrete pavement, etc.). ), Tableware, cooking utensils (pots, gas stove saucers, oil shield panels, electromagnetic cooker top plates, etc.), kitchen utensils, sporting goods, clothing (hats, shoes, gloves, coats, etc.), structures (buildings) It can be widely applied to walls, bridges, towers, etc.), transportation equipment (outer surface of the body of cars, bikes, trains, ships, etc.), cosmetics, pharmaceuticals, toys, identification jigs, housings of machines or devices, and the like.

(2) Adhesion prevention layer The adhesion prevention layer contains specific fluorine-containing composite particles. The content of the fluorine-containing composite particles in the adhesion prevention layer is not particularly limited, but is usually 80 to 100% by weight, and particularly preferably 95 to 100% by weight. As other components, a resin component such as polyolefin may be contained within a range that does not interfere with the effects of the present invention.

The amount of the adhesion prevention layer applied is usually 0.7 to 5.0 g / m ² , and more preferably 1.0 to 5.0 g / m ² . This makes it possible to more reliably impart a higher adhesion prevention effect (water repellency / oil repellency).

The thickness of the adhesion prevention layer can be appropriately set according to the particle size and the like of the fluorine-containing composite particles used, and is usually in the range of about 0.5 to 10.0 μm, but is not limited to this.

The adhesion prevention layer may be formed on the entire surface of the base material, or may be a part thereof. Further, the formation pattern of the adhesion prevention layer is not limited, and may be, for example, a stripe shape, a dot shape, a grid shape, or the like.

(2-1) Fluorine-containing composite particles
In the fluorine-containing composite particles (particles of the present invention), the surface of the silica-based fine particles is coated with at least one of 1) a fluorine-containing compound and 2) a fluorine-containing group formed by siloxane bonding with silicon of the silica-based fine particles. It ’s a composite particle,

The fluorine-containing compound is [-Si (OR) ₃ ] on the terminal side of at least one of the main chains made of perfluoropolyether (however, the three Rs are the same or different from each other and have hydrogen or 1 to 10 carbon atoms. It is a compound containing a functional group (hereinafter, also referred to as “functional group A”) represented by (indicating an alkyl group).

As shown in FIG. 1 (b), the particles 26a of the present invention have a structure in which silica-based fine particles 27 are used as core particles and a part or all of the surface thereof is coated with a fluorine-containing compound (or fluorine-containing group) 27. is doing. As the fluorine-containing compound, a polymer having a perfluoropolyether as a main chain (particularly a linear polymer) can be preferably used. In the present invention, the fluorine-containing compound 27 may be present on the surface of the silica-based fine particles without reacting (that is, while retaining the functional group A), but in particular, the functional group A may be present on the surface of the silica-based fine particles. It is preferable that it exists as a fluorine-containing group (fluorine-containing organic group) as a result of forming a chemical bond (particularly a siloxane bond) with a certain silica or another functional group (particularly a hydrophilic group such as an OH group). This makes it possible for the fluorine-containing compound to be more firmly fixed to the surface of the silica-based fine particles as a fluorine-containing group.

Silica-based fine particles The silica-based fine particles may be those containing silica (SiO ₂ ), and may be particles containing silica alone or particles containing silica and other components. In the present invention, the silica-based fine particles are preferably fine particles containing 50% by mass or more of silica, and more preferably 99% by mass or more of silica.

When the silica-based fine particles contain other components, the other components include, for example, iron (Fe), titanium (Ti), aluminum (Al), calcium (Ca), zirconium (Zr), sodium, in addition to unavoidable impurities. Examples thereof include elements such as (Na), potassium (K) and magnesium (Mg) or compounds thereof.

Further, since the silica-based fine particles may be obtained by surface-treating the silica particles, they may contain a compound (or a functional group) imparted by the surface treatment. Therefore, in the present invention, hydrophobic silica-based fine particles, hydrophilic silica-based fine particles, or a mixture thereof can be used as the silica-based fine particles.

In the present invention, hydrophilic silica-based fine particles having an OH group on the surface thereof can be preferably used as the silica-based fine particles. By providing an OH group on the surface of the silica-based fine particles, the functional group A becomes a siloxane bond [-Si-O-Si ^* ] by dehydration condensation reaction with the OH group on the surface of the silica-based fine particles (however, Si ^* becomes the silica-based fine particles. The contained Si) can be formed, and the fluorine-containing compound can be firmly fixed to the surface of the silica-based fine particles.

Even when hydrophobic silica-based fine particles are used, the hydrophilic silica-based fine particles are used by subjecting the hydrophobic silica-based fine particles to a hydrophilic treatment in advance to impart OH groups or the like to the surface of the silica-based fine particles. As in the case, the fluorine-containing compound can be fixed on the surface of silica-based fine particles.

The average primary particle size of the silica-based fine particles is usually 5 to 50 nm, and particularly preferably 7 to 30 nm. By setting the particle size within the range, more excellent water repellency and oil repellency can be obtained.

In the present invention, the measurement of the primary particle average diameter of the particles can be carried out by using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle diameter is obtained by taking a picture with a transmission electron microscope or a scanning electron microscope, measuring the diameters of 200 or more particles on the photograph, and calculating the arithmetic mean value thereof. be able to.

The specific surface area of the silica-based fine particles is not particularly limited, but is usually preferably 400 m ² / g or less, and particularly preferably 40 to 380 m ² / g. If the specific surface area exceeds 400 m ² / g, it becomes difficult to uniformly coat the fluorine compound or the fluorine-containing group described later, and the yield may decrease.

The shape of the silica-based fine particles is not particularly limited as long as it is in the form of particles, and any shape such as a spherical shape, a rod shape, a needle shape, a plate shape, an indefinite shape, a scale shape, or a spindle shape can be adopted. In particular, the silica-based fine particles are preferably spherical (substantially spherical) close to a true sphere in order to minimize the contact area with water or oil.

As these silica-based fine particles themselves, known or commercially available ones can be used. It can also be synthesized by a known production method. Therefore, for example, silica-based fine particles produced by high-temperature combustion of silane tetrachloride, silica-based fine particles produced by the sol-gel method, and the like can also be preferably used. Commercially available products include, for example, product names "AEROSIL 200" ("AEROSIL" is a registered trademark; the same applies hereinafter), "AEROSIL 130", "AEROSIL 300", "AEROSIL 50", "AEROSIL 200FAD", "AEROSIL 380" (and above). , Made by Nippon Aerosil Co., Ltd.) and the like.

Fluorine-containing compound The fluorine-containing compound present on the surface of silica-based fine particles has [-Si (OR) ₃ ] on the terminal side of at least one of the main chains made of perfluoropolyether (where R is hydrogen or carbon number 1). It is a compound containing a functional group represented by (1) to 10 alkyl groups.

In the present invention, as described above, a polymer having a perfluoropolyether as a main chain can be used. By using such a polymer having a perfluoropolyether as a main chain, it is possible to secure a chain length equivalent to or longer than C8 without containing a structure like C8 fluorotelomer (C8 telomer), which may cause environmental pollution. High water repellency and oil repellency can be obtained. Further, the presence of the ether bond in the main chain makes it possible to firmly coat the surface of the silica-based fine particles.

More specifically, the fluorine-containing compound used in the present invention has the following general formula (1):
X-CF ₂ -O- (Cn F _2n O) m-CF _{2 -} X ... (1)
The compound represented by is preferably used.

X in the above general formula is a terminal portion containing an alkoxysilane functional group [-Si (OR) ₃ ], and a perfluoropolyether having a functional group A can also be referred to as a perfluoropolyether silane.

Further, n and m in the above general formula are natural numbers that are independent of each other, and their values are not particularly limited. In particular, n is preferably 1 or more and 7 or less. m is preferably 7 or more and 100 or less. By setting it within such a range, the fine particles in which the surface of the silica-based fine particles is coated with the fluorine compound can exhibit high water repellency and oil repellency.

The functional group A in the fluorine-containing compound is [-Si (OR) ₃ ] as described above (however, the three Rs are the same or different from each other and represent hydrogen or an alkyl group having 1 to 10 carbon atoms). It is a functional group represented.

In particular, when R is an alkyl group, it is preferably an alkyl group having 1 to 10 carbon atoms (particularly a linear alkyl group), and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group.

Further, all three Rs of the functional group A may be different, or some or all of them may be the same. When at least one of the three OR groups in the functional group is bonded to the silicon of the silica-based fine particles, it becomes a fluorine-containing group and can be firmly bound to the silica-based fine particles. More preferably, when all two or three OR groups of the functional groups are bonded to the silica-based fine particles, the immobilization can be performed more strongly.

In particular, X in the above general formula may contain a functional group A. Therefore, all X may be a functional group A, or a part of X may be another functional group as long as the effect of the present invention is not impaired.

Further, the functional group A may be directly bonded to the main chain [-CF ₂ -O- (CF ₂ O) _p- (CF ₂ CF ₂ O) _q -CF _2- ] composed of perfluoropolyether. However, it may be bonded via a linker portion. The linker section specifically links CF ₂ and the functional group A in the above-mentioned general formula of perfluoropolyether. Examples of such a linker portion include an oxyalkylene group [-OR ^{1-O-] (R 1 indicates} an alkylene group), an ether bond [-O-], and an ester bond [-C (= O). O-], amide bond [-CONH-], urethane bond [-COHN-O-] and the like can be mentioned.

In the present invention, it is preferable that the linker portion contains an amide bond (-CONH-) because it is particularly easy to synthesize. Further, it is more preferable to contain —C (= O) NH— (CH ₂ ) _k − as the linker moiety. That is, it is preferable that X in the above-mentioned general formula of perfluoropolyether is, for example, −C (= O) NH— (CH ₂ ) _k —Si (OR) ₃ .

Therefore, as a suitable polymer having a perfluoropolyether as a main chain, the following general formula (2):
(RO) ₃ Si- (CH ₂ ) _k -NHC (= O) -CF ₂ -O- (CF ₂ O) _p- (CF ₂ CF ₂ O) _q -CF ₂ -C (= O) NH- ( CH ₂ ) _k -Si (OR) ₃ ... (2)
Fluorine-containing compounds shown in 1.

Here, k, p, and q are independent natural numbers. The value of k is preferably 1 to 6, and more preferably 2 to 3. When the value of k exceeds 6, it becomes difficult to coat the surface of the silica-based fine particles with the fluorine-containing compound. The sum of p and q corresponds to m in the general formula X-CF _{2 -} O- (Cn F _2n O) _m -CF ₂ -X. Further, (CF ₂ O) and (CF ₂ CF ₂ O) are defined as n = 1 and n = 2, respectively, in the above general formula.

The molecular weight of the polymer having perfluoropolyether as a main chain, which is a fluorine-containing compound, is not particularly limited, but the number average molecular weight measured by gel permeation chromatography is preferably 500 to 5000, more preferably 1000 to 3000. Of these, 1200 to 2500 are the most preferable. If the number average molecular weight exceeds 5000, it may be difficult to dissolve the polymer in a water-soluble organic solvent. If the polymer cannot be dissolved in a water-soluble organic solvent, for example, when the R of the functional group A is an alkyl group, the hydrolysis reaction for substituting the OR group with an OH group becomes difficult to proceed. If the OR group cannot be replaced with an OH group, the formation of a siloxane bond between the functional group A and the OH group on the surface of the silica-based fine particles does not proceed as described later, and the polymer is firmly bonded and coated on the surface of the silica-based fine particles. It becomes difficult. Further, if any of the OR groups cannot be replaced with an OH group, the dehydration condensation reaction between the functional groups A is less likely to occur, and the polymer is less likely to be long-chained, resulting in a decrease in water repellency and oil repellency. be.

(2-2) Method for producing fluorine-containing composite particles
The method for producing the fluorine-containing composite particles is not particularly limited. For example, the fluorine-containing compound may be used for silica-based fine particles, and a coating layer containing the fluorine-containing compound may be formed on the surface of the silica-based fine particles according to a known coating method, granulation method, or the like. In particular, the particles of the present invention can be suitably prepared by a production method including a step (coating step) of mixing silica-based fine particles or a dispersion thereof with a solution of a fluorine-containing compound.

The silica-based fine particles may be mixed with the solution of the fluorine-containing compound as they are, but are preferably mixed with the solution in the form of a dispersion liquid in terms of obtaining higher dispersibility. That is, a dispersion liquid in which silica-based fine particles are dispersed in a solvent can be preferably used.

As the solvent in this case, any solvent can be used as long as the silica-based fine particles are not dissolved or deteriorated. For example, in addition to water, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbon solvents such as methylcyclohexane and cyclohexane, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methylethylketone and acetone. , Isopropyl alcohol, organic solvents such as alcoholic solvents such as modified ethanol can be used. In particular, any of water, a water-soluble organic solvent, or a mixed solvent thereof can be preferably used. The water-soluble organic solvent is not limited, and examples thereof include methanol, ethanol, 2-propanol, propylene glycol monomethyl ether, and the like.

The content of the silica-based fine particles in the dispersion liquid may be usually set within the range of about 1 to 50% by weight from the viewpoint of the dispersibility of the silica-based fine particles in the dispersion liquid, but is not limited thereto.

Further, a pH adjuster may be added to the dispersion, if necessary. As the pH adjuster, an acid such as acetic acid or hydrochloric acid, or a base such as sodium hydroxide or ammonia can be appropriately used.

A solution of the fluorine-containing compound can be suitably prepared by dissolving the fluorine-containing compound in a solvent.

Examples of the fluorine-containing compound include the above 1. The compound shown in 1 can be preferably used. In this case, as the fluorine-containing compound used as a raw material, it is more preferable to use a fluorine-containing compound in which at least one of the three Rs of the functional group A is hydrogen (H). By containing an OH group in the functional group on at least one terminal side of the polymer having a perfluoropolyether as a main chain, a siloxane bond is formed with the OH group on the surface of the silica-based fine particles by a dehydration condensation reaction, and the surface of the silica-based fine particles is formed. It becomes easy to firmly bond the polymer to the coating. Furthermore, by having an OH group at the end of the polymer, a siloxane bond (that is, a fluorine-containing group) can be formed by a dehydration condensation reaction with an OH group on the surface of silica-based fine particles without using a water-soluble organic solvent. can.

Further, even when all the Rs of the functional groups A of the fluorine-containing compound used as a raw material are alkyl groups, the OR group is converted into an OH group by a hydrolysis reaction by using a water-soluble organic solvent in the coating step. A siloxane bond can be formed by a dehydration condensation reaction with an OH group on the surface of silica-based fine particles. As a result, the fluorine-containing compound can be strongly fixed to the surface of silica-based fine particles as a fluorine-containing group.

The polymer may have a functional group A on one terminal side, but it is more preferable to have a functional group A on both terminal sides. By having the functional groups A on both end sides of the polymer, in some polymers, both ends are bonded to the silica-based fine particles to be in a stronger state. Further, in some polymers, one end is bonded to silica-based fine particles, and the other end is bonded to the end of another polymer to lengthen the chain. Therefore, as a result of increasing the area of the perfluoropolyether on the surface of the silica-based fine particles, it becomes possible to exhibit higher water repellency and oil repellency.

As the solvent in the above solution, water, a water-soluble organic solvent or a mixed solvent thereof can be preferably used. The water-soluble organic solvent is not particularly limited as long as it is a solvent miscible with water such as methanol, ethanol, 2-propanol, propylene glycol monomethyl ether and the like. By reacting in an aqueous system in this way, it becomes possible to form a siloxane bond more reliably as described above.

The content of the fluorine-containing compound in the solution is not particularly limited, but is generally set within the range of 2 to 30% by weight, particularly 5 to 30% by weight, and more preferably 5 to 20% by weight.

When the silica-based fine particles or the dispersion liquid thereof and the solution of the fluorine-containing compound are mixed, the ratio of the silica-based fine particles to the solution may be appropriately set according to the desired coating amount of the fluorine-containing compound, and in particular, the above-mentioned It is preferable to adjust so that the coating amount is as shown.

Further, in the present invention, it is particularly preferable to further include a step of stirring the mixed solution after mixing the two. By stirring the mixture, a part or all of the functional group A can sufficiently react with the silica on the surface of the silica-based fine particles or the functional group on the surface of the silica to surely form a siloxane bond.

The stirring conditions are not particularly limited. For example, the stirring temperature is usually about 30 to 80 ° C, preferably 40 to 70 ° C. The stirring time is usually about 1 to 96 hours, preferably 6 to 84 hours. The stirring may be performed with a commercially available stirring device.

After the stirring is completed, the particles of the present invention can be obtained in the form of a slurry. Therefore, when the particles of the present invention are used for a predetermined purpose, they can be used as they are in the form of a slurry. Further, the slurry can be used in the form of a substantially dried powder after being subjected to treatments such as solid-liquid separation and washing as necessary. It can also be used in the form of a dispersion obtained by further dispersing the powder in a solvent. In addition, it is also possible to use it in the form of a dispersion liquid obtained by dispersing the cake obtained by solid-liquid separation of the slurry in another solvent.

(2-3) Method for Forming Anti-Adhesion Layer The method for forming the anti-adhesion layer is not particularly limited, but for example, a step of applying a coating liquid in which fluorine-containing composite particles are dispersed in a solvent to a substrate and drying the substrate is performed. The method including can be preferably adopted.

As the coating liquid, the slurry, dispersion liquid or the like described in (2-2) above can be used. Therefore, as the solvent used for the coating liquid, for example, in addition to water, various organic solvents can be used, but in the present invention, 1) water, 2) water-soluble organic solvent or 3) a mixed solvent thereof is used. It can be suitably used. As the water-soluble organic solvent, alcohols such as methanol and ethanol can be preferably used.

The content of the fluorine-containing composite particles in the coating liquid is not particularly limited, but is generally set within the range of 2 to 30% by weight, particularly 5 to 30% by weight, and more preferably 5 to 20%. ..

The method of applying the coating liquid to the surface of the base material may follow a known method, for example, a known method such as roll coating, gravure coating, bar coating, doctor blade coating, comma coater, part coating, brush coating, and spraying. Can be adopted.

After applying the coating liquid, the solvent may be removed by drying. The drying may be either natural drying or heat drying. In the case of heating and drying, it is usually preferably about 100 to 200 ° C, particularly preferably 140 to 180 ° C.

(3) Primer layer A fluorine-containing composite can be directly laminated on the base material, but in the case of a base material to which it is difficult to adhere, a primer layer may be formed between the base material and the silica fine particles. When the silica fine particles are laminated on the base material via the primer layer, the silica fine particles are firmly attached or adhered to the base material, so that the silica fine particles are difficult to peel off.

(3-1) Primer component The primer component used for the primer layer is not particularly limited and can be appropriately selected depending on the type of the base material and the like. In particular, the resin components shown below can be used as the primer components.

For example, low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear (linear) low-density polyethylene resin, polypropylene resin, polyester resin, polystyrene resin, epoxy resin, nitrocellulose resin, urethane resin, Melamine-based resin, ethylene-vinyl acetate copolymer, ionoma-resin, ethylene-acrylic acid copolymer, acrylic-salt vinegar bipolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, Polyethylene-based resins such as ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene are used as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumar. In addition to acid-modified polyolefin resins modified with unsaturated carboxylic acids such as acids and itaconic acids, polyvinyl acetate resins, poly (meth) acrylic resins, polyacrylonitrile resins, polyvinyl chloride resins, and other heat-adhesive resins. , These blend resins, copolymers containing a combination of the monomers constituting them, modified resins and the like can be used. For example, a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer or the like can also be preferably used.

(3-2) Filled particles The primer layer may contain filled particles. By including the packed particles in the primer layer, the surface area of the primer layer is increased, and the amount of silica fine particles coated with the fluorine compound described later can be increased, so that further higher water repellency and oil repellency can be exhibited. can.

The type of the packed particles is not particularly limited, but packed particles containing at least one of an organic component and an inorganic component can be adopted.

Examples of the inorganic component include 1) metals such as aluminum, copper, iron, titanium, silver and calcium or alloys or intermetal compounds containing these, and 2) silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, iron oxide and the like. Oxides, 3) inorganic acid salts or organic acid salts such as calcium phosphate and calcium stearate, 4) glass, 5) aluminum nitride, boron nitride, silicon carbide, silicon nitride and other ceramics can be preferably used.

Examples of the organic component include acrylic resin, urethane resin, melamine resin, amino resin, epoxy resin, polyethylene resin, polystyrene resin, polypropylene resin, polyester resin, cellulose resin, vinyl chloride resin, and polyvinyl. Organic polymer components (or resin components) such as alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, polyacrylonitrile, and polyamide can be preferably used.

As the packed particles, in addition to particles composed of an inorganic component or particles (powder) composed of an organic component, particles (powder) containing both an inorganic component and an organic component can be used. Among these, it is more preferable to use at least one of acrylic resin particles, hydrophilic silica particles, calcium phosphate particles, charcoal powder, calcined calcium particles, unfired calcium particles, calcium stearate particles and the like.

Among these packed particles, filled particles composed of organic components are preferable, and resin beads are more preferable. In particular, in the present invention, it is preferable to include at least one of polyethylene-based resin beads, polypropylene-based resin beads, and acrylic-based resin beads.

The average particle size of the packed particles is not particularly limited, but is usually 10 to 60 μm. The average particle size here means that the particle size of 20 packed particles is measured one by one in a field image in which the contour of the packed particles is observed using a scanning electron microscope, and the particle size and particle size distribution are obtained. It is a thing. Further, such filled particles may be substantially uniform in size, or particles having different particle diameters may be mixed and used.

The content of the packed particles in the primer layer can be appropriately set according to the type and particle size of the packed particles to be used, and can be, for example, in the range of 5 to 50% by weight, but is not limited thereto. ..

(3-3) Method for Forming Primer Layer When forming a primer layer, for example, a method including a step of applying a primer coating solution containing a primer component to the surface of a substrate and drying it can be preferably adopted. In this case, when the filling particles are contained in the primer layer, the filling particles may be mixed in the primer coating liquid.

Examples of the solvent used for the primer coating solution include water, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbon solvents such as methylcyclohexane and cyclohexane, and esters such as ethyl acetate and butyl acetate. A system solvent, a ketone solvent such as methyl ethyl ketone and acetone, and an organic solvent such as an alcohol solvent such as isopropyl alcohol and modified ethanol can be used.

The content of the primer component in the primer coating liquid is not particularly limited, but is generally set within the range of 10 to 80% by weight, particularly 15 to 40% by weight, and more preferably 20 to 30% by weight. ..

When the filled particles are blended, the content of the filled particles in the primer coating liquid is not particularly limited, but is generally 5 to 50% by weight, particularly 10 to 40% by weight, and further 10 to 30% by weight. It is preferable to set it within the range of.

The method of applying the primer coating liquid to the surface of the base material may follow a known method, for example, known roll coating, gravure coating, bar coating, doctor blade coating, comma coater, part coat, brush coating, spray and the like. Any method can be adopted.

After applying the primer coating solution to the substrate, the solvent may be removed by drying. The drying may be either natural drying or heat drying. In the case of heating and drying, it is usually preferably about 100 to 200 ° C, particularly preferably 140 to 180 ° C.

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

Example 1
(1) Preparation of base sheet As packed particles, 15 parts by weight of polymethyl methacrylate beads (product name "MBX-20" manufactured by Sekisui Plastics Co., Ltd., average particle size: 20 μm, melting point: 250 to 270 ° C.) are polyester-based. A base coat agent was prepared by adding to 100 parts by weight of a thermoplastic resin solution (solvent: toluene solid content: 20 wt%) and stirring at room temperature for 30 minutes. This undercoating agent is applied to the surface of a commercially available biaxially stretched polyethylene terephthalate film (abbreviated as "PET") having a thickness of 50 μm so as to have a weight of 3.5 g / m ² after drying using bar coater # 8. Subsequently, the substrate sheet was prepared by laminating a primer layer on a PET film by heating and drying in an oven at 160 ° C. for 10 seconds to evaporate toluene.

(2) Preparation of fluorine-containing composite particles 30.0 g of hydrophilic silica fine particles with a BET value of 200 m ² / g (AEROSIL200 manufactured by Nippon Aerosil Co., Ltd., average particle diameter D50 = 12 nm) is added to an ethanol-based solvent (Gordo Co., Ltd., GS Arco). EP-7) Dispersed in 626.0 g. Next, 4.0 g of acetic acid and 100.0 g of pure water were added thereto, and the mixture was stirred with a glass rod for 3 minutes to prepare a dispersion.
Separately from this, as a fluorine-containing compound, a perfluoropolyethersilane represented by the following formula (1) (the average of p + q is 14, the number average molecular weight is 2000, k is 3, and R is an ethyl group) 24. 0 g was prepared and 216.0 g of ethanol was mixed to prepare a mixed solution containing perfluoropolyethersilane.

(RO) ₃ Si- (CH ₂ ) _k -NHC (= O) -CF ₂ -O- (CF ₂ O) _p- (CF ₂ CF ₂ O) _q C (= O) NH- (CH ₂ ) _k -Si (OR) ₃ ... (1)

Then, 240.0 g of the mixed solution was added to the dispersion, and the mixture was stirred with a glass rod for 3 minutes. The obtained mixed slurry was stirred under the condition of 50 ° C. for 3 days. In this way, a coating liquid containing fluorine-containing composite particles was obtained. The weight (coating amount) of the fluorine-containing compound (the above-mentioned perfluoropolyethersilane) (hereinafter, also referred to as “polymer”) in the fluorine-containing composite particles was 44% by mass.

(3) Preparation of laminated body The coating liquid obtained in (2) above is coated on the surface on which the primer layer of the base material sheet is laminated by using bar coater # 6, and is placed in an oven at 180 ° C. By heating and drying for 10 seconds to evaporate ethanol, a sample of the laminate including the substrate sheet and the adhesion prevention layer was obtained. The target lamination amount of the fluorine-containing composite particles was set to 1.2 g / m ² as the weight after drying.

Example 2
A laminate was obtained in the same manner as in Example 1 except that the target lamination amount of the fluorine-containing composite particles after drying in the laminate was set to 2.4 g / m ² .

Example 3
The mixed solution containing perfluoropolyethersilane added to the silica-based fine particle-dispersed ethanol solution was 48.0 g, the weight of the polymer in the fluorine-containing composite particles was 62% by mass, and the dried fluorine compound in the laminate was coated with silica. A laminated body was obtained in the same manner as in Example 1 except that the target laminated amount of the system fine particles was set to 1.2 g / m ² .

Example 4
The weight of the polymer in the fluorine-containing composite particles is 62% by mass, with 48.0 g of the mixed solution containing perfluoropolyethersilane added to the silica-based fine particle-dispersed ethanol solution, and the target stacking amount of the fluorine-containing composite particles after drying in the laminate. A laminated body was obtained in the same manner as in Example 1 except that the value was 2.4 g / m ² .

Example 5
A laminate was obtained in the same manner as in Example 1 except that the target lamination amount of the fluorine-containing composite particles after drying in the laminate was set to 4.8 g / m ² .

Comparative Example 1
5 g of silica-based fine particles (product name "AEROSIL200" manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 200 m ² / g, average primary particle diameter 12 nm) are placed in a reaction vessel, and a commercially available fluorine compound is stirred in a nitrogen gas atmosphere. 500 g of the surface treatment agent containing the above was sprayed, and then the mixture was stirred at 200 ° C. for 30 minutes and then cooled. As a result, silica-based fine particles coated with a fluorine compound were obtained.
As the surface treatment agent, an aqueous dispersion (solid content concentration) of a copolymer of polyfluorooctyl methacrylate, 2-N, N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate and 2,2'-ethylenedioxydiethyldimethacrylate. : 20% by weight) was used.
The silica-based fine particles coated in this manner were dispersed in 100 ml of ethanol to prepare a coating liquid. A laminate was prepared in the same manner as in Example 1 using this coating liquid. The target lamination amount of the silica-based fine particles coated with the fluorine compound after drying was set to 1.2 g / m ² .

Comparative Example 2
The amount of perfluoropolyethersilane in the mixed solution containing perfluoropolyethersilane is 12.0 g, the weight of the polymer in the fluorine-containing composite particles is 28% by mass, and the target stacking amount of the fluorine-containing composite particles after drying in the laminate is 28% by mass. A laminated body was obtained in the same manner as in Example 1 except that the value was 1.2 g / m ² .

Comparative Example 3
A laminate was obtained in the same manner as in Example 1 except that the target lamination amount of the fluorine-containing composite particles after drying in the laminate was set to 0.6 g / m ² .

Comparative Example 4
The weight of the polymer in the fluorine-containing composite particles is 62% by mass, with 48.0 g of the mixed solution containing perfluoropolyethersilane added to the silica-based fine particle-dispersed ethanol solution, and the target stacking amount of the fluorine-containing composite particles after drying in the laminate. A laminated body was obtained in the same manner as in Example 1 except that the value was 0.6 g / m ² .

Test Example 1 (sliding angle)
The sliding angle at 25 ° C. was measured for the sample of the laminated body obtained in Examples and Comparative Examples. The results are shown in Table 2.
The device shown in FIG. 2 was used as the method for measuring the sliding angle. As shown in FIG. 2A, an electric lab jack 30 (autolab jack ALJ200-H, manufactured by AS ONE) and a base 20 are installed, and the width is 30 cm x length so as to straddle the electric lab jack 30 and the base 20. An aluminum plate 36 having a size of 70 cm and a thickness of 3 mm was placed on the plate 36, and a digital angle meter 38 (digital angle meter mini DPM-1, manufactured by Toei Kogyo Co., Ltd.) was placed on the plate 36. At this time, the power of the digital goniometer 38 was turned on, and the elevating height of the electric lab jack 30 was adjusted so that the plate 36 was horizontal (tilt 0 °). The side 32 on the side of the plate 36 in contact with the base 20 and the base 20 were fixed with commercially available tape so that the plate 36 did not move in the horizontal direction. On the other hand, it was decided not to fix the side of the plate 36 supported by the electric lab jack 30. As a result, as shown in FIG. 2B, when the electric lab jack 30 is jacked up, the plate 36 is rubbed while being in constant contact with the upper end portion 34 of the electric lab jack 30, and the plate 36 is tilted. The distance Y between one side 32 of the plate 36 fixed to the base 20 and the upper end portion 34 of the electric lab jack 30 was set to 50 cm.
Next, the coating liquid was applied to the laminate 1 obtained in each Example and Comparative Example on the plate 36, and the plate 36 was installed with the side on which the fine particles were laminated face up. Commercially available tapes were attached to the four corners of the laminate 1 and fixed to the plate 36.
Next, a micropipette tip (ibis pipette tip, manufactured by Ibis) 40 was attached to a micropipette (pipetman P20, manufactured by GILSON), 20 μl of the sample 42 was taken, and the sample 42 was gently dropped onto the laminate 1. Here, as the sample 42, pure water, oleic acid (NAA-34, manufactured by Nichiyu Co., Ltd., content: 98% by mass or more as fatty acid) and edible olive oil (AJINOMOTO olive oil) were used.
After that, the electric lab jack 30 was jacked up at a speed of 1 cm / sec, the plate 36 was tilted, and when it was confirmed that the sample 42 had begun to roll visually, the jacking up was stopped and displayed on the digital angle meter 38. The angle was recorded as the sliding angle.
In each Example and Comparative Example, each sample was measured 5 times to determine the average sliding angle. The results are shown in Table 2. In addition, even if the plate 36 was tilted up to 45 degrees, the sample 42 was partially or wholly attached to the laminate 1 and did not roll, so that the jack-up was stopped at 45 degrees.

Test Example 2 (contact angle)
The contact angle at 25 ° C. was measured for the sample of the laminate obtained in each Example and Comparative Example. Specifically, the surface on which the coating liquids of each sample are laminated is used as the test surface, and a contact angle measuring device (solid-liquid interface analyzer "Drop Master 300" manufactured by Kyowa Interface Science Co., Ltd.) is used in the same manner as in Test Example 1. Pure water, oleic acid and olive oil (5 μl) were added dropwise to the test surface as samples, and the contact angle of each sample was measured. In the measurement result, the N number was set to 5 times, and the average value was used as the contact angle. The results are shown in Table 3.

Test Example 3 (Maintenance of water repellency and oil repellency)
The sustainability of water repellency and oil repellency was examined for each sample obtained in Examples and Comparative Examples. Specifically, the surface on which the coating liquid of each sample was laminated was used as the test surface, and a few drops of olive oil and oleic acid were dropped as samples, and the rolling property of each sample was observed after being left at 25 ° C. for 24 hours. .. As the olive oil, a commercially available product "AJINOMOTO olive oil (edible olive oil), manufactured by Ajinomoto Co., Inc.) was used. Twenty-four hours after dropping the sample, tilt each sample to 20 degrees to maintain water repellency and oil repellency, and mark the sample rolled on the sample as "○", so that the oil repellency is slightly reduced and a tail is drawn. The one that rolled in was marked with "Δ", and the one in which the oil repellency was significantly reduced and the sample did not roll was marked with "x". The results are shown in Table 4.

Test Example 4 (friction resistance)
The friction resistance was examined for each sample obtained in Examples and Comparative Examples. Specifically, each sample was cut into a size of 220 mm × 30 mm, and the surface on which the coating liquid of each sample was laminated was designated as the test surface and No. After rubbing the test surface a predetermined number of times with a 428 Gakushin-type dyeing friction fastness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the state was observed by dropping olive oil to maintain water repellency and oil repellency. The test conditions are as follows: Attach an additional weight to a stainless steel friction element (surface radius R45 mm, 20 mm x 20 mm) so that the total load is 11.8 N, install it on a fixed test surface, and have a friction distance of 100 mm and a friction speed of 30 reciprocations. As / min, 40 round trips, 80 round trips, 120 round trips, and 160 round trips were performed. The evaluation standard is that after rubbing the test surface, each sample is tilted to 20 degrees, and the sample that rolls on the sample while maintaining oil repellency is marked with "○", and the oil repellency is slightly reduced and it rolls like a tail. The sample was marked with "Δ", and the sample with significantly reduced oil repellency and almost no rolling was marked with "x". The results are shown in Table 5.

As shown in Table 2, all the examples showed a slightly lower sliding angle than the comparative example with respect to the sliding angle of water, but the sliding angle of the oleic acid or olive oil was extremely lower in the examples. Had horns. That is, it was confirmed that the laminate of the present invention has high water repellency and oil repellency.

Further, as shown in Table 3, all the examples had a contact angle of around 150 degrees (particularly 150 degrees or more), but the contact angles were significantly reduced in Comparative Examples 2 to 4. In this respect as well, it was confirmed that the laminate of the present invention has high water repellency and oil repellency.

As shown in Table 4, even after 24 hours had passed since the sample was dropped, the sample rolled in all the examples, but the olive oil did not roll in all the comparative examples. As described above, it was confirmed that the laminate of the present invention can exhibit higher water repellency and oil repellency than the conventional one for a relatively long period of time.

Further, as shown in Table 5, the sample rolled in all the examples even after rubbing the test surface 160 times in a reciprocating manner, but in Comparative Examples 2 to 4, the sample did not roll after rubbing 80 times in a reciprocating manner. rice field. Further, in Comparative Example 1, the water repellency and oil repellency as in the examples were not observed after rubbing the test surface 80 times back and forth. In this respect, it was confirmed that the laminate of the present invention can maintain water repellency and oil repellency more than before.

As is clear from the above results, the laminate of the present invention can exhibit higher water repellency and oil repellency than the conventional laminate. In particular, it can be seen that high oil repellency can be exhibited even for specific oil components such as oleic acid and olive oil.

Claims (3)

A laminate containing a base material and an adhesion prevention layer,
(1) The adhesion prevention layer contains fluorine-containing composite particles, and the adhesion prevention layer contains fluorine-containing composite particles.
(2) Fluorine-containing composite particles are composite particles in which the surface of the silica-based fine particles is coated with at least one of 1) a fluorine-containing compound and 2) a fluorine-containing group formed by siloxane bonding with silicon of the silica-based fine particles. And,
The fluorine-containing compound is [-Si (OR) ₃ ] on the terminal side of at least one of the main chains made of perfluoropolyether (however, the three Rs are the same or different from each other and have hydrogen or 1 to 10 carbon atoms. It is a compound containing a functional group represented by () and is a compound containing an alkyl group.
(3) The laminated weight of the silica-based fine particles coated with the fluorine compound per unit area of the surface of the base material is 0.7 to 5.0 g / m ² .
(4) A primer layer is provided between the substrate and the adhesion prevention layer, and the primer layer further contains packed particles having an average particle size of 10 to 60 μm.
A laminated body characterized by that. The laminate according to claim 1 , wherein the silica-based fine particles have an average primary particle diameter of 3 to 500 nm. The laminate according to claim 1 or 2 , wherein the base material is at least one of a resin, a rubber, a metal material, an inorganic material, and a composite material containing these.

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