WO2017057403A1 - Method for manufacturing antifouling sheet - Google Patents

Abstract

Provided is a method for manufacturing an antifouling sheet having an antifouling layer, the method comprising the following sequential steps of: (1) preparing an antifouling composition which contains a tetrafunctional silane compound having a specific structure as component (A), a trifunctional silane compound having a specific structure as component (B), a metal catalyst as component (C), and an organic solvent as component (D); (2) coating a support with the antifouling composition prepared in step (1) to form a coating film; and (3) heating, at a temperature lower than or equal to the boiling point of the organic solvent, the coating film formed on the support in step (2) to form an antifouling layer.

Description

Method for producing antifouling sheet

The present invention relates to a method for producing an antifouling sheet having an antifouling layer.

In general, it is installed in windshields for buildings, windshields for automobiles, windshields for vehicles, aircraft, ships, etc., water tanks, bottom windows, films for preventing marine organisms from sticking to the bottom, road panels such as soundproof walls, bathrooms, etc. In addition, it is desirable that the surface of a molded product such as a mirror, a glass container, or a glass decorative article does not adhere to the surface such as water droplets, scratches, and dirt.
The surface of such a molded product is provided with water repellency and antifouling properties by coating with a film made of an antifouling substance, or by applying an antifouling sheet. Yes.
For example, Patent Document 1 discloses a substrate such as glass by a laminate having a base layer formed of an inorganic compound and a water-repellent film that covers the surface of the base layer and is formed of a fluorine-containing compound. A water-repellent film-coated article coated with a material is disclosed.

JP 2010-285574 A

However, since the water-repellent coated article described in Patent Document 1 has a water-repellent film formed from a fluorine-containing compound, it is not preferable from the viewpoint of environmental protection.
Further, the antifouling layer of the antifouling sheet is also required to have a good surface condition and curability.
By forming a coating film using an antifouling composition containing a tetrafunctional silane compound having a specific structure, a trifunctional silane compound having a specific structure, and a metal catalyst, the inventors have obtained a surface state. And found that an antifouling layer having good curability can be formed.
On the other hand, the present inventors said that gelation may occur in the process of forming the antifouling layer from the coating film comprising the antifouling composition, and the surface state of the antifouling layer may be deteriorated. I found a problem.

An object of the present invention is to provide a method for producing an antifouling sheet having an antifouling layer having a good surface state and curability.

The inventors of the present invention formed a coating film using an antifouling composition containing a tetrafunctional silane compound having a specific structure, a trifunctional silane compound having a specific structure, a metal catalyst, and an organic solvent. The inventors have found that the above problems can be solved by initiating and accelerating the curing reaction of the coating film under the above conditions, thereby completing the present invention.
That is, the present invention provides the following [1] to [10].
[1] A method for producing an antifouling sheet having an antifouling layer, comprising the following steps (1) to (3) in this order.
Step (1): Step of preparing an antifouling composition containing the following components (A) to (D): Component (A): tetrafunctional silane compound represented by the following general formula (a) Si (OR ¹ _P (X ¹ ) _4-p (a)
[In the general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (b)
[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
Component (C): Metal catalyst (D) Component: Organic solvent Step (2): Step (3) for coating the antifouling composition prepared in Step (1) on a support to form a coating film: Step (2) of forming the antifouling layer by heating the coating film on the support formed in step (2) at a temperature not higher than the boiling point of the organic solvent [2] The organic solvent is butyl acetate, butanol, cyclohexanone, The method for producing an antifouling sheet according to the above [1], which is at least one selected from the group consisting of methyl isobutyl ketone, toluene, and mineral spirits.
[3] The method for producing an antifouling sheet according to the above [1] or [2], wherein the heating temperature in the step (3) is a boiling point of the organic solvent −10 ° C. or lower.
[4] The method for producing an antifouling sheet according to any one of the above [1] to [3], wherein in the step (1), the component (B) contains at least one of the following components (B-1).
Component (B-1): Trifunctional silane compound represented by the following general formula (b-1) R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (b-1)
[In general formula (b-1), R ⁴ represents an alkyl group having 15 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3. ]
[5] The method for producing an antifouling sheet according to any one of the above [1] to [4], wherein in step (1), the component (B) contains at least one of the following components (B-2).
Component (B-2): Trifunctional silane compound represented by the following general formula (b-2) R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (b-2)
[In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3. ]
[6] The method for producing an antifouling sheet according to any one of [1] to [5], wherein in the step (1), the following condition (I) is further satisfied.
Condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 0.01 or more [7] In step (1), Furthermore, the method for producing an antifouling sheet according to the above [5] or [6], which satisfies the following condition (II).
Condition (II): Ratio of molar amount of component (B-1) to total molar amount of component (B-1) and component (B-2) [(B-1) / {(B-1) + (B -2)}] (molar ratio) is 0.020 or more [8] In step (1), the content of component (C) is 100 mol% in total of component (A) and component (B). 0.010 mol% or more and 50.000 mol% or less, The method for producing an antifouling sheet according to any one of the above [1] to [7].
[9] The method for producing an antifouling sheet according to any one of [1] to [8], wherein the support is a substrate or a release material.
[10] In the step (1), an acid catalyst that is the component (E) is further contained, and the content of the component (E) is 0.002% relative to 100 mol% in total of the components (A) and (B). The method for producing an antifouling sheet according to any one of [1] to [9], wherein the content is 010 mol% or more and 1.000 mol% or less.

According to the present invention, it is possible to provide a method for producing an antifouling sheet having an antifouling layer with good surface condition and curability.

It is sectional drawing of an example of the antifouling sheet | seat which has a base material obtained by the manufacturing method of this embodiment. It is sectional drawing of an example of the antifouling sheet | seat which does not have the base material obtained by the manufacturing method of this embodiment.

[Production method of antifouling sheet]
The method for producing an antifouling sheet having an antifouling layer of the present invention comprises the following steps (1) to (3) in this order.
Step (1): Step of preparing an antifouling composition containing the following components (A) to (D): Component (A): tetrafunctional silane compound represented by the following general formula (a) Si (OR ¹ _P (X ¹ ) _4-p (a)
[In the general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (b)
[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
Component (C): Metal catalyst (D) Component: Organic solvent Step (2): Step (3) for coating the antifouling composition prepared in Step (1) on a support to form a coating film: The step of heating the coating film on the support formed in step (2) at a temperature not higher than the boiling point of the organic solvent to form an antifouling layer

In the antifouling sheet having an antifouling layer obtained by the production method of the present invention, the condensation reaction of the silane compounds in the antifouling composition described in the step (1) proceeds to become a polymer. As a result, an antifouling layer is formed.
Even when the antifouling composition having the same composition is used, the present inventors can prevent the antifouling formed from the coating film by a difference in the curing acceleration method of the coating film formed from the antifouling composition. We found that the state of the dirty layer changes. More specifically, when the step (3) is not introduced, it has been found that the coating film formed from the antifouling composition may be gelated in the process of forming the antifouling layer. .
In the above step (2), when the antifouling composition used in the present invention is applied on a support to form a coating film, the antifouling composition prepared in step (1) is dissolved in an organic solvent. Applied as a solution.
In the process of forming the antifouling layer, the inventors of the present invention applied the coating of the organic solvent by volatilization or evaporation and drying of the coating film before the coating reaction sufficiently proceeds. It was estimated that the film would gel.

Therefore, the present inventors have introduced the above step (3), whereby the organic solvent in the coating film formed from the antifouling composition is volatilized and / or evaporated from the coating surface side. It was noticed that the curing reaction of the coating film can be promoted before it becomes dry.
Further, the inventors have focused on the fact that by using a metal catalyst as the component (C), the condensation reaction between the silane compounds can be effectively advanced to further accelerate the curing reaction of the coating film.
As a result, the inventors have found that an antifouling layer having a good surface state can be formed while suppressing gelation of the coating film, and thus completed the present invention.
Hereinafter, the manufacturing method of the antifouling sheet of the present invention will be described.

<< Step (1) >>
Step (1) used in the present invention is a step of preparing an antifouling composition containing the components (A) to (D).

<Anti-fouling composition>
The antifouling composition used in step (1) is a tetrafunctional silane compound represented by the general formula (a) as the component (A), and a trifunctional represented by the general formula (b) as the component (B). A silane compound, a metal catalyst as the component (C), and an organic solvent as the component (D).
The antifouling composition preferably further contains an acid catalyst as the component (E), and contains other additives other than the components (A) to (E) as long as the effects of the present invention are not impaired. May be.
Hereinafter, each component contained in the antifouling composition used in step (1) will be described.

((A) component: tetrafunctional silane compound represented by general formula (a))
The antifouling composition used in the present invention contains a tetrafunctional silane compound represented by the following general formula (a) as the component (A).
Si (OR ¹ ) _p (X ¹ ) _4-p (a)
In the general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4.

Examples of the alkyl group that can be selected as R ¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, Examples thereof include an n-hexyl group, a neopentyl group, and a methylpentyl group. Among these, from the viewpoint of obtaining better curability, a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.
The alkyl group that can be selected as R ¹ may be either linear or branched, but is preferably linear.

The halogen atom that can be selected as X ¹ is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.
In addition, you may use the silane type compound represented by said general formula (a) individually or in combination of 2 or more types.
Moreover, as (A) component, it is preferable to contain the silane type compound whose p in the said general formula (a) is 4.

The content of the component (A) in the antifouling composition has a viewpoint of improving the curability of the antifouling layer formed from the antifouling composition, a viewpoint of obtaining a good surface state, and a high surface hardness. From the viewpoint of obtaining, the total of 100 mol% of the component (A) and the component (B) is preferably 0.80 mol% or more, more preferably 10.00 mol% or more, still more preferably 30.00 mol%. More preferably, it is 45.00 mol% or more, more preferably 55.00 mol% or more, still more preferably 65.00 mol% or more, and still more preferably 75.00 mol% or more. And preferably it is 98.00 mol% or less, More preferably, it is 96.00 mol% or less, More preferably, it is 94.00 mol% or less, More preferably, it is 90.00 mol% or less. In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

((B) component: trifunctional silane compound represented by general formula (b))
The antifouling composition used in the present invention contains a trifunctional silane compound represented by the following general formula (b) as the component (B) together with the component (A).
R ² Si (OR ³ ) _q (X ² ) _3-q (b)
In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3.

The alkyl group that can be selected as R ² has 1 to 24 carbon atoms.
When the carbon number of the alkyl group exceeds 24, the curability of the antifouling layer formed from the antifouling composition is poor. In addition, as the carbon number of the alkyl group increases, the antifouling composition tends to gel, and the surface state of the antifouling layer formed from the antifouling composition tends to deteriorate. From such a viewpoint, the carbon number of the alkyl group is preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less.
The carbon number of the alkyl group that can be selected as R ² does not include the carbon number of any substituent that the alkyl group may have.

Examples of the alkyl group that can be selected as R ² include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -Nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group , Tert-pentyl, methylpentyl, isohexyl, pentylhexyl, butylpentyl, and 2-ethylhexyl Groups and the like.
The alkyl group that can be selected as R ² may be either linear or branched, but from the viewpoint of improving the curability and surface state of the antifouling layer formed from the antifouling composition. The straight chain is preferable.

The alkyl group that can be selected as R ² may have a substituent.
Examples of such substituents include halogen atoms such as chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; amino group; cyano group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group A cycloalkyl group having 3 to 12 ring carbon atoms (preferably 6 to 10 ring carbon atoms); an aryl group having 6 to 12 ring carbon atoms; a heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom; A heteroaryl group having 6 to 12 ring atoms, an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms), an aryloxy group having 6 to 12 ring carbon atoms, and the like. The group may be further substituted.
However, the alkyl group that can be selected as R ² is preferably an alkyl group having no substituent.

The alkyl group that can be selected as R ³ and the halogen atom that can be selected as X ² are the same as the alkyl group that can be selected as R ¹ and the halogen atom that can be selected as X ^{1 in} the general formula (a). Is mentioned.
In addition, you may use the trifunctional silane type compound represented by said general formula (b) individually or in combination of 2 or more types.
The component (B) preferably contains a trifunctional silane compound in which q in the general formula (b) is 3.

The content of the component (B) in the antifouling composition used in the present invention is preferably 2.50 mol% or more, more preferably with respect to 100 mol% in total of the components (A) and (B). It is 5.00 mol% or more, More preferably, it is 10.00 mol% or more. Further, from the viewpoint of improving the surface state of the antifouling layer formed from the antifouling composition, from the viewpoint of improving curability, and from the viewpoint of obtaining high surface hardness, preferably 99.00 mol% or less, more Preferably it is 80.00 mol% or less, More preferably, it is 50.00 mol% or less, More preferably, it is 30.00 mol% or less, More preferably, it is 25.00 mol% or less. In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

(Condition (I))
The antifouling composition used in the present invention is preferably an antifouling composition satisfying the following condition (I) in the relationship between the component (A) and the component (B).
Condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 0.01 or more [(A) / (B) ] (Molar ratio) is 0.01 or more, the curability and surface hardness of the antifouling layer formed from the antifouling composition are excellent. From such a viewpoint, the [(A) / (B)] (molar ratio) is preferably 0.01 or more, more preferably 0.20 or more, still more preferably 2.00 or more, and still more preferably 3 .00 or more.
The [(A) / (B)] (molar ratio) is preferably 50.00 or less. When the [(A) / (B)] (molar ratio) is 50.00 or less, the proportion of the alkyl group represented by R ² in the component (B) can be prevented without extremely decreasing. The antifouling layer formed from the fouling composition has better water repellency. From such a viewpoint, the [(A) / (B)] (molar ratio) is more preferably 50.00 or less, further preferably 25.00 or less, still more preferably 12.50 or less, and still more preferably. Is 10.00 or less.

[(B-1) component: trifunctional silane compound represented by general formula (b)]
The antifouling composition used in the present invention contains, as the component (B), at least one component (B-1) that is a trifunctional silane compound represented by the following general formula (b-1). preferable.
R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (b-1)
In general formula (b-1), R ⁴ represents an alkyl group having 15 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3.

It is preferable for the alkyl group represented by R ⁴ to have 15 or more carbon atoms because an antifouling layer having a high water contact angle and a low water sliding angle can be obtained. From such a viewpoint, the R ⁴ is preferably 16 or more. Moreover, the preferable upper limit of the carbon number of the alkyl group represented by R ⁴ is the same as the preferable upper limit of R ² described above, preferably 22 or less, more preferably 20 or less, and still more preferably 18 or less. . Setting reasons of each of upper preferable values are also as described above for R ^2.
The carbon number of the alkyl group that can be selected as R ⁴ does not include the carbon number of any substituent that the alkyl group may have.
On the other hand, as described above, when the carbon number of the alkyl group represented by R ⁴ increases, the curability of the antifouling layer formed from the antifouling composition is inferior, and the antifouling composition is more easily gelled. The present inventors have found that the surface state of the antifouling layer formed tends to deteriorate.
However, by using the production method of the present invention, the antifouling composition can suppress gelation, and the surface state of the antifouling layer to be formed can be improved. Therefore, an antifouling composition containing at least one component (B-1) can be used as the component (B), and an antifouling layer having excellent curability and surface condition and excellent water repellency can be used. Obtainable.

Examples of the alkyl group that can be selected as R ⁴ include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n- Examples include docosyl group, n-tricosyl group, and n-tetracosyl group.
The alkyl group that can be selected as R ⁴ may be either linear or branched, but from the viewpoint of improving the curability and surface state of the antifouling layer formed from the antifouling composition. The straight chain is preferable. As the alkyl group that can be selected as R ⁴ , n-pentadecyl group or n-hexadecyl group is preferable from the viewpoint of curability and surface state of the antifouling layer, and from the viewpoint of obtaining better water repellency, An n-hexadecyl group, an n-pentadecyl group, or an n-octadecyl group is preferable.
The alkyl group that can be selected as R ⁴ may have a substituent. The substituent that the alkyl group that can be selected as R ⁴ has is as described above for the substituent that the alkyl group that can be selected as R ² has. However, the alkyl group that can be selected as R ⁴ is preferably an alkyl group having no substituent.

The alkyl group that can be selected as R ⁵ and the halogen atom that can be selected as X ³ are the same as the alkyl group that can be selected as R ¹ and the halogen atom that can be selected as X ^{1 in} the general formula (a). Is mentioned.
The trifunctional silane compounds represented by the general formula (b-1) may be used alone or in combination of two or more.
The component (B-1) preferably contains a trifunctional silane compound in which r in the general formula (b-1) is 3.

[(B-2) component: trifunctional silane compound represented by general formula (b-2)]
The antifouling composition used in the present invention contains at least one component (B-2) which is a trifunctional silane compound represented by the following general formula (b-2) as the component (B). preferable.
R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (b-2)
In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3.

The alkyl group that can be selected as R ⁶ has 1 to 3 carbon atoms.
When the carbon number of the alkyl group is within this range, the curability of the antifouling layer formed from the antifouling composition is excellent, and the surface hardness is also improved. The carbon number of the alkyl group that can be selected as R ⁶ does not include the carbon number of any substituent that the alkyl group may have.
Examples of the alkyl group that can be selected as R ⁶ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group or an ethyl group is preferable from the viewpoint of obtaining better water slidability. From the viewpoint of obtaining a higher surface hardness and a lower friction coefficient, a methyl group is more preferable.
The alkyl group that can be selected as R ⁶ may have a substituent. The substituent that the alkyl group that can be selected as R ⁶ has is as described above for the substituent that the alkyl group that can be selected as R ² has. However, the alkyl group that can be selected as R ⁶ is preferably an alkyl group having no substituent.

The alkyl group that can be selected as R ⁷ and the halogen atom that can be selected as X ⁴ are the same as the alkyl group that can be selected as R ¹ and the halogen atom that can be selected as X ^{1 in} the general formula (a). Is mentioned.
The trifunctional silane compounds represented by the general formula (b-2) may be used alone or in combination of two or more.
The component (B-2) preferably contains a trifunctional silane compound in which s is 3 in the general formula (b-2).

The antifouling composition used in the present invention more preferably contains both the component (B-1) and the component (B-2) as the component (B). (B) Component (B-1) and Component (B-2) are used together as component (B), so that the surface state and curability are better than when either of them is used alone, water repellency and water It is possible to form an antifouling layer having a good balance of properties such as good sliding properties and high surface hardness and low coefficient of friction.

When the component (B-1) and the component (B-2) are used as the component (B), the content of the component (B-1) in the antifouling composition is formed from the antifouling composition. From the viewpoint of improving the curability of the antifouling layer, from the viewpoint of obtaining a good surface state, and from the viewpoint of obtaining high surface hardness, a total of 100 components (A), (B-1) and (B-2) Preferably, it is 0.30 mol% or more, more preferably 0.50 mol% or more, still more preferably 1.00 mol% or more, still more preferably 2.00 mol% or more, and still more preferably with respect to mol%. 4.00 mol% or more, and preferably 36.00 mol% or less, more preferably 26.00 mol% or less, still more preferably 24.00 mol% or less, even more preferably 19.00 mol% or less. It is. In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

When the component (B-1) and the component (B-2) are used as the component (B), in the relationship between the component (A) and the component (B-1), The molar ratio [(A) / (B-1)] (molar ratio) of component A) is preferably 1.40 or more.
When the [(A) / (B-1)] (molar ratio) is 1.40 or more, the curability and surface hardness of the antifouling layer formed from the antifouling composition are excellent. From such a viewpoint, the [(A) / (B-1)] (molar ratio) is preferably 1.50 or more, more preferably 1.90 or more, still more preferably 2.10 or more, and still more preferably Is 2.50 or more, more preferably 5.00 or more, and still more preferably 6.00 or more.
The [(A) / (B-1)] (molar ratio) is preferably 300.00 or less. When the [(A) / (B-1)] (molar ratio) is 300.00 or less, the antifouling composition is present due to the presence of the alkyl group represented by R ⁴ in the component (B-1). The antifouling layer formed from a product has better water repellency. From such a viewpoint, the [(A) / (B-1)] (molar ratio) is more preferably 200.00 or less, still more preferably 150.00 or less, still more preferably 100.00 or less, more More preferably, it is 90.00 or less, More preferably, it is 50.00 or less, More preferably, it is 20.00 or less.

When the component (B-1) and the component (B-2) are used as the component (B), the content of the component (B-2) in the antifouling composition is formed from the antifouling composition. From the viewpoint of improving the curability of the antifouling layer, from the viewpoint of obtaining a good surface state, and from the viewpoint of obtaining high surface hardness, a total of 100 components (A), (B-1) and (B-2) Preferably, it is 0.50 mol% or more, more preferably 1.00 mol% or more, still more preferably 1.30 mol% or more, still more preferably 2.00 mol% or more, with respect to mol%, and Preferably it is 40.00 mol% or less, More preferably, it is 38.00 mol% or less, More preferably, it is 35.00 mol% or less, More preferably, it is 20.00 mol% or less. In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

When the component (B-1) and the component (B-2) are used as the component (B), in the relationship between the component (A) and the component (B-2), The molar ratio [(A) / (B-2)] (molar ratio) of the component A) is not particularly limited, and is preferably 1.00 or more, more preferably 4.00 or more. The [(A) / (B-2)] (molar ratio) is preferably 70.00 or less, more preferably 40.00 or less, and still more preferably 35.00 or less.

(Condition (II))
The antifouling composition used in the present invention is preferably an antifouling composition satisfying the following condition (II) in relation to the components (B-1) and (B-2).
Condition (II): Ratio of molar amount of component (B-1) to total molar amount of component (B-1) and component (B-2) [(B-1) / {(B-1) + (B -2)}] (molar ratio) is 0.020 or more When the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is 0.020 or more The antifouling layer formed from the antifouling composition has a low static friction coefficient and a dynamic friction coefficient, and is excellent in friction characteristics. Further, since the alkyl group represented by R ⁴ in the component (B-1) is appropriately present, the water contact angle of the antifouling layer formed from the antifouling composition is improved, and the water repellency is improved. Excellent. From such a viewpoint, the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is preferably 0.025 or more, more preferably 0.035 or more, and further Preferably it is 0.080 or more, More preferably, it is 0.180 or more, More preferably, it is 0.220 or more.
The upper limit of the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is not particularly limited, and the [(B-1) / {(B-1) + (B-2)}] (molar ratio) is preferably 0.995 or less, more preferably 0.990 or less, still more preferably 0.980 or less, and still more preferably 0.950 or less.

The antifouling composition used in the present invention contains (B-1) component and (B-2) component as a trifunctional silane compound so as to satisfy the above conditions (I) and (II). Thus, it is possible to achieve both a higher surface hardness and a lower coefficient of friction of the antifouling layer formed from the antifouling composition. Further, by including the component (B-2), an improvement in the weather resistance of the antifouling layer formed from the antifouling composition can be expected.

Further, the antifouling composition used in the present invention is the sum of the components (B-1) and (B-2) in the relationship of the components (A), (B-1) and (B-2). The ratio of the molar amount of the component (A) to the molar amount [(A) / {(B-1) + (B-2)}] (molar ratio) is preferably 0.50 or more, more preferably 0.90. That's it. The [(A) / {(B-1) + (B-2)}] (molar ratio) is preferably 25.00 or less, more preferably 20.00 or less.

((C) component: metal catalyst)
The antifouling composition used in the present invention further contains a metal catalyst as the component (C) together with the components (A) and (B). When the metal catalyst is not included, the condensation reaction of the component (A) and the component (B) cannot be effectively promoted, and the curability of the antifouling layer formed from the antifouling composition is sufficiently improved. I can't let you.
Further, in the case of the antifouling composition not containing the component (C), the curing reaction cannot sufficiently proceed at a relatively low temperature (130 ° C. or lower). Therefore, for example, when it is desired to form an antifouling layer formed from the antifouling composition on a support having low heat resistance such as a vinyl chloride resin, the antifouling is prevented under a low temperature that can suppress the thermal shrinkage of the support. If an attempt is made to form a dirty layer, the curability of the antifouling layer may be insufficient. On the other hand, in order to sufficiently advance the curing reaction, if the curing is attempted at a relatively high temperature (exceeding 130 ° C.), the support may cause thermal shrinkage.

The metal catalyst is preferably a metal catalyst that does not require light irradiation for the expression of catalytic action.
In the present specification, the “metal catalyst that does not require light irradiation for the expression of a catalytic action” means light irradiation in order to develop a catalytic action for the condensation reaction of the components (A) and (B). It refers to a metal catalyst that does not require. For example, light irradiation is required for the expression of a catalytic action such as titanium oxide (TiO ₂ ) and zinc oxide (ZnO), which causes oxidation and reduction reactions by generating electrons and holes by light irradiation. What is commonly called photocatalyst is excluded.
In the case where the antifouling layer contains the above-mentioned “metal catalyst that does not require light irradiation for the expression of the catalytic action”, it is possible to avoid problems that may occur when a photocatalyst is used. The troubles that may occur when using the photocatalyst are, for example, a decrease in water repellency due to an increase in the surface roughness of the antifouling layer due to the fact that the photocatalyst itself is a solid substance, There are problems such as a decrease in water repellency due to the effect of imparting hydrophilicity and a decrease in durability of the antifouling layer by promoting hydrolysis of the polymer of the silane compound.

The metal catalyst is preferably at least one selected from the group consisting of a titanium catalyst, a zirconium catalyst, a palladium catalyst, a tin catalyst, an aluminum catalyst, and a zinc catalyst.

The titanium-based catalyst is preferably a compound other than a photocatalyst containing a titanium atom, for example, titanium alkoxide, titanium chelate, titanium acylate, etc., including titanium hydroxide, acetate, carbonate, It may be sulfate, nitrate, chloride or the like.
Examples of the titanium alkoxide include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, and the like.
Examples of the titanium chelate include titanium acetylacetonate such as titanium diisopropoxybis (acetylacetonate) and titanium tetraacetylacetonate; titanium ethylacetoacetate such as titanium diisopropoxybis (ethylacetoacetate); Titanium triethanolamate such as propoxybis (triethanolaminate); titanium tetraoctylene glycolate, titanium dioctyloxybis (octylene glycolate), titanium di-2-ethylhexoxybis (2-ethyl-3- And titanium octylene glycolate such as hydroxy hexoxide); titanium lactate, titanium lactate ammonium salt and the like.
Examples of titanium acylate include polyhydroxy titanium stearate.

The zirconium-based catalyst is preferably a compound other than a photocatalyst containing a zirconium atom, and examples thereof include zirconium alkoxide, zirconium chelate, zirconium acylate, and the like, zirconium hydroxide, acetate, carbonate, It may be sulfate, nitrate, chloride or the like.
Examples of the zirconium alkoxide include zirconium tetranormal propoxide, zirconium tetranormal butoxide and the like.
Examples of the zirconium chelate include zirconium acetylacetonate such as zirconium tributoxy monoacetylacetonate and zirconium tetraacetylacetonate; zirconium ethylacetoacetate such as zirconium dibutoxybis (ethylacetoacetate); zirconyl chloride compound and zirconium lactate ammonium. Examples include salts.
Examples of the zirconium acylate include a zirconium octylate compound and zirconium stearate.

The palladium-based catalyst is preferably a compound other than a photocatalyst containing a palladium atom, and examples thereof include palladium, palladium chloride, palladium hydroxide, palladium carbon catalyst (Pd / C) and the like.

The tin-based catalyst is preferably a compound other than a photocatalyst containing a tin atom. For example, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin dithiocarboxylate, dibutyltin Examples thereof include an organic tin compound such as dimaleate, dioctyltin mercaptide, and dioctyltin thiocarboxylate, or an inorganic tin compound.

The aluminum-based catalyst is preferably a compound other than a photocatalyst containing an aluminum atom, and examples thereof include an aluminum acetoacetate complex and an aluminum acetylacetonate complex.
Examples of aluminum acetoacetate complexes include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, Examples thereof include isopropoxyaluminum monostearyl acetoacetate, diisopropoxyaluminum monoisostearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl-β-alanate monolauryl acetoacetate, and aluminum trisacetylacetonate.
Examples of aluminum acetylacetonate complexes include monoacetylacetonate aluminum bis (isobutyl acetoacetate) chelate, monoacetylacetonate aluminum bis (2-ethylhexyl acetoacetate) chelate, monoacetylacetonate aluminum bis (dodecylacetoacetate) Chelate, monoacetylacetonate aluminum bis (oleyl acetoacetate) chelate, and the like.

The zinc-based catalyst is preferably a compound other than a photocatalyst containing a zinc atom, such as zinc-chromium oxide, zinc-aluminum oxide, zinc-aluminum-chromium oxide, zinc-chromium-manganese oxidation. Products, zinc-iron oxide, zinc-iron-aluminum oxide, and the like.

In addition, as said metal catalyst, you may use individually or in combination of 2 or more types.
In addition, it effectively promotes the condensation reaction between the silane compounds, improves the curability of the antifouling layer formed from the antifouling composition, and cures even at relatively low temperatures (130 ° C. or lower). From the viewpoint of making the antifouling composition capable of proceeding, it is preferable to contain at least the titanium-based catalyst.
The titanium catalyst is preferably a titanium chelate, more preferably titanium ethyl acetoacetate, titanium acetylacetonate or titanium octylene glycolate, still more preferably titanium ethyl acetoacetate, and titanium diisopropoxybis (ethyl acetoacetate). Even more preferred.

Content of (C) component in antifouling composition is a viewpoint which improves the sclerosis | hardenability of the antifouling layer formed from an antifouling composition, and a hardening reaction also at comparatively low temperature (130 degrees C or less) From the viewpoint of making the antifouling composition capable of proceeding, it is preferably 0.010 mol% or more, more preferably 0.100 mol% or more, with respect to 100 mol% in total of the components (A) and (B). More preferably, it is 0.150 mol% or more, more preferably 0.300 mol% or more, still more preferably 0.500 mol% or more, and still more preferably 1.000 mol% or more. The content is preferably 50.000 mol% or less, more preferably 30.000 mol% or less, still more preferably 20.000 mol% or less, still more preferably 10.000 mol% or less, and even more preferably. It is 6.000 mol% or less, more preferably 3.000 mol% or less.
In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

((D) component: organic solvent)
The antifouling composition used in the present invention further contains an organic solvent as the component (D) together with the component (A), the component (B), and the component (C).
The boiling point of the organic solvent is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of easily adjusting the heating temperature in the step (3) described later to a temperature at which the surface state of the antifouling layer becomes better. More preferably, it is 100 ° C. or higher, and still more preferably 110 ° C. or higher. And preferably it is 160 degrees C or less, More preferably, it is 150 degrees C or less, More preferably, it is 140 degrees C or less, More preferably, it is 130 degrees C or less.
When using 2 or more types of the said organic solvent together, it is preferable to select so that the organic solvent with a higher boiling point may become the above-mentioned boiling point at least.
Examples of the organic solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene and the like. The organic solvent is preferably at least one selected from the group consisting of butyl acetate, butanol, cyclohexanone, methyl isobutyl ketone, toluene, and mineral spirits, more preferably from butyl acetate, butanol, cyclohexanone, and methyl isobutyl ketone. It is 1 or more types selected from the group which consists of, More preferably, it is 1 or more types selected from the group which consists of butyl acetate and butanol.

When the component (A) and the component (B) are effective components, the concentration of the effective component in the organic solvent that is the component (D) and the solution composed of the component (A) and the component (B) is applied. From the viewpoint of easily forming an antifouling layer having an appropriate coating thickness on the support, it is preferably 0.01 M (mol / L) or more, more preferably 0.10 mol / L or more, and still more preferably 0.50 mol. / L or more. From the same viewpoint, it is preferably 5.00 M (mol / L) or less, more preferably 3.00 mol / L or less, and still more preferably 2.00 mol / L or less.

((E) component: acid catalyst)
The antifouling composition used in the present invention preferably further contains an acid catalyst as the component (E) from the viewpoint of further improving the curability of the antifouling layer formed from the antifouling composition.
By containing an acid catalyst in the antifouling composition, hydrolysis of the reactive functional group of the component (A) and the component (B) is promoted. As a result, the condensation polymerization reaction between silane compounds is further promoted, and an antifouling layer having excellent curability can be formed.
The acid catalyst is not particularly limited as long as it has a function of promoting hydrolysis of the reactive functional groups of the component (A) and the component (B). For example, from the viewpoint of further improving the curability of the antifouling layer formed from the antifouling composition, hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, odorous acid, p-toluenesulfonic acid, It is preferable to include at least one selected from the group consisting of fluoroacetic acid, and it is more preferable to include hydrochloric acid.
In addition, as said acid catalyst, you may use individually or in combination of 2 or more types.

From the viewpoint of further improving the curability of the antifouling layer formed from the antifouling composition, the content of the component (E) in the antifouling composition is a total of 100 of the component (A) and the component (B). Preferably it is 0.010 mol% or more with respect to mol%, More preferably, it is 0.030 mol% or more, More preferably, it is 0.050 mol% or more, More preferably, it is 0.060 mol% or more. And the said content becomes like this. Preferably it is 1.000 mol% or less, More preferably, it is 0.500 mol% or less, More preferably, it is 0.100 mol% or less, More preferably, it is 0.075 mol% or less. In addition, the said content can also be computed from the compounding quantity at the time of mix | blending each component.

(Other additives)
In addition to the components (A) to (E) described above, the antifouling composition used in the present invention may contain other additives as long as the effects of the present invention are not impaired.
Examples of other additives include a resin component, a curing agent, an anti-aging agent, a light stabilizer, a flame retardant, a conductive agent, an antistatic agent, and a plasticizer.
The content of each of these additives is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, and still more based on the total amount of the antifouling composition. The content is preferably 0 to 2% by mass.

In addition, the total content of the component (A), the component (B), the component (C), and the component (E) included as necessary, in the antifouling composition used in the present invention, excluding the component (D). The amount is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass with respect to the total amount (solid content 100% by mass) of the antifouling composition excluding the component (D). % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. The total content is more preferably 100% by mass. When the component (E) is not contained in the antifouling composition, the preferred range of these contents represents the preferred range of the total content of the components (A) to (C). In addition, the said total content can also be computed from the compounding quantity at the time of mix | blending each component.

<< Step (2) >>
The step (2) used in the present invention is a step of forming a coating film by applying the antifouling composition prepared in the above step (1) on a support.
The antifouling composition prepared in the step (1) is in the form of a solution with the organic solvent, and can be applied on the support by a known application method.
Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, die coating, and gravure coating.

<Support>
The support used in the step (2) can form a coating film made of the antifouling composition on the support and does not cause a problem in the later-described step (3). There is no particular limitation. As the support, it is preferable to use a base material or a release material described later.
In addition, the said support body may be a support body included as it is in the structure of the antifouling sheet | seat obtained, and the support body removed by the process after the process (3) mentioned later may be sufficient as it.

(Base material)
Examples of the base material that can be used as the support include a paper base material, a resin film, a resin sheet, a base material obtained by laminating a paper base material with a resin, and the like, depending on the use of the antifouling sheet. You can choose.
Examples of the paper constituting the paper substrate include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper and the like.
Examples of the resin constituting the resin film or resin sheet include polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. , Ethylene-methacrylic acid copolymer vinyl resin; polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane; Examples thereof include urethane resins such as polyurethane.

Examples of the base material obtained by laminating a paper base material with a resin include laminated paper obtained by laminating the paper base material with a thermoplastic resin such as polyethylene.
Among these substrates, a resin film or a resin sheet is preferable, a resin film or a resin sheet made of a polyester resin is more preferable, and a resin film or a resin sheet made of polyethylene terephthalate (PET) is more preferable.

As a base material that can be used as the support, a base material with a primer layer in which a primer layer is provided on the surface of the base material is used from the viewpoint of improving adhesion with an antifouling layer or a weathering layer described later. May be.
As a component which comprises a primer layer, a polyester-type resin, a urethane type resin, a polyester urethane type resin, an acrylic resin etc. are mentioned, for example, These resin may be used individually or in combination of 2 or more types. .

In addition, as a base material that can be used as the support, the base material with a weathering layer in which a weathering layer made of a polymer ultraviolet absorber is further provided on the surface of the base material or the surface of the base material with a primer layer. (A primer layer may be provided between the weather resistant layer and the substrate) may be used. The polymer ultraviolet absorber has a structure in which an ultraviolet absorption skeleton is covalently bonded in a polymer structure, and preferably has a weight average molecular weight of 5,000 or more, more preferably 10,000 or more. is there.
In addition, as a substrate that can be used as the support, a substrate with a hard coat layer (a hard coat layer and a hard coat layer) in which a hard coat layer is further provided on the surface of the substrate described above or the surface of a substrate with a primer layer. You may use a primer layer between the base materials). There is no restriction | limiting in particular as a material which forms the said hard-coat layer, According to the use of an antifouling sheet | seat, it can select suitably from well-known hard-coat layer forming materials.

Moreover, when the base material which can be used as the support is a resin film or a resin sheet, from the viewpoint of improving the adhesion with the antifouling layer, if necessary, with respect to the surface of the resin film or the resin sheet. Then, a surface treatment such as an oxidation method or a roughening method may be performed.
The oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
Moreover, it does not specifically limit as an uneven | corrugated method, For example, a sandblasting method, a solvent processing method, etc. are mentioned.
These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the antifouling layer and the operability.

The thickness of the substrate is appropriately set according to the use of the antifouling sheet, but is preferably 10 to 250 μm, more preferably 15 to 200 μm, and still more preferably 20 to 150 μm from the viewpoints of handleability and economy. It is.
In addition, the base material that can be used as the support further includes an ultraviolet absorber other than the above-described polymer ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a coloring agent. An agent or the like may be contained.

(Peeling material)
As the release material that can be used as the support, a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used, and a release agent is applied on a base material for the release material. Etc.
As the base material for the release material, for example, a paper base material, a resin film, a resin sheet, and a base material obtained by laminating a paper base material with a resin, which can be used as a base material of one aspect of the antifouling sheet of the present invention Etc.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
The thickness of the release material is not particularly limited, and is preferably 10 to 200 μm, more preferably 25 to 150 μm.

In addition, when the said antifouling layer has a configuration sandwiched between two release materials, the two release materials may be the same as or different from each other.
Moreover, the said peeling material may be included as it is in the structure of the antifouling sheet | seat obtained, and may be used as a peeling material removed by the process after the process (3) mentioned later. Examples of the case where the release material is removed in the steps after the step (3) include the following examples. First, an antifouling composition is applied on the release material in step (2), and an antifouling layer is formed in step (3) described below. And the case where the said peeling | exfoliation material is removed after bonding the said antifouling layer with the base material mentioned above or the adhesive layer mentioned later, etc. is mentioned.

<< Step (3) >>
The step (3) used in the present invention is a step of forming the antifouling layer by heating the coating film on the support formed in the step (2) at a temperature not higher than the boiling point of the organic solvent.
As described above, by heating the coating film on the support at a temperature not higher than the boiling point of the organic solvent, the organic solvent in the coating film volatilizes and / or evaporates from the coating film surface. It was noted that the curing reaction of the coating film can be started and accelerated before the coating film dries.
When not introducing the said process (3), compared with the case where the said process (3) is introduce | transduced, gelatinization of a coating film will advance easily. As a result, the surface state of the antifouling layer is likely to deteriorate, the curability of the antifouling layer is lowered, and the surface hardness may be reduced. Moreover, when the antifouling composition in which the coating film is more easily gelled is used, the coating film is gelled, the curability of the antifouling layer is lowered, and the surface state of the antifouling layer is deteriorated. Furthermore, it may become impossible to form an antifouling layer.

About the heating temperature in a process (3), although it can set suitably with the kind of organic solvent in the previous period, as above-mentioned, it heats at the temperature below the boiling point of the said organic solvent, and the organic in a coating film from the coating-film surface. The temperature is such that the curing reaction of the coating film can be started and accelerated before the solvent volatilizes and / or evaporates and the coating film dries.
Therefore, from the above viewpoint, the temperature is preferably the boiling point of the organic solvent −10 ° C. or less, more preferably the boiling point of the organic solvent −20 ° C. or less, and still more preferably the boiling point of the organic solvent −30 ° C. or less. .
In addition, the antifouling composition used in the present invention can cause a curing reaction to proceed even at a relatively low temperature of 130 ° C. or lower. When a low heat resistant support such as vinyl chloride is used, the support Can be suppressed.
Therefore, from the above viewpoints and productivity viewpoints, the temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher, still more preferably 40 ° C or higher, still more preferably 50 ° C or higher, and still more preferably 60 ° C. ℃ or more. And preferably it is 130 degrees C or less, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less, More preferably, it is 95 degrees C or less.

The heating time in the step (3) is not particularly limited as long as the effect of the present invention is exhibited, and can be appropriately set.
In addition, from the viewpoint of suppressing the loss due to volatilization or evaporation of the organic solvent in the coating film formed in the step (2) as much as possible, the time from the formation of the coating film in the step (2) to the step (3) is as follows. The shortest possible time is preferred. Preferably it is 60 seconds or less, More preferably, it is 30 seconds or less, More preferably, it is 20 seconds or less, More preferably, it is 10 seconds or less.

The coating film whose curing reaction has been promoted in the step (3) finally becomes an antifouling layer by solidifying the coating film without gelation.
The step is preferably a step of forming the antifouling layer by introducing the coating film into a drying mechanism.
Examples of the drying mechanism include a batch-type drying mechanism such as an air oven, a heat roll, and a hot air through mechanism (equipment that is heated and dried while an object to be dried moves and passes through an open drying oven). And a continuous drying mechanism. An apparatus that can also be used as a part of these drying mechanisms, for example, a heating medium circulating heater such as an oil heater, and a heater such as a far-infrared heater itself can be used as the drying mechanism.

In addition, you may laminate | stack a new release material further on the antifouling layer formed with the manufacturing method mentioned above in order to protect the surface of the antifouling layer at the time of storage.
Furthermore, the antifouling sheet 1b in FIG. 1 (b) or the antifouling in FIG. 2 (b) is obtained by laminating the pressure-sensitive adhesive layer formed on another release material on the formed antifouling layer or substrate. An antifouling sheet with an adhesive layer, such as the adhesive sheet 2b, can also be produced.
Moreover, when the support body used at the step (2) is a release material, after the antifouling layer is formed, the antifouling layer is bonded to the above-described base material or a new release material, and then used as a support body. The used release material may be removed.

[Anti-fouling sheet]
The antifouling sheet obtained by the production method of the present invention is not particularly limited as long as it is obtained by the above-described method for producing an antifouling sheet of the present invention.
<Configuration example of antifouling sheet>
FIG. 1 is a cross-sectional view illustrating an example of an antifouling sheet having a base material, which is obtained by a manufacturing method that is an example of this embodiment.
As an antifouling sheet | seat which has a base material, the antifouling sheet | seat 1a which has the antifouling layer 11 on the base material 12 as shown to Fig.1 (a) is mentioned, for example.
Moreover, as shown in FIG.1 (b), as the antifouling sheet | seat 1b which further provided the adhesive layer 13 and the peeling material 14 on the surface on the opposite side to the surface which has the antifouling layer 11 of the base material 12. Also good.
Note that a release material may be further provided on the antifouling layer 11 of the antifouling sheets 1a and 1b in order to protect the antifouling layer during storage.

FIG. 2 is a cross-sectional view showing an example of an antifouling sheet having no base material, which is obtained by the manufacturing method as an example of this embodiment.
As the antifouling sheet having no base material, for example, as shown in FIG. 2A, the antifouling sheet 2a has a configuration in which the antifouling layer 11 is sandwiched between two release materials 14 and 14 ′. Is mentioned.
In addition, in the configuration shown in FIG. 2A as shown in FIG. 2B, the antifouling sheet 2b is further provided with an adhesive layer 13 between the antifouling layer 11 and the release material 14 ′. Also good.

(Anti-fouling layer)
The antifouling layer of the antifouling sheet obtained by the production method of the present invention is formed from the above antifouling composition.
The thickness of the antifouling layer is preferably 0.001 μm or more, more preferably 0.005 μm or more, still more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and still more preferably 0.10 μm or more. It is. The thickness is preferably 40 μm or less, more preferably 25 μm or less, still more preferably 15 μm or less, still more preferably 5.0 μm or less, still more preferably 1.0 μm or less, and even more preferably 0.80 μm or less. It is.

(Base material)
When the antifouling sheet of the present invention has a substrate, the substrate can be appropriately selected according to the use of the antifouling sheet, and can be used in the method for producing an antifouling sheet of the present invention. The material is as described above.

(Peeling material)
When the antifouling sheet of the present invention has a release material, the release material can be appropriately selected according to the use of the antifouling sheet, and can be used in the method for producing an antifouling sheet of the present invention. The material is as described above.

(Adhesive layer)
When the antifouling sheet of the present invention has an adhesive layer, the adhesive constituting the adhesive layer can be appropriately selected according to the use of the antifouling sheet.
Specific adhesives include, for example, acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, polyester adhesives, and curable adhesives that are cured by energy rays such as ultraviolet rays. It is done.
These pressure-sensitive adhesives may be used alone or in combination of two or more.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1 to 100 μm, more preferably 5 to 80 μm.

Example 1
An antifouling sheet was produced by the following steps (1) to (3).
Step (1):
(A) component and (B) component are mix | blended by the kind and compounding ratio (active ingredient ratio, mol%) shown in Table 1, and the butyl acetate (boiling point: 126 degreeC) which is (D) component is added and diluted, A solution having an active ingredient concentration of 1.80 M was obtained. The solution was further blended with hydrochloric acid as component (E) at the blending ratio (active ingredient ratio, mol%) shown in Table 1 and stirred for 1 minute. After stirring, the solution was allowed to stand for 15 minutes.
Subsequently, titanium diisopropoxybis (ethyl acetoacetate) which is (C) component was mix | blended with the compounding ratio (active ingredient ratio, mol%) shown in Table 1, and the antifouling composition was prepared.
Step (2):
As the substrate, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A-4100”, thickness 50 μm) provided with a primer layer on one side was used.
On the primer layer of the said base material with a primer layer, the antifouling composition prepared as mentioned above was apply | coated using the Mayer bar, and the coating film was formed.
Step (3):
The coating film on the support formed in the step (2) is put into an oven set at 80 ° C. which is lower than the boiling point of the organic solvent and heated for 2 minutes to prevent the thickness shown in Table 3. An antifouling sheet having a fouling layer was produced. It should be noted that the time from the formation of the coating film on the mount in the step (2) to the introduction into the oven in the step (3) was within 10 seconds.

Examples 2-8, Comparative Examples 1-4
The same method as in Example 1 was used, except that the types and blending ratios of component (A), component (B-1), component (B-2) and component (D) were changed to the contents shown in Table 1. Thus, each antifouling sheet was produced.

The detail of each component of Table 1 used in the preparation of the antifouling composition in each Example and each Comparative Example is as follows.
<(A) component: tetrafunctional silane compound represented by general formula (a)>
"TEOS": Tetraethoxysilane, a tetrafunctional silane compound in which p = 4 and R ¹ = ethyl group (carbon number: 2) in the general formula (a).
<(B) component: trifunctional silane compound represented by general formula (b)>
“Hexadecyltrimethoxysilane”: trifunctional in which q = 3, R ² = n-hexadecyl group (carbon number: 16), and R ³ = methyl group (carbon number: 1) in the general formula (b) Silane compounds.
“Octadecyltrimethoxysilane”: a trifunctional silane in which q = 3, R ² = n-octadecyl group (carbon number: 18), and R ³ = methyl group (carbon number: 1) in the general formula (b) Compounds.
These compounds are compounds represented by the general formula (b-1) when R ² is read as R ⁴ , R ³ as R ⁵ , and q as r, that is, (B-1) It is a compound expressed as a component.
“Methyltrimethoxysilane”: a trifunctional silane compound in which q = 3, R ² = methyl group (carbon number: 1), and R ³ = methyl group (carbon number: 1) in the general formula (b) .
Note that when R ² is read as R ⁶ , R ³ as R ⁷ , and q as s, the compound is expressed as the compound represented by the general formula (b-2), that is, as the component (B-2). It is a compound.
<Component (C): Metal-based catalyst>
"Titanium catalyst": Titanium diisopropoxybis (ethyl acetoacetate) [manufactured by Matsumoto Fine Chemical Co., Ltd., product name "Orgatechs TC-750"].
<Component (D): Organic solvent>
・ "Butyl acetate": Boiling point 126 ℃
・ "Butanol": Boiling point 117 ℃
・ "Cyclohexanone": boiling point 155 ° C
・ Methyl isobutyl ketone boiling point: 117 ° C
・ "Toluene": boiling point 111 ℃
・ "Mineral spirit": boiling point 140 ~ 180 ℃
・ "Methanol": Boiling point 65 ℃
"Ethanol": boiling point 78 ° C
<(E) component: acid catalyst>
"Hydrochloric acid": 0.01M hydrochloric acid.

The characteristics of the antifouling sheet produced using the antifouling composition shown in Table 1 prepared in each Example and each Comparative Example were evaluated based on the following methods. The results are shown in Table 2.

<Thickness of antifouling layer>
The thickness of the antifouling layer is J. A. Measurement was performed with a spectroscopic ellipsometer (product name “M-2000”) manufactured by Woollam.

<Stain condition of antifouling layer>
The surface of the antifouling layer of the antifouling sheet prepared in each Example and each Comparative Example was visually observed, and the surface state of the antifouling layer was evaluated according to the following criteria.
A: Transparent.
B: Slight cloudiness was confirmed.
C: Cloudy and no longer transparent.
In addition, about what was evaluation of the surface state of the pollution protection layer was "C", since it cannot endure use, evaluation other than the curability evaluation of a pollution protection layer shown below is not performed.

<Curability of antifouling layer>
The surface of the antifouling layer of the antifouling sheet produced in each Example and each Comparative Example was visually observed after rubbing 20 times with a finger, and the curability of the antifouling layer was observed according to the following criteria. Evaluated.
-A: A change was not seen compared with before rubbing with a finger.
B: Discolored slightly white, but acceptable.
C: Discolored white.
-D: The antifouling layer could not be formed because the coating film made of the antifouling composition was not cured.
In addition, about the thing whose curability evaluation of a pollution protection layer was "C" or "D", since it cannot endure use, the thickness of a pollution protection layer is not measured.

From Tables 1 and 2, the anti-smudge composition having poor surface condition and curability of the anti-smudge layers of Examples 1 to 8 but having an alkyl group with a large number of carbon atoms that contributes to improved water repellency The antifouling sheet produced by the above-described production method using the antifouling composition containing a compound was excellent in surface condition and curability.
In each Example, the heating temperature in process (3) is below the boiling point of the organic solvent which is (D) component. It is considered that the curing reaction of the coating film was promoted preferentially over evaporation of the organic solvent from the surface of the coating film by heating at a temperature not higher than the boiling point of the organic solvent as the component (D). As a result, in the examples using the production method of the present invention, the antifouling sheet having an antifouling layer having a good surface state and curability without causing the coating film to gel as in Comparative Examples 1 to 4. It is thought that I was able to get.

On the other hand, the antifouling layers formed from the antifouling compositions of Comparative Examples 1 to 4 were heated at a temperature exceeding the boiling point of the organic solvent as the component (D) in the step (3). The result was inferior. Therefore, it is judged that the antifouling sheet having these antifouling layers cannot be used, and the thickness of the antifouling layers is not measured.

By using the production method of the present invention, the surface state and curability of the antifouling layer can be improved even in the case of the antifouling composition inferior to the surface state and curability of the antifouling layer.
As a result, the antifouling sheet obtained by the production method of the present invention has good surface condition and curability of the antifouling layer. Further, an antifouling composition comprising a trifunctional silane compound having an alkyl group having a large carbon number that contributes to improvement in water repellency, although the antifouling composition is inferior in surface condition and curability of the antifouling layer. Even when cured by the production method of the present invention, it was confirmed that an antifouling layer having a good surface state and curability could be obtained.
Therefore, the production method of the present invention is an antifouling sheet having an antifouling layer, for example, window glass for buildings, window glass for automobiles, windshield glass for vehicles, aircraft, ships, etc., aquarium, ship bottom window, underwater to the ship bottom. Films for preventing biological adhesion, panels for roads such as soundproof walls, mirrors installed in bathrooms, glass containers, glass ornaments, etc. It is suitable as a method for producing an antifouling sheet for prevention.

1a, 1b, 2a, 2b Antifouling sheet 11 Antifouling layer 12 Base material 13 Adhesive layer 14, 14 'Release material

Claims (10)

1. A method for producing an antifouling sheet having an antifouling layer, comprising the following steps (1) to (3) in this order.
   Step (1): Step of preparing an antifouling composition containing the following components (A) to (D): Component (A): tetrafunctional silane compound represented by the following general formula (a) Si (OR ¹ _P (X ¹ ) _4-p (a)
   [In the general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When R ¹ and ^{X 1} there are a plurality, the plurality of ^{R 1} and ^{X 1} are also identical to each other or may be different. p represents an integer of 0 to 4. ]
   Component (B): Trifunctional silane compound represented by the following general formula (b) R ² Si (OR ³ ) _q (X ² ) _3-q (b)
   [In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group having 1 to 6 carbon atoms, and X ² represents a halogen atom. If R ³ and ^{X 2} there are a plurality, the plurality of ^{R 3} and ^{X 2} are either identical to one another or may be different. q represents an integer of 0 to 3. ]
   Component (C): Metal catalyst (D) Component: Organic solvent Step (2): Step (3) for coating the antifouling composition prepared in Step (1) on a support to form a coating film: The step of heating the coating film on the support formed in step (2) at a temperature not higher than the boiling point of the organic solvent to form an antifouling layer
2. The method for producing an antifouling sheet according to claim 1, wherein the organic solvent is at least one selected from the group consisting of butyl acetate, butanol, cyclohexanone, methyl isobutyl ketone, toluene, and mineral spirits.
3. The method for producing an antifouling sheet according to claim 1 or 2, wherein the heating temperature in the step (3) is a boiling point of the organic solvent of -10 ° C or lower.
4. The method for producing an antifouling sheet according to any one of claims 1 to 3, wherein in the step (1), the component (B) contains at least one of the following components (B-1).
   Component (B-1): Trifunctional silane compound represented by the following general formula (b-1) R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (b-1)
   [In general formula (b-1), R ⁴ represents an alkyl group having 15 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. If R ⁵ and ^{X 3} there are a plurality, the plurality of ^{R 5} and ^{X 3} are either identical to one another or may be different. r represents an integer of 0 to 3. ]
5. The method for producing an antifouling sheet according to any one of claims 1 to 4, wherein in step (1), at least one of the following components (B-2) is contained as component (B).
   Component (B-2): Trifunctional silane compound represented by the following general formula (b-2) R ⁶ Si (OR ⁷ ) _s (X ⁴ ) _3-s (b-2)
   [In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. If R ⁷ and ^{X 4} there are a plurality, a plurality of ^{R 7} and ^{X 4,} are identical to each other or may be different. s represents an integer of 0 to 3. ]
6. The method for producing an antifouling sheet according to any one of claims 1 to 5, wherein in the step (1), the following condition (I) is further satisfied.
   Condition (I): Ratio of molar amount of component (A) to molar amount of component (B) [(A) / (B)] (molar ratio) is 0.01 or more
7. The method for producing an antifouling sheet according to claim 5 or 6, further satisfying the following condition (II) in the step (1).
   Condition (II): Ratio of molar amount of component (B-1) to total molar amount of component (B-1) and component (B-2) [(B-1) / {(B-1) + (B -2)}] (molar ratio) is 0.020 or more
8. In the step (1), the content of the component (C) is 0.010 mol% or more and 50.000 mol% or less with respect to 100 mol% in total of the components (A) and (B). Item 8. The method for producing an antifouling sheet according to any one of Items 1 to 7.
9. The method for producing an antifouling sheet according to any one of claims 1 to 8, wherein the support is a substrate or a release material.
10. In the step (1), an acid catalyst as the component (E) is further included, and the content of the component (E) is 0.010 mol% with respect to 100 mol% in total of the components (A) and (B). The method for producing an antifouling sheet according to any one of claims 1 to 9, wherein the content is 1.000 mol% or less.

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