KR20180061180A - Manufacturing method of antifouling sheet - Google Patents

Abstract

(1) preparing an antifouling composition containing a tetrafunctional silane compound having a specific structure as a component (A), a trifunctional silane compound having a specific structure as a component (B), and a metal catalyst as a component (C) ; (2) a step of coating the antifouling composition prepared in the step (1) on a support to form a coating film; (3) heating the coating film on the support formed in the step (2) from the side of the support to initiate the curing reaction of the coating film from the side of the support; (4) of solidifying the coating film to form an antifouling layer; Having an antifouling layer in this order.

Description

Manufacturing method of antifouling sheet

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

Generally, a windshield glass, a water tank, a bottom window, a film for preventing adhesion of marine life on the bottom of a ship, a road panel such as a soundproof wall, a mirror installed in a bathroom, a glass container, a glass It is desired that the surface of a molded product such as a decorative article is not adhered with something that can interfere with the field of view such as water drops, scratches, and contamination.

Water repellency and antifouling property are imparted to the surface of such a molded article by coating with a film made of an antifouling material or by sticking an antifouling sheet to the surface.

For example, Patent Document 1 discloses a laminate comprising a base layer formed of an inorganic compound and a water repellent film covering the surface of the base layer and formed of a fluorine-containing compound, A water-repellent film-coated article is disclosed.

Japanese Laid-Open Patent Publication No. 2010-285574

However, the water-repellent coated article disclosed in Patent Document 1 has a water-repellent film formed of a fluorine-containing compound and therefore is not preferable from the viewpoint of environmental protection.

It is also required that the antifouling layer of the antifouling sheet has good surface properties and curability of the layer.

The present inventors have found that a coating film is formed using a tetrafunctional silane-based compound having a specific structure, a trifunctional silane-based compound having a specific structure, and an antifouling composition containing a metal catalyst to form an antifouling layer having excellent surface properties and curability I found out I could.

On the other hand, the inventors of the present invention have found a problem that gelation occurs in the process of forming an antifouling layer from a coating film made of the antifouling composition, and the surface condition of the antifouling layer is deteriorated.

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

The present inventors have found that a coating film is formed using a tetrafunctional silane-based compound having a specific structure, a trifunctional silane-based compound having a specific structure, and an antifouling composition containing a metal catalyst to initiate a curing reaction of the coating film under specific conditions , The present inventors have found out that the above problems can be solved, thereby completing the present invention.

That is, the present invention provides the following [1] to [15].

[1] A method for producing an antifouling sheet having an antifouling layer, which comprises the following steps (1) to (4) in this order.

Step (1): A step of preparing an antifouling composition containing the following components (A) to (C)

Component (A): A tetrafunctional silane compound represented by the following 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 are a plurality is present, a plurality of R ¹ and X ¹ is be same or different from each other. and p represents an integer of 0 to 4.]

Component (B): A trifunctional silane compound represented by the following general formula (b)

R ² Si (OR ³ ) _q (X ² ) _3-q (b)

[In the 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. When R ³ and X ² are a plurality is present, a plurality of R ³ and X ² may be the same or different from each other. and q represents an integer of 0 to 3.]

(C) Component: Metal catalyst

Step (2): A step of coating the antifouling composition prepared in the step (1) on a support to form a coating film

Step (3): A step of heating the coated film formed on the support formed in the step (2) from the side of the support to initiate the curing reaction of the coated film from the side of the support

Step (4): Step of solidifying the coating film to form an antifouling layer

[2] In the step (3), the curing reaction of the coating film is started from the surface on the support side by heating so that the temperature of the surface of the coating film on the side of the support is faster than the temperature of the side opposite to the support , And the method for producing an antifouling sheet according to [1] above.

[3] The method for producing an antifouling sheet according to [2] above, wherein in step (3), the surface of the support on the side opposite to the coated film side is heated to initiate the curing reaction of the coated film from the side of the support .

[4] The method according to any one of [1] to [3], wherein the coating film on the support is heated by bringing the surface of the support opposite to the coating film side into contact with a heating mechanism previously heated in the step (3) A method for producing the antifouling sheet.

[5] The method for producing an antifouling sheet according to any one of [1] to [4], wherein the heating temperature is 40 ° C or higher in the step (3).

[6] The method for producing an antifouling sheet according to any one of [1] to [5], wherein the time from the step (2) to the step (3) is 20 seconds or less.

[7] The method for producing an antifouling sheet according to any one of [1] to [6], wherein the step (4) is put into a drying apparatus to form an antifouling layer.

[8] The method for producing an antifouling sheet according to [7], wherein the time from the step (3) to the step (4) is 60 seconds or less.

[9] The method for producing an antifouling sheet according to any one of [1] to [8], wherein as the component (B) in the step (1), at least one of the following components (B-1)

(B-1): a trifunctional silane-based compound represented by the following general formula (b-1)

R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (b-1)

[In the formula (b-1), R ⁴ represents an alkyl group having from 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. When R ⁵ and X ³ are a plurality is present, a plurality of R ⁵ and X ³ are be same or different from each other. and r represents an integer of 0 to 3.]

[10] The method for producing an antifouling sheet as described in any one of [1] to [9] above, which comprises at least one of the following components (B-2) as the component (B) in the step (1).

(B-2) Component: A trifunctional silane-based compound represented by the following general formula (b-2)

_{^{R 6 Si (OR 7) s}} (X 4) 3-s (b-2)

[In the 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. When R ⁷ and X ⁴ are a plurality is present, a plurality of R ⁷ and X ⁴ may be the same or different from each other. and s represents an integer of 0 to 3.]

[11] The method for producing an antifouling sheet according to any one of [1] to [10], wherein the step (1) further satisfies the following condition (I).

(A) / (B) (molar ratio) of the molar amount of the component (A) to the molar amount of the component (B)

[12] The method for producing an antifouling sheet according to the above [10] or [11], further comprising the following condition (II) in the step (1).

The ratio of the molar amount of the component (B-1) to the molar amount of the component (B-1) to the total molar amount of the component (B-1) 2)}] (molar ratio) of not less than 0.020

[13] The method according to any one of [1] to [6], wherein in the step (1), the content of the component (C) is 0.010 mol% or more and 50.000 mol% or less based on the total amount of 100 mol% [12] The method for producing an antifouling sheet as described in any one of [1] to [12].

[14] The method for producing an antifouling sheet according to any one of [1] to [13], wherein the support is a substrate or a peeling material.

(15) A process for producing a polycarbonate resin according to any one of (1) to (7), wherein the step (1) further comprises an acid catalyst as the component (D), and the content of the component (D) %, And not more than 1.000 mol% of the total weight of the antifouling layer.

According to the present invention, it is possible to provide a method for producing an antifouling sheet having an antifouling layer excellent in surface state and curability.

1 is a cross-sectional view of an example of an antifouling sheet having a base material obtained by the production method of this embodiment.
2 is a cross-sectional view of an example of an antifouling sheet having no base material obtained by the production method of this embodiment.

[Production method of antifouling sheet]

The method for producing an antifouling sheet having an antifouling layer according to the present invention has the following steps (1) to (4) in this order.

Step (1): A step of preparing an antifouling composition containing the following components (A) to (C)

Component (A): A tetrafunctional silane compound represented by the following 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 are a plurality is present, a plurality of R ¹ and X ¹ is be same or different from each other. and p represents an integer of 0 to 4.]

Component (B): A trifunctional silane compound represented by the following general formula (b)

R ² Si (OR ³ ) _q (X ² ) _3-q (b)

[In the 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. When R ³ and X ² are a plurality is present, a plurality of R ³ and X ² may be the same or different from each other. and q represents an integer of 0 to 3.]

(C) Component: Metal catalyst

Step (2): A step of coating the antifouling composition prepared in the step (1) on a support to form a coating film

Step (3): A step of heating the coated film formed on the support formed in the step (2) from the side of the support to initiate the curing reaction of the coated film from the side of the support

Step (4): Step of solidifying the coating film 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-based compounds in the antifouling composition described in the step (1) proceeds to form a polymer, thereby forming an antifouling layer.

The present inventors have found that even when an antifouling composition having the same composition is used, the state of the antifouling layer formed of the coating film changes due to the difference in the curing acceleration method of the coating film formed from the antifouling composition. More specifically, it has been found that, in the case where the step (3) is not introduced, the coating film formed of the antifouling composition sometimes gels in the process of forming the antifouling layer.

In the step (2), when the antifouling composition used in the present invention is coated on a support to form a coating film, the antifouling composition is usually dissolved in an organic solvent and applied in the form of a solution. The present inventors speculated that in the process of forming an antifouling layer, before the curing reaction of the coating film sufficiently progressed, the organic solvent volatilized or evaporated and the drying of the coating film proceeded, thereby causing the coating film to gel.

Therefore, the inventors of the present invention have found that by introducing the above-described step (3), the organic solvent in the coating film formed of the antifouling composition evaporates and / or evaporates from the surface side of the coating film to accelerate the curing reaction of the coating film .

It has also been noted that by using a metal catalyst as the component (C), the condensation reaction between the silane-based compounds can be effectively promoted and the curing reaction of the coating film can be promoted more.

As a result, it has been found that an antifouling layer having a good surface state can be formed while suppressing the gelation of the coating film, thereby completing the present invention.

Hereinafter, a method for producing the antifouling sheet of the present invention will be described.

<< Process (1) >>

The step (1) used in the present invention is a step of preparing an antifouling composition containing the above components (A) to (C).

&Lt; Antifouling composition >

The antifouling composition used in the step (1) comprises a tetrafunctional silane compound represented by the general formula (a) as the component (A), a trifunctional silane compound represented by the general formula (b) ) &Lt; / RTI &gt; component.

The antifouling composition preferably further contains an acid catalyst as the component (D), and it is preferable to add other additives other than the components (A) to (D) within the range that does not impair the effect of the present invention You can.

Hereinafter, each component contained in the antifouling composition used in the step (1) will be described.

(Component (A): tetrafunctional silane-based compound represented by the general formula (a)

The antifouling composition used in the present invention contains, as the component (A), a tetrafunctional silane compound represented by the following 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 are a plurality is present, a plurality of R ¹ and X ¹ is be same or different from each other. p represents an integer of 0 to 4;

Examples of the alkyl group which can be selected as R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, , n-hexyl group, neopentyl group, methylpentyl group and the like. Among these, a methyl group, an ethyl group or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable from the viewpoint of obtaining better curability.

The alkyl group which can be selected as R ¹ may be any of a linear chain and a branched chain, but is preferably a linear chain.

As the halogen atom which can be selected as X ¹ , a chlorine atom, a bromine atom or an iodine atom is preferable, and a chlorine atom is more preferable.

The silane-based compounds represented by the general formula (a) may be used alone or in combination of two or more.

It is preferable that the component (A) contains a silane-based compound having p in the general formula (a).

The content of the component (A) in the antifouling composition is preferably in the range of from the viewpoint of improving the curability of the antifouling layer formed from the antifouling composition, from the viewpoint of obtaining a good surface state, and from the viewpoint of obtaining a high surface hardness. , More preferably not less than 10.00 mol%, more preferably not less than 30.00 mol%, still more preferably not less than 45.00 mol%, still more preferably not less than 55.00 Mol% or more, still more preferably 65.00 mol% or more, still more preferably 75.00 mol% or more. It is preferably 98.00 mol% or less, more preferably 96.00 mol% or less, still more preferably 94.00 mol% or less, still more preferably 90.00 mol% or less. In addition, the content may be calculated from the compounding amount when each component is blended.

(Component (B): trifunctional silane-based compound represented by the general formula (b)

The antifouling composition used in the present invention contains, together with the component (A), the trifunctional silane compound represented by the following general formula (b) as the component (B).

R ² Si (OR ³ ) _q (X ² ) _3-q (b)

In the 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. When R ³ and X ² are a plurality is present, a plurality of R ³ and X ² may be the same or different from each other. q represents an integer of 0 to 3;

The number of carbon atoms of the alkyl group which can be selected as R ² is 1 to 24.

When the number of carbon atoms of the alkyl group exceeds 24, the curing property of the antifouling layer formed of the antifouling composition is deteriorated. Further, as the number of carbon atoms of the alkyl group increases, the antifouling composition tends to gel, and the surface condition of the antifouling layer formed of the antifouling composition also tends to deteriorate. From such a viewpoint, the number of carbon atoms in the alkyl group is preferably 22 or less, more preferably 20 or less, further preferably 18 or less.

The carbon number of the alkyl group which can be selected as the R ² does not include the carbon number of any substituent which the alkyl group may have.

Examples of the alkyl group which can be selected as R ² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, N-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-pentadecyl group, n-pentadecyl group, N-hexadecyl group, n-hexadecyl group, n-hexadecyl group, octadecyl group, n-nonadecyl group, butyl group, isopentyl group, neopentyl group, tert-pentyl group, methylpentyl group, isohexyl group, pentylhexyl group, butylpentyl group, and 2-ethylhexyl group.

The alkyl group which can be selected as R ² may be either a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of improving the curability and surface state of the antifouling layer formed of the antifouling composition.

The alkyl group which can be selected as R ² may have a substituent.

Examples of such a substituent include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom; A hydroxyl group; A nitro group; An amino group; Cyano; Thiol group; An epoxy group; Glycidoxin timing; (Meth) acryloyloxy group; A cycloalkyl group having 3 to 12 ring-forming carbon atoms (preferably 6 to 10 ring-forming carbon atoms); An aryl group having 6 to 12 ring-forming carbon atoms; A heteroaryl group having 6 to 12 ring-forming atoms containing a hetero atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom; An alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms); And an aryloxy group having 6 to 12 ring-forming carbon atoms, and these substituents may be further substituted.

However, the alkyl group which can be selected as R ² is preferably an alkyl group having no substituent.

Examples of the alkyl group which can be selected as R ³ and the halogen atom which can be selected as X ² include the same alkyl groups that can be selected as R ¹ in the above-mentioned general formula (a), and halogen atoms that can be selected as X ¹ .

The trifunctional silane compounds represented by the above general formula (b) may be used alone or in combination of two or more.

The component (B) preferably contains a trifunctional silane-based compound having q of 3 in the general formula (b).

The content of the component (B) in the antifouling composition used in the present invention is preferably not less than 2.50 mol%, more preferably not less than 5.00 mol%, and more preferably not less than 5.00 mol%, based on the total amount of 100 mol% More preferably at least 10.00 mol%. From the viewpoint of improving the surface condition of the antifouling layer formed from the antifouling composition, from the viewpoint of improving the curability, and from the viewpoint of obtaining a high surface hardness, it is preferably 99.00 mol% or less, more preferably 80.00 mol% , More preferably not more than 50.00 mol%, still more preferably not more than 30.00 mol%, still more preferably not more than 25.00 mol%. In addition, the content may be calculated from the compounding amount when each component is blended.

(For 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).

(A) / (B) (molar ratio) of the molar amount of the component (A) to the molar amount of the component (B)

When the [(A) / (B)] (molar ratio) is 0.01 or more, the anti-streaking layer formed of the antifouling composition has excellent curability and surface hardness. From this viewpoint, the [(A) / (B)] (molar ratio) is preferably 0.01 or more, more preferably 0.20 or more, further preferably 2.00 or more, still more preferably 3.00 or more.

It is preferable that the [(A) / (B)] (molar ratio) is 50.00 or less. (A) / (B)] (molar ratio) is 50.00 or less, an antifouling layer formed of an antifouling composition can be obtained without significantly decreasing the proportion of the alkyl group represented by R ² in the component (B) And has good water repellency. From such a viewpoint, the [(A) / (B)] (molar ratio) is more preferably 50.00 or less, still more preferably 25.00 or less, even more preferably 12.50 or less, still more preferably 10.00 or less .

[Component (B-1): trifunctional silane-based compound represented by general formula (b)] [

The antifouling composition used in the present invention preferably contains, as the component (B), at least one component (B-1) which is a trifunctional silane compound represented by the following general formula (b-1)

R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (b-1)

In the general formula (b-1), R ⁴ represents an alkyl group having from 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. When R ⁵ and X ³ are a plurality is present, a plurality of R ⁵ and X ³ are be same or different from each other. r represents an integer of 0 to 3;

When the number of carbon atoms of the alkyl group represented by R ⁴ is 15 or more, a water repellent layer having a high water contact angle and a low water slip angle is obtained. From such a viewpoint, the R ⁴ is preferably at least 16. The preferable upper limit value of the carbon number of the alkyl group represented by R ⁴ is the same as the preferable value of the upper limit value of R ² described above, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less. The reason for setting each preferable upper limit value is also as described above for R ² .

The carbon number of the alkyl group which can be selected as the R ⁴ does not include the carbon number of any substituent which the alkyl group may have.

On the other hand, as described above, when the number of carbon atoms of the alkyl group represented by R ⁴ is increased, the curability of the antifouling layer formed of the antifouling composition is lowered, the antifouling composition tends to gel more and the surface condition of the formed antifouling layer tends to deteriorate The inventors of the present invention have found out.

However, by using the production method of the present invention, gelation of the antifouling composition can be suppressed, and the surface condition of the antifouling layer can be improved. Therefore, it is possible to use an antifouling composition containing at least one component of (B-1) as the component (B), so that an antifouling layer having excellent curability and surface condition and excellent water repellency can be obtained.

Examples of the alkyl group which can be selected as R ⁴ include n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, -Hexocyclyl group, an n-dococyl group, an n-tricyclyl group, and an n-tetracosyl group.

The alkyl group which can be selected as R ⁴ may be either a straight chain or a branched chain, but it is preferably a straight chain from the viewpoint of improving the curability and surface state of the antifouling layer formed of the antifouling composition. The alkyl group which can be selected as R ⁴ is preferably an n-pentadecyl group or an n-hexadecyl group from the viewpoint of the curability and surface state of the antifouling layer, and from the viewpoint of obtaining better water repellency, An n-pentadecyl group, or an n-octadecyl group is preferable.

The alkyl group which can be selected as R ⁴ may have a substituent. The substituent of the alkyl group which can be selected as R ^{4 is} as described above for the substituent that the alkyl group which can be selected as R ² has. However, the alkyl group which can be selected as R ⁴ is preferably an alkyl group having no substituent.

Examples of the alkyl group which can be selected as R ⁵ and the halogen atom which can be selected as X ³ include the same ones as the halogen atom which can be selected as the alkyl group and X ¹ which can be selected as R ¹ in the general formula (a) .

The trifunctional silane-based compounds represented by the above-mentioned general formula (b-1) may be used alone or in combination of two or more.

The component (B-1) preferably contains a trifunctional silane-based compound represented by the general formula (b-1) wherein r is 3.

[Component (B-2): trifunctional silane-based compound represented by general formula (b-2)] [

The antifouling composition used in the present invention preferably contains, as the component (B), at least one component (B-2) which is a trifunctional silane compound represented by the following general formula (b-2)

_{^{R 6 Si (OR 7) s}} (X 4) 3-s (b-2)

In the 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. When R ⁷ and X ⁴ are a plurality is present, a plurality of R ⁷ and X ⁴ may be the same or different from each other. s represents an integer of 0 to 3;

The number of carbon atoms of the alkyl group which can be selected as R ⁶ is 1 to 3.

When the number of carbon atoms of the alkyl group is within this range, the hardening property of the antifouling layer formed of the antifouling composition is excellent and the surface hardness is also improved. The carbon number of the alkyl group which can be selected as the R ⁶ does not include the carbon number of any substituent which 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- And from the viewpoint of obtaining a low coefficient of friction, a methyl group is more preferable.

The alkyl group which can be selected as R ⁶ may have a substituent. The substituent of the alkyl group which can be selected as R ⁶ is the same as described above for the substituent of the alkyl group which can be selected as R ² . However, the alkyl group which can be selected as R ⁶ is preferably an alkyl group having no substituent.

Examples of the alkyl group which can be selected as R ⁷ and the halogen atom which can be selected as X ⁴ include the same ones as the halogen atom which can be selected as the alkyl group and X ¹ which can be selected as R ¹ in the general formula (a) .

Further, the trifunctional silane-based compound represented by the above-mentioned general formula (b-2) may be used singly or in combination of two or more kinds.

The component (B-2) preferably contains a trifunctional silane-based compound wherein s in the general formula (b-2) is 3.

It is more preferable that the antifouling composition used in the present invention contains the component (B-1) and the component (B-2) together as the component (B). (B-1) and (B-2) are used in combination as the component (B), the surface state and the curability are good, the water repellency and the water-solubility are good , It is also possible to form an antifouling layer having balanced characteristics of high surface hardness and low friction coefficient.

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 preferably within a range from the viewpoint of improving the curability of the antifouling composition Is preferably not less than 0.30 mol%, more preferably not less than 0.30 mol%, based on 100 mol% of the total amount of the component (A), the component (B-1) and the component (B-2) from the viewpoint of obtaining a good surface state, , More preferably not less than 0.50 mol%, more preferably not less than 1.00 mol%, still more preferably not less than 2.00 mol%, still more preferably not less than 4.00 mol%, and preferably not more than 36.00 mol% More preferably not more than 26.00 mol%, still more preferably not more than 24.00 mol%, still more preferably not more than 19.00 mol%. In addition, the content may be calculated from the compounding amount when each component is blended.

(B-1) and the component (B-1) in the relation of the component (A) and the component (B-1) (A) / (B-1)] (molar ratio) of the molar amount of the component (A) to the component (A) is preferably 1.40 or more.

When the [(A) / (B-1)] (molar ratio) is 1.40 or more, the stainproofing layer formed of the antifouling composition has excellent curability and surface hardness. From this point of view, the ratio of [(A) / (B-1)] (molar ratio) is preferably 1.50 or more, more preferably 1.90 or more, still more preferably 2.10 or more, still more preferably 2.50 or more, Still more preferably not less than 5.00, still more preferably not less than 6.00.

It is also preferable that the ratio of [(A) / (B-1)] (molar ratio) is 300.00 or less. The antioxidant layer formed of the antifouling composition is more excellent in water repellency due to the presence of the alkyl group represented by R ⁴ in the component (B-1) because the [(A) / (B-1)] (molar ratio) Respectively. From this point of view, the ratio of [(A) / (B-1)] (molar ratio) is more preferably 200.00 or less, still more preferably 150.00 or less, even more preferably 100.00 or less, still more preferably 90.00 Still more preferably not more than 50.00, even more preferably not more than 20.00.

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 preferably within a range from the viewpoint of improving the curability of the antifouling composition Is preferably not less than 0.50 mol%, more preferably not less than 0.5 mol% based on the total amount of 100 mol% of the component (A), the component (B-1) and the component (B-2) from the viewpoint of obtaining a good surface state, , More preferably not less than 1.00 mol%, still more preferably not less than 1.30 mol%, still more preferably not less than 2.00 mol%, and preferably not more than 40.00 mol%, more preferably not more than 38.00 mol% Preferably not more than 35.00 mol%, still more preferably not more than 20.00 mol%. In addition, the content may be calculated from the compounding amount when each component is blended.

(B-1) and (B-2) are used as the component (B), the molar amount of the component (B-2) (A) / (B-2)] (molar ratio) of the molar amount of the component (A) to the component (A) is not particularly limited and is preferably 1.00 or more, and 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 further preferably 35.00 or less.

(For condition (II))

The antifouling composition used in the present invention is preferably an antifouling composition satisfying the following condition (II) in the relation of the component (B-1) and the component (B-2).

The ratio of the molar amount of the component (B-1) to the molar amount of the component (B-1) to the total molar amount of the component (B-1) 2)}] (molar ratio) of not less than 0.020

When the molar ratio of (B-1) / {(B-1) + (B-2)}] is 0.020 or more, the static friction coefficient and the dynamic friction coefficient of the antifouling layer formed of the antifouling composition become low, Is excellent. The presence of an alkyl group represented by R ⁴ in the component (B-1) improves the water contact angle of the antifouling layer formed of the antifouling composition and is excellent in water repellency. (B-1) / {(B-1) + (B-2)}] (molar ratio) is preferably 0.025 or more, more preferably 0.035 or more, still more preferably 0.080 More preferably not less than 0.180, even more preferably not less than 0.220.

The upper limit of the ratio of [(B-1) / {(B-1) + (B-2)}]] is not particularly limited, B-2)}] (molar ratio) is preferably 0.995 or less, more preferably 0.990 or less, further preferably 0.980 or less, still more preferably 0.950 or less.

Further, the antifouling composition used in the present invention contains the antifouling composition (B-1) and the component (B-2) as the trifunctional silane compound so as to satisfy the conditions (I) and It is possible to combine a higher surface hardness of the antifouling layer and a lower friction coefficient. Also, by containing the component (B-2), improvement in weatherability of the antifouling layer formed of the antifouling composition can be expected.

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

(Component (C): metal catalyst)

The antifouling composition used in the present invention, in addition to the components (A) and (B), further contains a metal catalyst as the component (C). When the metal catalyst is not contained, the condensation reaction of the component (A) and the component (B) can not be effectively promoted, and the curability of the antifouling layer formed of the antifouling composition can not be sufficiently improved.

Further, in the case of the antifouling composition containing no component (C), the curing reaction can not proceed sufficiently at a relatively low temperature (130 ° C or lower). Therefore, when it is intended to form an antifouling layer formed of the antifouling composition on a support having low heat resistance such as a vinyl chloride resin, for example, an antifouling layer is formed at a low temperature at which heat shrinkage of the support can be suppressed There is a possibility that the curability of the antifouling layer becomes insufficient. On the other hand, in order to sufficiently accelerate the curing reaction, if the curing is attempted at a relatively high temperature (higher than 130 deg. C), the support may be thermally shrunk.

The metal catalyst is preferably a metal catalyst which does not require light irradiation for the purpose of exhibiting catalytic action.

In the present specification, the "metal catalyst which does not require light irradiation for the purpose of exhibiting the catalytic action" means that the component (A) and the component (B) are subjected to light irradiation Refers to a metal catalyst that is not required. For example, there is a method in which an oxidation reaction and a reduction reaction are caused by generating an electron and a hole by light irradiation, such as titanium oxide (TiO ₂ ) or zinc oxide (ZnO) , Except for what is generally referred to as a photocatalyst.

Further, when the antifouling layer contains the above-mentioned "metal catalyst that does not require light irradiation for the purpose of exhibiting catalytic action", it is possible to avoid a problem that may occur when a photocatalyst is used. A problem that may occur in the case of using the photocatalyst is that the photocatalyst itself is a solid, resulting in a decrease in water repellency due to increase in surface roughness of the antifouling layer, And a decrease in the durability of the antifouling layer by promoting the 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 the photocatalyst containing a titanium atom, and examples thereof include titanium alkoxide, titanium chelate, titanium acylate, etc., and hydroxides, acetates, carbonates, Sulfate, nitrate, chloride, and the like.

Examples of the titanium alkoxide include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide and the like.

Examples of the titanium chelate include titanium acetylacetonate such as titanium diisopropoxy bis (acetylacetonate) and titanium tetraacetylacetonate; Titanium ethylacetoacetate such as titanium diisopropoxybis (ethylacetoacetate); Titanium triethanolaminate such as titanium diisopropoxybis (triethanolaminate); Titanium octylene glycolate such as titanium tetraoctyleneglycolate, titanium dioctyloxybis (octyleneglyconate), and titanium di-2-ethylhexybis (2-ethyl-3-hydroxyhexoxide); Titanium lactate, and titanium lactate ammonium salt.

Examples of the titanium acylate include polyhydroxytitanium stearate and the like.

The zirconium-based catalyst is preferably a compound other than the photocatalyst containing a zirconium atom, and examples thereof include zirconium alkoxide, zirconium chelate, and zirconium acylate, and hydroxides, Sulfate, nitrate, chloride, and the like.

Examples of the zirconium alkoxide include zirconium tetra n-propoxide, zirconium tetra-n-butoxide and the like.

Examples of the zirconium chelate include zirconium acetylacetonate such as zirconium tributoximo monoacetylacetonate and zirconium tetraacetylacetonate; Zirconium ethyl acetoacetate such as zirconium dibutoxybis (ethylacetoacetate); Zirconyl chloride compounds, zirconium lactate ammonium salts and the like.

The zirconium acylate includes, for example, zirconium octylate compounds and zirconium stearate.

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

The tin-based catalyst is preferably a compound other than the photocatalyst containing a tin atom, and examples thereof include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide , Dibutyltin dithiocarboxylate, dibutyltin dimaleate, dioctyltin mercuridate, dioctyltin thiocarboxylate, and the like, or inorganic tin compounds.

The aluminum-based catalyst is preferably a compound other than the photocatalyst containing an aluminum atom, and examples thereof include an acetoacetate complex of aluminum or an acetylacetonate complex of aluminum.

As the acetoacetate complex of aluminum, for example, diisopropoxy aluminum monooleate acetoacetate, monoisopropoxy aluminum bisoleyl acetoacetate, monoisopropoxy aluminum monooleate monoethylacetoacetate, diisopropoxide Diisopropoxyaluminum monostearyl acetoacetate, monoisopropoxy aluminum mono-N-lauroyl-beta-alanate mono-N-lauroyl monoauryl acetoacetate, diisopropoxy aluminum monostearyl acetoacetate, diisopropoxy aluminum monoisostearyl acetoacetate, Acetylacetone, aluminum trisacetylacetonate, and the like.

Examples of the acetylacetonate complex of aluminum include monoacetylacetonate aluminum bis (isobutyl acetoacetate) chelate, monoacetylacetonate aluminum bis (2-ethylhexyl acetoacetate) chelate, monoacetylacetonate aluminum bis Dodecyl acetoacetate) chelate, and monoacetylacetonate aluminum bis (oleyl acetoacetate) chelate.

The zinc-based catalyst is preferably a compound other than the photocatalyst containing a zinc atom, and examples thereof include a zinc-chromium oxide, a zinc-aluminum oxide, a zinc-aluminum-chromium oxide, a zinc- Zinc-iron oxide, and zinc-iron-aluminum oxide.

The metal catalyst may be used alone or in combination of two or more.

In addition, from the viewpoints of effectively accelerating the condensation reaction between the silane-based compounds to improve the curability of the antifouling layer formed of the antifouling composition and the antifouling composition capable of promoting the curing reaction even at a relatively low temperature , It is preferable that at least the titanium-based catalyst is contained.

As the titanium-based catalyst, a titanium chelate is preferable, and titanium ethylacetoacetate, titanium acetylacetonate or titanium octylene glyonate is more preferable, titanium ethylacetoacetate is more preferable, and titanium diisopropoxy bis (ethyl Acetoacetate) is even more preferred.

From the viewpoint of improving the curability of the antifouling layer formed of the antifouling composition and the antifouling composition capable of promoting the curing reaction even at a relatively low temperature (130 DEG C or less), the content of the component (C) in the antifouling composition More preferably 0.100 mol% or more, more preferably 0.150 mol% or more, still more preferably 0.300 mol% or more, based on 100 mol% of the total of the components (A) and (B) , Still more preferably not less than 0.500 mol%, still more preferably not less than 1.000 mol%. The content is preferably not more than 50.000 mol%, more preferably not more than 30.000 mol%, more preferably not more than 20.000 mol%, even more preferably not more than 10.000 mol%, still more preferably not more than 6.000 mol% , Still more preferably not more than 3.000 mol%.

In addition, the content may be calculated from the compounding amount when each component is blended.

(Component (D): acid catalyst)

The antifouling composition used in the present invention preferably further contains an acid catalyst as the component (D) from the viewpoint of further improving the curability of the antifouling layer.

By containing an acid catalyst in the antifouling composition, the hydrolysis of the reactive functional groups of the component (A) and the component (B) is promoted. As a result, the polycondensation reaction between the silane-based compounds is further promoted, and an antifouling layer having excellent curability can be formed.

The acid catalyst is not particularly limited so long as it is a component having an action of promoting the hydrolysis of the reactive functional groups of the component (A) and the component (B). From the viewpoint of further improving the curability of the antifouling layer formed of the antifouling composition, for example, a group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, bromic acid, p- toluenesulfonic acid and trifluoroacetic acid It is preferable to contain at least one selected from among them, and it is more preferable to contain hydrochloric acid.

The acid catalyst may be used alone or in combination of two or more.

The content of the component (D) in the antifouling composition is preferably 0.010 mol% or more, more preferably 0.02 mol% or less, and more preferably 0.02 mol% or less, in terms of the total amount of the components (A) , More preferably 0.030 mol% or more, still more preferably 0.050 mol% or more, still more preferably 0.060 mol% or more. The content is preferably 1.000 mol% or less, more preferably 0.500 mol% or less, still more preferably 0.100 mol% or less, still more preferably 0.075 mol% or less. In addition, the content may be calculated from the compounding amount when each component is blended.

(Other additives)

In addition to the components (A) to (D) described above, the antifouling composition used in the present invention may contain other additives insofar as the effect of the present invention is not impaired.

Other additives include, for example, a resin component, a curing agent, an antioxidant, 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, still more preferably 0 to 5% by mass, relative to the total amount of the antifouling composition 0 to 2% by mass.

The total content of the components (A), (B), (C) and optionally (D) in the antifouling composition used in the present invention is such that the total amount of the antifouling composition (solid content: 100% , More preferably not less than 65 mass%, more preferably not less than 80 mass%, still more preferably not less than 90 mass%, still more preferably not less than 95 mass% , More preferably not less than 99 mass%, and preferably not more than 100 mass%. The content is more preferably 100% by mass. When the component (D) is not contained in the antifouling composition, the preferable range of these contents represents a preferable range of the total content of the components (A) to (C). In addition, the content may be calculated from the compounding amount when each component is blended.

<< Process (2) >>

The step (2) used in the present invention is a step of coating the antifouling composition prepared in the step (1) on a support to form a coating film.

When the antifouling composition used in the present invention is applied, it is preferably dissolved in an organic solvent and applied in the form of a solution by a known coating method on a support.

Examples of the solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene and the like.

Examples of the application method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, die coating, gravure coating and the like .

<Support>

The support used in the step (2) is not particularly limited as long as it can form a coating film composed of the antifouling composition on the support and does not cause any problems in the following steps (3) and (4). As the support, it is preferable to use a substrate or a release material to be described later.

The support may be a support which is contained in the structure of the obtained antifouling sheet, or may be a support which is removed in the step after step (3) to be described later.

(materials)

Examples of the substrate that can be used as the support include a paper substrate, a resin film, a resin sheet, a substrate laminated with a paper substrate by a resin, and the like, and can be appropriately selected depending on the use of the antifouling sheet.

Examples of the paper constituting the paper substrate include a thin paper, a heavy paper, a top paper, an impregnated paper, a coated paper, an art paper, a sulfur paper, and a gloss paper.

Examples of the resin constituting the resin film or the resin sheet include polyolefin resins such as polyethylene and polypropylene; Vinyl-based resins of ethylene-methacrylic acid copolymer such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polystyrene; Acrylonitrile-butadiene-styrene copolymers; 3 cellulose acetate; Polycarbonate; Urethane resins such as polyurethane and acrylic modified polyurethane, and the like.

Examples of the substrate laminated with a paper substrate with a resin include a laminate paper obtained by laminating the above paper substrate with a thermoplastic resin such as polyethylene.

Of these substrates, a resin film or a resin sheet is preferable, and a resin film or a resin sheet made of a polyester-based resin is more preferable, and a resin film or a resin sheet made of polyethylene terephthalate (PET) is more preferable.

As a substrate usable as the support, a substrate having a primer layer formed thereon with a primer layer on the surface of the substrate described above may be used from the viewpoint of improving the adhesion to the scattering layer or a later-described inner layer to be described later.

Examples of the component constituting the primer layer include a polyester resin, a urethane resin, a polyester urethane resin and an acrylic resin, and these resins may be used alone or in combination of two or more thereof .

In addition, as a substrate which can be used as the support, a substrate having an inner layer formed by further forming an inner layer of a polymeric ultraviolet absorber on the surface of the substrate described above or on the surface of the substrate on which the primer layer is adhered And a primer layer may be provided between the back layer and the substrate). The polymeric ultraviolet absorbent has a structure in which an ultraviolet absorption skeleton is covalently bonded to the polymer structure, and preferably has a weight average molecular weight of 5,000 or more, more preferably 10,000 or more.

As a substrate usable as the support, a substrate (a hard coat layer and a hard coat layer) having a hard coat layer on which a hard coat layer is further formed is formed on the surface of the substrate described above or on the surface of the substrate to which the primer layer is attached And a primer layer may be provided between the substrates). The material for forming the hard coat layer is not particularly limited and may be appropriately selected from known hard coat layer forming materials according to the use of the antifouling sheet.

When the substrate usable as the support is a resin film or a resin sheet, the surface of the resin film or the resin sheet may be subjected to a surface treatment such as an oxidation method or a surface irregularity method The surface treatment 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), a flame treatment, a hot air treatment, an ozone / ultraviolet ray irradiation treatment and the like.

The unevenness method is not particularly limited, and examples thereof include a sand blast method and a solvent treatment method.

These surface treatments are appropriately selected according to the kind of the substrate, but from the viewpoint of improving the adhesion with the antifouling layer and from the viewpoint of operability, the corona discharge treatment method is preferable.

The thickness of the substrate is appropriately set in accordance with the use of the antifouling sheet, but is preferably 10 to 250 占 퐉, more preferably 15 to 200 占 퐉, and still more preferably 20 to 150 占 퐉 in view of handleability and economy.

In addition, the substrate usable as the support may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an anti-blocking agent, a colorant, and the like in addition to the polymeric ultraviolet absorber described above.

(Peeling material)

Examples of the release material usable as the support include a release sheet subjected to both-side separation treatment and a release sheet subjected to one-side separation treatment, and a material coated with a release agent on the release material.

Examples of the base material for peeling material include a paper base material, a resin film, a resin sheet, a base material laminated with a paper base material resin, and the like, which can be used as a base material of one embodiment of the antifouling sheet of the present invention.

Examples of the releasing agent include rubber-based 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 占 퐉, more preferably 25 to 150 占 퐉.

In the case where the antifouling layer is sandwiched between two peeling members, the two peeling members may be mutually the same or different.

The release material may be contained as it is in the structure of the obtained antifouling sheet or may be used as a release material to be removed in the step after step (3) to be described later. Examples of the case where the release material is removed in the step after step (3) include, for example, the following examples. First, the antifouling composition is coated on the release material in the step (2), and the antifouling layer is formed through the steps (3) and (4) described later. Then, there is a case in which the antifouling layer is bonded to the base material, the new release material, a pressure-sensitive adhesive layer or the like described later, and then the release material is removed.

<< Process (3) >>

The step (3) used in the present invention is a step of heating the coating film formed on the support formed in the step (2) from the support side to initiate the curing reaction of the coating film from the surface on the support side.

As described above, the present inventors have found that, by heating the coating film on the support from the side of the support, the organic solvent in the coating film evaporates and / or evaporates from the coating film surface opposite to the support side, The curing reaction can be initiated and promoted.

When the step (3) is not introduced, the gelation of the coating film tends to proceed as compared with the case where the step (3) is introduced. As a result, the surface condition of the antifouling layer is liable to be deteriorated, the hardenability of the antifouling layer is lowered, and the surface hardness is lowered. Further, when an antifouling composition which is more likely to gel the coating film is used, the coating film becomes gelled, the curability of the antifouling layer is lowered, and the surface condition of the antifouling layer is deteriorated. There is a possibility that the antifouling layer can not be formed.

Here, "to initiate the curing reaction of the coating film from the side of the support" means that the curing reaction in the interior of the coating film close to the support side is preferential for the curing reaction inside the coating film close to the side opposite to the support side To initiate and accelerate the curing reaction.

From this viewpoint, in the step (3), the temperature of the surface of the coating film on the support side is heated so as to rise faster than the temperature of the surface opposite to the support, and the curing reaction It is preferable to start and accelerate.

In order to satisfy such a condition, the surface of the support opposite to the coating film side of the support on which the coating film is formed (hereinafter also referred to as &quot; coating film formation sheet &quot;) is heated so that the curing reaction of the coating film Initiation and promotion of the gene.

When the coating film is heated, a coating film-forming sheet on which the coating film is formed is usually held using a supporting mechanism, or the coated film-forming sheet is placed on the supporting mechanism. Examples of the support mechanism include a support mechanism such as a base paper, a metal and / or a plastic sheet, a belt conveyor, and a guide roll.

In this heating method, for example, in the case of heating by hot air or the like, the temperature of the hot air jetted from the surface of the support of the coating film forming sheet is changed from the temperature of the hot air Is set to a higher value. In addition, a method of spraying hot air only on the support side of the above-mentioned coat-forming sheet is also cited.

From the viewpoint of obtaining the effect of the present invention more surely, a method of heating the coating film by bringing the surface of the support on the opposite side of the coating film side of the coating film forming sheet into contact with a heating mechanism previously heated is preferable.

As the heating mechanism used in the heating method, a drying mechanism described later in the following step (4) may be used.

The heating temperature in the step (3) can be appropriately set. However, as described above, the temperature of the surface of the coating film on the support side is heated so as to rise faster than the temperature of the surface opposite to the support, It is preferable to initiate and accelerate the curing reaction of the coating film. Therefore, it is preferable to heat at least at a temperature higher than the temperature of the surface of the coated film opposite to the surface on the support side.

Further, the antifouling composition used in the present invention can proceed the curing reaction even at a relatively low temperature of 130 캜 or lower, and can suppress the heat shrinkage of the support in the case where a support having low heat resistance such as vinyl chloride is used.

Therefore, the heating temperature is preferably 40 占 폚 or higher, more preferably 50 占 폚 or higher, further preferably 60 占 폚 or higher, even more preferably 70 占 폚 or higher, from the viewpoint of the above viewpoint and productivity. It is preferably 130 占 폚 or lower, more preferably 120 占 폚 or lower, even more preferably 110 占 폚 or lower, still more preferably 95 占 폚 or lower.

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 suitably set.

The time from the formation of the coating film in the step (2) to the step (3) is preferably as short as possible from the viewpoint of minimizing the loss due to the volatilization or evaporation of the organic solvent in the coating film formed in the step (2) . Preferably 20 seconds or less, more preferably 10 seconds or less, further preferably 5 seconds or less, still more preferably 3 seconds or less.

<< Process (4) >>

The step (4) used in the present invention is a step of forming the antifouling layer by solidifying the coating film.

In the coating film in which the curing reaction is promoted in the step (3), in the step (4), the surface of the coating film forming sheet opposite to the support side is dried and the coating film is cured. Finally, the coated film is solidified without being gelled, and becomes an antifouling layer.

In this step, it is preferable that the coating film in which the curing reaction is promoted in the step (3) is put into a drying mechanism to form a scattering layer.

Examples of the drying apparatus include a batch type drying apparatus such as an air oven, a heat roll, a hot air through apparatus (an apparatus that is heated and dried while an object to be dried moves and passes through an open type drying furnace, etc.) And a continuous drying apparatus such as a dryer. In addition, a device that can be used as a part of these drying mechanisms, for example, a heat transfer type heater such as an oil heater, and a heater such as a far infrared heater can be used as a drying mechanism.

The drying temperature and the drying time in the step (4) are not particularly limited and can be appropriately set.

Further, the antifouling composition used in the present invention can proceed the curing reaction even at a relatively low temperature of 130 캜 or lower, and can suppress the heat shrinkage of the support in the case where a support having low heat resistance such as vinyl chloride is used.

Therefore, in view of the above viewpoint and productivity, the temperature is preferably 10 ° C or more, more preferably 20 ° C or more, further preferably 40 ° C or more, still more preferably 50 ° C or more Preferably 60 DEG C or more. It is preferably 130 占 폚 or lower, more preferably 120 占 폚 or lower, even more preferably 110 占 폚 or lower, still more preferably 95 占 폚 or lower.

From the viewpoint of smooth transition from the step (3) and from the viewpoint of continuously promoting the curing reaction in the step (3), the temperature of the step (4) It is preferable to set the temperature to the same temperature.

The heating time in the step (4) is not particularly limited as long as the effect of the present invention can be exhibited, and can be appropriately set.

The time from the start of the step (3) to the step (4) is not particularly limited as long as the effect of the present invention is exerted. However, from the viewpoint of productivity that the solidification of the final antifouling layer is completed quickly, Preferably 60 seconds or less, more preferably 30 seconds or less, still more preferably 20 seconds or less, even more preferably 10 seconds or less, still more preferably 5 seconds or less.

In the step (4), the heating treatment in the step (3) may be continued as it is, and the coating film may be solidified so as to finally become the antifouling layer.

Further, a new release material may be further laminated on the antifouling layer formed by the above-described manufacturing method in order to protect the surface of the antifouling layer at the time of storage.

The antifouling sheet 1b of Fig. 1 (b) or the antifouling sheet 2b of Fig. 2 (b) can be obtained by bonding the pressure-sensitive adhesive layer formed on another release agent onto the formed antifouling layer or substrate, An antifouling sheet to which a pressure-sensitive adhesive layer is adhered may be produced.

In the case where the support used in the step (2) is a release agent, the release agent used as the support may be removed after the release layer is formed and then the release agent layer is pasted with the above-described base material or new release agent .

[Antifouling 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 aforementioned method of producing the antifouling sheet of the present invention.

&Lt; Configuration Example of Antifouling Sheet >

Fig. 1 is a cross-sectional view showing an example of an antifouling sheet having a substrate, which is obtained by a production method which is an example of this embodiment.

As the antifouling sheet having a substrate, for example, antifouling sheet 1a having antifouling layer 11 on substrate 12 as shown in Fig. 1 (a) can be mentioned.

It is also possible to form the pressure-sensitive adhesive layer 13 and the release material 14 on the surface of the base material 12 opposite to the surface having the antifouling layer 11 as shown in Fig. 1 (b) The sheet 1b may be used.

Further, on the antifouling layer 11 of the antifouling sheets 1a and 1b, a release material may be further formed for protection of the antifouling layer at the time of storage.

Fig. 2 is a cross-sectional view showing an example of an antifouling sheet having no substrate, which is obtained by a manufacturing method which is an example of this embodiment.

As the antifouling sheet having no base material, for example, an antifouling sheet 2a having a configuration in which the antifouling layer 11 is sandwiched between two peeling materials 14 and 14 'as shown in Fig. 2 (a) .

2 (b), the antifouling sheet 11 in which the pressure-sensitive adhesive layer 13 is formed between the antifouling layer 11 and the release material 14 ' (2b).

(Stratum corneum)

The antifouling layer of the antifouling sheet obtained by the production method of the present invention is formed from the antifouling composition described above.

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, still more preferably 0.10 μm or more. 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 Lt; / RTI &gt;

(materials)

When the antifouling sheet of the present invention has a base material, the base material can be appropriately selected according to the use of the antifouling sheet and is the same as described above with respect to the base material usable in the method of producing the antifouling sheet of the present invention.

(Peeling material)

When the antifouling sheet of the present invention has a release material, the release material may be appropriately selected according to the use of the antifouling sheet, and the release material usable in the production method of the antifouling sheet of the present invention is as described above .

(Pressure-sensitive adhesive layer)

When the antifouling sheet of the present invention has a pressure-sensitive adhesive layer, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may be appropriately selected depending on the use of the antifouling sheet.

Specific examples of the pressure sensitive adhesive include acrylic pressure sensitive adhesives, urethane pressure sensitive adhesives, silicone pressure sensitive adhesives, rubber pressure sensitive adhesives, polyester pressure sensitive adhesives, and curable pressure sensitive adhesives that are cured by energy rays such as ultraviolet rays.

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 占 퐉, more preferably 5 to 80 占 퐉.

Example

Examples 1 to 6

Each antifouling sheet was produced by the following steps (1) to (4).

Step (1):

The components (A) and (B) were mixed with the kind and mixing ratio (effective ingredient ratio, mol%) shown in Table 1 and diluted by adding ethanol to obtain a solution having an effective ingredient concentration of 1.8M. Hydrochloric acid as component (D) was further added to the solution at the compounding ratio shown in Table 1 (effective component ratio, mol%) and stirred for 1 minute. After stirring, the solution was allowed to stand still for 15 minutes.

Subsequently, titanium diisopropoxybis (ethylacetoacetate) as component (C) was blended with the compounding ratio (effective component ratio, mol%) shown in Table 1 to prepare a solution of the antifouling composition.

Step (2):

A polyethylene terephthalate (PET) film (product name: Cosmo Shine A-4100, thickness: 50 占 퐉, manufactured by Toyobo Co., Ltd.) having a primer layer on one side was used as the base material.

On the primer layer of the base material to which the primer layer was adhered, a solution of the antifouling composition prepared as above was applied using Meyer bar to form a coating film.

Step (3):

The coating film on the substrate obtained in the step (2) was placed on the substrate (product name "Adavel", thickness: 1 mm, manufactured by Fuji Paper Co., Ltd.) heated to 80 캜 so that the substrate side was in contact with the substrate, Lt; / RTI &gt;

The time from the formation of the coating film on the substrate in the step (2) to the placing of the substrate on which the coating film was formed on the ground in the step (3) was within 3 seconds.

Step (4):

Subsequently, the coated film was placed in an oven set at 80 DEG C for each site and dried at 80 DEG C for 2 minutes to produce an antifouling sheet having an antifouling layer having a thickness shown in Table 3. [ Further, the time from the placing of the substrate on which the coating film is formed on the ground in step (3) to the putting into the oven in step (4) was within 5 seconds.

Comparative Examples 1 to 6

Each of the antifouling sheets was produced in the same manner as in Examples 1 to 6 except that the soil used in the step (3) was used in advance at 80 ° C without being heated to room temperature (25 ° C).

The details of each component shown in Table 1 used in the preparation of the antifouling composition in each example and each comparative example are as follows.

<Component (A): tetrafunctional silane-based compound represented by formula (a)>

&Quot; TEOS &quot;: tetrafunctional silane compound having tetraethoxysilane, p = 4 and R ¹ = ethyl group (number of carbon atoms: 2) in the general formula (a).

<Component (B): trifunctional silane-based compound represented by general formula (b)>

· "Hexadecyltrimethoxysilane": a trifunctional silane-based compound having q = 3, R ² = n-hexadecyl group (carbon number: 16) and R ³ = methyl group (carbon number: 1) in the above- .

Octadecyltrimethoxysilane ": a trifunctional silane compound having q = 3, R ² = n-octadecyl group (carbon number: 18) and R ³ = methyl group (carbon number: 1) in the general formula .

When these compounds are alternately read with R ² as R ⁴ , R ³ as R ⁵ , and q as r, the compounds represented by the above-mentioned general formula (b-1), that is, &Lt; / RTI &gt;

Methyltrimethoxysilane: A trifunctional silane-based compound represented by the general formula (b) wherein q = 3, R ² = methyl group (carbon number: 1) and R ³ = methyl group (carbon number: 1).

In addition, when the compound is read by changing R ² to R ⁶ , R ³ to R ⁷ and q to s, the compound represented by the above formula (b-2), that is, the compound represented by the formula (B-2) to be.

&Lt; Component (C): Metal-based catalyst >

Titanium-based catalyst: Titanium diisopropoxybis (ethylacetoacetate) [product name "ORGATICS TC-750" manufactured by Matsumoto Fine Chemicals Co., Ltd.].

&Lt; Component (D): acid catalyst >

&Quot; hydrochloric acid &quot;: 0.01 M hydrochloric acid.

The characteristics of the antifouling sheet prepared 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.

&Lt; Thickness of the antifouling layer &

The thickness of the antifouling layer was measured by a spectroscopic ellipsometer (product name "M-2000" manufactured by J. A. Woollam).

&Lt; Surface state of stagnant osmosis &

The surface of the antifouling layer of the antifouling sheet prepared in each example and each comparative example was visually observed and the surface condition of the antifouling layer was evaluated by the following criteria.

A: It was transparent.

B: Slightly cloudy.

C: Cloudiness has occurred and it is no longer transparent.

Further, since evaluation of the surface condition of the antifouling layer is "C", since it can not withstand use, evaluation other than the curability evaluation of the antifouling layer described below was not carried out.

&Lt; Curability of an antifouling layer >

The surface of the antifouling layer of the antifouling sheet prepared in each of the Examples and Comparative Examples was rubbed with a finger 20 times and the antifouling layer was visually observed and the curability of the antifouling layer was evaluated according to the following criteria.

A: No change was seen compared to before finger rubbing.

· B: It was discolored slightly white, but acceptable.

C: White discoloration.

D: The coating film composed of the antifouling composition was not cured and the antifouling layer could not be formed.

In addition, regarding the evaluation of the curability of the antifouling layer as &quot; C &quot; or &quot; D &quot;

<Water contact angle of stagnant water>

The water contact angle of the antifouling layer was measured with respect to the antifouling layer surface of each of the antifouling sheets prepared in each of the Examples and Comparative Examples using a full contact angle measuring instrument (product name: DM-701) manufactured by Kyowa Interface Science Co., 2 &lt; / RTI &gt;

<Water slope in the stratum pentagon>

The antifouling sheets prepared in each of the examples and comparative examples were placed on a sample table (glass plate) wetted with water and having an inclination angle of 0 DEG. Next, 14 μl of pure water was dropped onto the surface of the antifouling layer of the antifouling sheet to form a droplet, and when the sample was inclined, the inclination angle of the sample stand when the retraction angle of the droplet was moved was defined as the water inclination angle.

&Lt; Surface hardness of the antifouling layer >

(At a depth of 45 nm from the surface layer of the antifouling layer of the antifouling sheet prepared in each example and each comparative example (toward the substrate in the vertical direction) using a nanoindenter (product name: "Nano Indenter SA2" The hardness modulus was measured.

The value of the modulus of the hardness was defined as the surface hardness.

&Lt; Frictional coefficient of the antifouling layer >

The test was conducted using a universal tensile tester Tensilon manufactured by A & D Co., Ltd. according to JIS K7312. A sample made of the antifouling sheet prepared in each of the Examples and Comparative Examples was stuck to a weight of a flat and smooth metal sheet (200 g) having a side of 63.5 mm, and a polyethylene terephthalate film (trade name: T-60 &quot;, thickness: 50 mu m).

From Table 1 and Table 2, using the antifouling composition of Examples 1 to 4, the antifouling sheet produced by the above-mentioned production method had good surface condition and curability. It was confirmed that the water contact angle was large, the water sliding angle was small, and water repellency and water fastness were also excellent. In addition, as shown in Examples 1 and 4, the surface hardness was high, the friction coefficient was low, and both properties were good.

Using the antifouling compositions of Examples 5 and 6, the antifouling sheets produced by the above-mentioned production method were inferior to those of Examples 1 to 4 having different surface conditions, but were acceptable for actual use. Also, the curability of the antifouling layer was good. Further, it was confirmed that the water contact angle was large, the water sliding angle was small, and water repellency and water fastness were also excellent.

On the other hand, the antifouling layer formed of the antifouling composition of Comparative Examples 1 to 6 had a surface state and curability deteriorated because a room temperature ground was used in the step (3). Therefore, the antifouling sheet having these antifouling layers was judged not to be able to withstand use, and evaluation other than the evaluation of the surface condition and the curability was not carried out.

In each of the examples and comparative examples, the drying was carried out at a temperature of 80 DEG C in the same manner as the ground used in the step (3) of each example in the step (4). However, in each of the examples, the substrate heated in the step (3) is directly heated before the drying in the step (4). The temperature of the coating film on the side contacting the substrate and the inside of the coating film close to the surface are increased faster than the temperature on the surface opposite to the substrate by being heated in order from the coating film surface on the side contacting the substrate, It is considered that the curing reaction of the coating film is preferentially promoted rather than evaporation of the organic solvent from the surface of the coating film. As a result, it was considered that in the example using the production method of the present invention, the antifouling sheet having the antifouling layer with excellent surface condition and curability was obtained without gelation of the coating film as in the comparative example.

Industrial availability

By using the production method of the present invention, even in the case of the antifouling composition in which the surface state of the antifouling layer and the curability are poor, the surface condition and curability of the antifouling layer can be improved.

As a result, the antifouling sheet obtained by the production method of the present invention has favorable surface condition and curability of the antifouling layer. Further, when an antifouling composition containing a trifunctional silane-based compound having an alkyl group having a large number of carbon atoms, which is an antifouling composition having a poor antifouling layer state and poor curability, is cured by the production method of the present invention, the water repellency and water- , And also had a high surface hardness and a low friction coefficient.

For this reason, the production method of the present invention can be applied to an antifouling sheet having an antifouling layer such as windshield glass, water tank, bottom window and bottom of a building such as windowpane for construction, windowpane for automobile, vehicle, Production of an antifouling sheet for preventing adherence of something that might interfere with the field of view such as water drops, scratches, and dirt on the surface of a molded article such as a mirror, a glass container, a glass ornamental product, etc. installed on a road panel such as a film, Method.

1a, 1b, 2a, 2b Antifouling sheets
11 Ore layer
12 substrate
13 Pressure-sensitive adhesive layer
14, 14 'peeling material

Claims (15)

A method for producing an antifouling sheet having an antifouling layer, which comprises the following steps (1) to (4) in this order.
Step (1): A step of preparing an antifouling composition containing the following components (A) to (C)
Component (A): A tetrafunctional silane compound represented by the following 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 are a plurality is present, a plurality of R ¹ and X ¹ is, and may be same or different from each other. and p represents an integer of 0 to 4.]
Component (B): A trifunctional silane compound represented by the following general formula (b)
R ² Si (OR ³ ) _q (X ² ) _3-q (b)
[In the 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. R ³ and X ² if a plurality is present, a plurality of R ³ and X ² are, and may be same or different from each other. and q represents an integer of 0 to 3.]
(C) Component: Metal catalyst
Step (2): A step of coating the antifouling composition prepared in the step (1) on a support to form a coating film
Step (3): A step of heating the coated film formed on the support formed in the step (2) from the side of the support to initiate the curing reaction of the coated film from the side of the support
Step (4): Step of solidifying the coating film to form an antifouling layer The method according to claim 1,
In the step (3), the temperature of the surface of the coating film on the support side is heated so as to rise faster than the temperature of the surface on the side opposite to the support, and the curing reaction of the coating film is started from the surface of the support &Lt; / RTI &gt; 3. The method of claim 2,
In the step (3), the surface of the support on the side opposite to the coating film side is heated to initiate the curing reaction of the coating film from the side of the support. 4. The method according to any one of claims 1 to 3,
The method for producing an antifouling sheet according to claim 3, wherein the coating film on the support is heated by bringing the surface of the support opposite to the coating film side into contact with a heating mechanism previously heated. 5. The method according to any one of claims 1 to 4,
The method for producing an antifouling sheet according to (3), wherein the heating temperature is not lower than 40 占 폚. 6. The method according to any one of claims 1 to 5,
Wherein the time from the step (2) to the step (3) is 20 seconds or less. 7. The method according to any one of claims 1 to 6,
The process for producing an antifouling sheet according to any one of claims 1 to 3, wherein the step (4) is a step of introducing the antifouling layer into a dryer. 8. The method of claim 7,
Wherein the time from the step (3) to the step (4) is 60 seconds or less. 9. The method according to any one of claims 1 to 8,
The method for producing an antifouling sheet according to (1), wherein the component (B) contains at least one of the following components (B-1).
(B-1): a trifunctional silane-based compound represented by the following general formula (b-1)
R ⁴ Si (OR ⁵ ) _r (X ³ ) _3-r (b-1)
[In the general formula (b-1), R ⁴ represents an alkyl group having from 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. R ⁵ and X ³ if a plurality is present, a plurality of R ⁵ and X ³ are, and may be same or different from each other. and r represents an integer of 0 to 3.] 10. The method according to any one of claims 1 to 9,
The method for producing an antifouling sheet according to (1), wherein the component (B) contains at least one of the following components (B-2).
(B-2) Component: A trifunctional silane-based compound represented by the following general formula (b-2)
_{^{R 6 Si (OR 7) s}} (X 4) 3-s (b-2)
[In the 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. R ⁷ and X ⁴ if a plurality is present, a plurality of R ⁷ and X ⁴ are, and may be same or different from each other. and s represents an integer of 0 to 3.] 11. The method according to any one of claims 1 to 10,
The method for producing an antifouling sheet according to the above (1), further comprising the following condition (I).
(A) / (B) (molar ratio) of the molar amount of the component (A) to the molar amount of the component (B) The method according to claim 10 or 11,
The method for producing an antifouling sheet according to the above item (1), further satisfying the following condition (II).
The ratio of the molar amount of the component (B-1) to the molar amount of the component (B-1) to the total molar amount of the component (B-1) 2)}] (molar ratio) of not less than 0.020 13. The method according to any one of claims 1 to 12,
Wherein the content of the component (C) in the step (1) is 0.010 mol% or more and 50.000 mol% or less based on 100 mol% of the total of the components (A) and (B). 14. The method according to any one of claims 1 to 13,
Wherein the support is a substrate or a release material. 15. The method according to any one of claims 1 to 14,
The process according to any one of (1) to (3), further comprising an acid catalyst as the component (D), wherein the content of the component (D) is 0.010 mol% 1.000 mol% or less.

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