TWI713595B - Method for manufacturing antifouling sheet - Google Patents

Abstract

The present invention relates to a method for manufacturing an antifouling sheet with an antifouling layer, which is a manufacturing method having steps (1) to (4) in sequence; step (1): preparation containing as component (A) has a specific structure The antifouling composition of the tetrafunctional silane-based compound of the (B) component, the trifunctional silane-based compound with a specific structure, and the metal catalyst of the (C) component; Step (2): Step (1) The prepared antifouling composition is coated on the support to form a coating film; step (3): the coating film on the support formed in step (2) is heated from the support side, from the support side The hardening reaction of the coating film begins on the surface; Step (4): solidify the coating film to form an antifouling layer.

Description

Method for manufacturing antifouling sheet

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

Generally speaking, window glass for construction, window glass for automobiles, windshields for vehicles, aircrafts, ships, water tanks, ship bottom windows, films to prevent sea creatures from adhering to the bottom of ships, soundproof walls and other road plates, mirrors installed in bathrooms, etc. It is better to prevent visible water droplets, scratches, dirt, etc. that do not adhere to the surface of molded articles such as glass containers and glass ornaments.

The surface of such a molded article can be provided with water repellency or antifouling properties by coating it with a film made of an antifouling substance, or by bonding an antifouling sheet.

For example, Patent Document 1 discloses that a base layer made of an inorganic compound and a laminate of a water-repellent film formed of a compound containing fluorine on the surface of the base layer are combined with a substrate such as a coated glass. Water-repellent film-coated items.

[Advanced Technical Literature] [Patent Literature]

[Patent Document 1] 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.

In addition, for an antifouling layer having an antifouling sheet, it is also required that the surface state or hardenability of the layer is good.

The inventors of the present invention have discovered that when a coating film is formed 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, a surface state can be formed Or an antifouling layer with good curability.

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

The present invention aims to provide a method for manufacturing an antifouling sheet having an antifouling layer with good surface condition and curability.

The inventors of the present invention have found that the use of a trifunctional silane-based compound containing a specific structure and a trifunctional silane-based compound The antifouling composition of the metal catalyst and the antifouling composition form a coating film, and the above-mentioned problems can be solved by starting and promoting the curing reaction of the coating film under specific conditions, and the present invention has been completed.

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

[1] A method for manufacturing an antifouling sheet having an antifouling layer is a method for manufacturing an antifouling sheet having the following steps (1) to (4) in sequence.

Step (1): Step to prepare an antifouling composition containing the following (A) to (C) components

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

Si(OR ¹ ) _p (X ¹ ) _4-p (a) [In 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 plural, the plural R ¹ and X ¹ may be the same or different from each other. p represents an integer from 0 to 4]

(B) Component: a 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 this 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 plural, the plural R ³ and X ² may be the same or different from each other. q represents an integer from 0 to 3]

(C) Ingredient: Metal catalyst

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

Step (3): heat the coating film on the support formed in step (2) from the support side, and start the curing reaction of the coating film from the support side

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

[2] For step (3), the temperature of the support side of the coating film is heated faster than the temperature of the side opposite to the support, and the hardening reaction of the coating film starts from the support side. The method for producing the antifouling sheet described in [1] above.

[3] For step (3), heat is applied to the surface of the support opposite to the side of the coating film, and the curing reaction of the coating film starts from the side of the support. The prevention described in [2] above Manufacturing method of dirty flakes.

[4] For step (3), by contacting the surface on the side opposite to the coating film side of the support with a previously heated support, heating the coating film on the support [1] to [3] The method of manufacturing an antifouling sheet described in any one of the above.

[5] For step (3), the method for producing the antifouling sheet described in any one of [1] to [4] above with a heating temperature of 40°C or higher.

[6] The method for producing the antifouling sheet described in any one of [1] to [5] above in which the time required from step (2) to step (3) is 20 seconds or less.

[7] Step (4) is a method for producing the antifouling sheet described in any one of [1] to [6] above, which is a step of forming an antifouling layer in a drying mechanism.

[8] The method for producing the antifouling sheet described in [7] above in which the time required from step (3) to step (4) is 60 seconds or less.

[9] For step (1), as the component (B), the method for producing the antifouling sheet described in any one of the above [1] to [8] containing at least one of the following (B-1) components as the component (B).

(B-1) Component: 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 15 to 24 carbon atoms, and this 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 plural, the plural R ⁵ and X ³ may be the same or different from each other. r represents an integer from 0 to 3].

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

(B-2) Component: 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 this 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 plural, the plural R ⁷ and X ⁴ may be the same or different from each other. s represents an integer from 0 to 3].

[11] For step (1), the method for manufacturing the antifouling sheet described in any one of [1] to [10] of the following condition (I) law.

Condition (I): The ratio of the molar amount of the component (A) to the molar amount of the component (B) [(A)/(B)] (molar ratio) is 0.01 or more.

[12] For step (1), the method for producing the antifouling sheet described in [10] or [11] further satisfying the following condition (II).

Condition (II): The ratio of the molar amount of (B-1) component to the total molar amount of (B-1) component and (B-2) component [(B-1)/{(B-1) +(B-2)}] (molar ratio) is 0.020 or more.

[13] Regarding step (1), the content of (C) component is 0.010 mol% or more and 50.000 mol% or less for the total 100 mol% of (A) component and (B) component. [1 ]~[12] The method for producing the antifouling sheet described in any one of them.

[14] The method for producing the antifouling sheet described in any one of [1] to [13] in which the support is a substrate or a release material.

[15] For step (1), the acid catalyst of component (D) is further contained, and the content of component (D) is 0.010 mol% for the total 100 mol% of component (A) and component (B) Above, the method for producing the antifouling sheet described in any one of [1] to [14] above 1.000 mol% or less.

According to the present invention, there is provided a method for manufacturing an antifouling sheet having an antifouling layer with good surface state and curability.

1a, 1b, 2a, 2b‧‧‧Antifouling sheet

11‧‧‧Antifouling layer

12‧‧‧Substrate

13‧‧‧Adhesive layer

14, 14’‧‧‧Striping material

[Fig. 1] A cross-sectional view showing an example of an antifouling sheet having a base material obtained by the manufacturing method of this embodiment.

[FIG. 2] A cross-sectional view showing an example of an antifouling sheet without a substrate obtained by the manufacturing method of this embodiment.

[The form of implementing the invention] 〔Method of manufacturing antifouling sheet〕

The manufacturing method of the antifouling sheet with the antifouling layer of the present invention has the following steps (1) to (4) in sequence.

Step (1): Step to prepare an antifouling composition containing the following (A) to (C) components

(A) Component; a 4-functional silane compound represented by the following general formula (a)

Si(OR ¹ ) _p (X ¹ ) _4-p (a) [In 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 plural, the plural R ¹ and X ¹ may be the same or different from each other. p represents an integer from 0 to 4].

(B) Component: a 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 this 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 plural, the plural R ³ and X ² may be the same or different from each other. q represents an integer from 0 to 3].

(C) Ingredient: Metal catalyst

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

Step (3): The step of heating the coating film on the support formed in step (2) from the support side, and starting the hardening reaction of the coating film from the support side

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

The antifouling sheet having the antifouling layer obtained by the production method of the present invention is that the silane-based compounds in the antifouling composition described in the above step (1) undergo condensation reaction with each other to form a polymer to form an antifouling layer .

The present inventors found that even when the antifouling composition of the same composition is used, the difference in the curing promotion method of the coating film formed by the antifouling composition is caused by the state of the antifouling layer formed by the coating film. Variety. More specifically, when the step (3) is not introduced, the coating film formed of the antifouling composition may gel in the process of forming the antifouling layer.

In the above step (2), when the antifouling composition used in the present invention is applied to a support to form a coating film, the antifouling composition is usually dissolved in an organic solvent and applied as a solution. The inventors speculate that the curing reaction of the coating film is fully carried out in the process of forming the antifouling layer Previously, since the organic solvent evaporates or evaporates to dry the coating film, the coating film becomes gelled.

Among them, the present inventors introduced the above step (3) to volatilize and/or evaporate the organic solvent in the coating film formed from the antifouling composition from the surface of the coating film to dry the coating film. Promote the hardening reaction of the coating film.

In addition, when a metal catalyst is used as the component (C), the condensation reaction between silane-based compounds can proceed effectively, and further emphasis is placed on promoting the curing reaction of the coating film.

As a result, it was found that a good antifouling layer can be formed in the surface state while suppressing the gelation of the coating film, and the present invention has been completed.

The method of manufacturing the antifouling sheet of the present invention will be described below.

<<Step (1)>>

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

<Antifouling composition>

The antifouling composition used in step (1) contains a tetrafunctional silane compound represented by general formula (a) as component (A) and a trifunctional silane compound represented by general formula (b) as component (B) Compound and metal catalyst as component (C).

In addition, the antifouling composition preferably further contains an acid catalyst as the component (D), and it may be used within a range that does not impair the effects of the present invention Contains other additives other than (A) to (D) components.

The following describes the components contained in the antifouling composition used in step (1).

((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 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 plural, the plural R ¹ and X ¹ may be the same or different from each other. p represents an integer from 0 to 4.

Examples of alkyl groups that can be selected for R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and n-pentyl. Group, n-hexyl, neopentyl, methylpentyl, etc. Among them, from the viewpoint of obtaining better curability, methyl, ethyl, or n-propyl is preferred, and methyl or ethyl is preferred.

The alkyl group that can be selected as R ¹ may be either straight chain or branched chain, and straight chain is preferred.

As the optional halogen atom for X ¹ , a chlorine atom, a bromine atom or an iodine atom is preferred, and a chlorine atom is preferred.

In addition, the silane compound represented by the above general formula (a) can be used alone or in combination of two or more kinds.

Moreover, as the (A) component, it is preferable to contain a silane compound whose p is 4 in the aforementioned general formula (a).

The content of the (A) component in the antifouling composition is based on the viewpoint of improving the curability of the antifouling layer formed by the antifouling composition, the viewpoint that a good surface condition can be obtained, and the viewpoint that a high surface hardness can be obtained In view of the total 100 mol% of the (A) component and (B) component, 0.80 mol% or more is preferable, 10.00 mol% or more is more preferable, and 30.00 mol% or more is more preferable. 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. Preferably, it is 98.00 mol% or less, preferably 96.00 mol% or less, more preferably 94.00 mol% or less, and even more preferably 90.00 mol% or less. Moreover, this content can also be calculated from the addition amount when each component is added.

((B) component: trifunctional silane compound represented by general formula (b))

The antifouling composition used in the present invention contains the aforementioned (A) component and at the same time contains a trifunctional silane compound represented by the following general formula (b) as the (B) component.

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 this 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 plural, the plural R ³ and X ² may be the same or different from each other. q represents an integer from 0 to 3.

The number of carbon atoms of the alkyl group that can be selected as R ^{2 is} 1-24.

If the carbon number of the alkyl group exceeds 24, the hardenability of the antifouling layer formed of the antifouling composition will deteriorate. In addition, the more the carbon number of the alkyl group increases, the The easier the stain composition is to gel, the surface condition of the anti-fouling layer formed by the stain resistance composition tends to deteriorate. From such a viewpoint, the carbon number of the alkyl group is preferably 22 or less, preferably 20 or less, and more preferably 18 or less.

In addition, the number of carbon atoms of the alkyl group that can be selected as the above-mentioned R ² does not contain the number of carbon atoms that may have any substituent of the alkyl group.

Examples of alkyl groups that can be selected for R ² include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n -Heptadecanyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-docosyl, n-docosyl, n-tricosyl , N-tetracosyl, isopropyl, isobutyl, scc-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, methylpentyl, isohexyl, pentyl Hexyl, butylpentyl, and 2-ethylhexyl, etc.

In addition, the optional alkyl group for R ² may be either linear or branched. From the viewpoint of improving the curability and surface state of the antifouling layer formed from the antifouling composition, linear The one is better.

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

Examples of such substituents include halogen atoms such as chlorine atoms, bromine atoms, and iodine atoms; hydroxyl groups; nitro groups; amine groups; cyano groups; thiol groups; epoxy groups; glycidoxy groups; (methyl) Allyloxy; ring-forming carbon number 3~12 (preferably ring-forming carbon number 6~10) cycloalkyl; ring forming carbon number 6~12 aryl group; containing selected from nitrogen atom, oxygen atom, And sulfur atoms A ring of atoms forms a heteroaryl group with 6 to 12 atoms; an alkoxy group with 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms); a ring forms an aryloxy group with 6 to 12 carbon atoms, etc., these substitutions The group can be further substituted.

However, as an optional alkyl group for R ² , an alkyl group having no substituent is preferred.

The alkyl group selectable as R ³ and the halogen atom selectable as X ² are the same as the alkyl group selectable as R ^{1 and} the halogen atom selectable as X ^{1 in} the general formula (a).

In addition, the trifunctional silane-based compound represented by the above general formula (b) can be used alone or in combination of two or more kinds.

In addition, as the component (B), it is preferable to contain a trifunctional silane compound in which q in the general formula (b) is 3.

The content of the (B) component in the antifouling composition used in the present invention is preferably 2.50 mol% or more for the total of 100 mol% of the (A) component and (B) component, which is more It is preferably 5.00 mol% or more, and more preferably 10.00 mol% or more. In addition, from the viewpoint of improving the surface condition of the antifouling layer formed of the antifouling composition, the viewpoint of improving the curability, and the viewpoint of obtaining high surface hardness, 99.00 mol% or less is preferable , Preferably 80.00 mol% or less, more preferably 50.00 mol% or less, more preferably 30.00 mol% or less, and even more preferably 25.00 mol% or less. In addition, the content can be calculated from the addition amount when each component is added.

(For condition (I))

The antifouling composition used in the present invention has the effect of the aforementioned (A) component The relationship with (B) component is preferably an antifouling composition that satisfies the following condition (I).

Condition (I): The ratio [(A)/(B)] (molar ratio) of (A) component to the molar quantity of component (B) is 0.01 or more

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

In addition, the [(A)/(B)] (mole ratio) is preferably 50.00 or less. When the [(A)/(B)] (molar ratio) is 50.00 or less, the ratio of the alkyl group represented by R ² in the component (B) will not be extremely reduced, and the antifouling composition formed by the antifouling composition The dirt layer has better water repellency. From such a viewpoint, the [(A)/(B)] (molar ratio) is preferably 50.00 or less, more preferably 25.00 or less, more preferably 12.50 or less, and still more preferably 10.00 or less.

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

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

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 this 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 plural, the plural R ⁵ and X ³ may be the same or different from each other. r represents an integer from 0 to 3.

When the carbon number of the alkyl group representing R ⁴ is 15 or more, the water contact angle will be high, and an antifouling layer with a low water slip angle can be obtained, which is preferable. From such a viewpoint, the R ⁴ is preferably 16 or more. In addition, 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 the above-mentioned R ² , and is preferably 22 or less, preferably 20 or less, and more preferably 18 or less. The reason for setting each preferable upper limit is also the same as that described above for R ² .

In addition, the number of carbon atoms of the alkyl group selectable as R ⁴ does not contain the number of carbon atoms of any substituent that the alkyl group may have.

On the other hand, as shown above, if the carbon number of the alkyl group represented by R ^{4 is} increased, the antifouling layer formed of the antifouling composition will deteriorate and the antifouling composition will be more likely to gel. The present inventors discovered that the surface condition of the formed antifouling layer also tends to deteriorate.

However, by using the manufacturing method of the present invention, gelation of the antifouling composition can be suppressed, and the surface condition of the formed antifouling layer can also be improved. Therefore, as the (B) component, an antifouling composition containing at least one (B-1) component can be used, which can provide an antifouling layer having excellent curability and surface condition and also good water repellency.

Examples of alkyl groups that can be selected for R ⁴ include n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n- Eicosyl, n-docosyl, n-docosyl, n-tricosyl, and n-tetracosyl, etc.

In addition, the optional alkyl group for R ⁴ may be either linear or branched. From the viewpoint of improving the curability and surface state of the antifouling layer formed by the antifouling composition, straight The chain is better. As an optional alkyl group for R ⁴ , n-pentadecyl or n-hexadecyl is preferred from the standpoint of hardening and surface state of the antifouling layer, and from the standpoint of obtaining better water repellency In view of this, n-hexadecyl, n-pentadecyl or n-octadecyl is preferred.

The alkyl group that can be selected as R ⁴ may have a substituent. The substituents of the alkyl group that can be selected as R ⁴ are as described above for the substituents of the alkyl group that can be selected as R ² . However, the alkyl group that can be selected for 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 in the above general formula (a) and the halogen atom that can be selected as X ¹ By.

In addition, the trifunctional silane-based compound represented by the above general formula (b-1) can be used alone or in combination of two or more kinds.

In addition, as the component (B-1), it is preferable to contain 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)]

In the antifouling composition used in the present invention, as the aforementioned component (B), one containing at least one component (B-2) of a trifunctional silane compound represented by the following general formula (b-2) is good.

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 this 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 plural, the plural R ⁷ and X ⁴ may be the same or different from each other. s represents an integer from 0 to 3.

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

When the carbon number of the alkyl group is in this range, the antifouling layer formed of the antifouling composition has excellent hardenability and can also increase the surface hardness. In addition, the number of carbon atoms of the alkyl group that can be selected as the above-mentioned R ⁶ does not contain the number of carbon atoms of an optional substituent of the alkyl group.

The alkyl groups that can be selected for R ⁶ include methyl, ethyl, n-propyl or isopropyl. From the viewpoint of obtaining relatively good water sliding properties, methyl or ethyl is preferred. From the viewpoint of obtaining higher surface hardness and low friction coefficient, methyl is preferred.

The alkyl group selected as R ⁶ may have a substituent. The substituents of the alkyl group that can be selected as R ⁶ are as described above regarding the substituents of the alkyl group that can be selected as R ² . However, the alkyl group that can be selected for R ^{6 is} preferably an alkyl group having no substituent.

The alkyl group selectable as R ⁷ and the halogen atom selectable as X ⁴ are the same as the alkyl group selectable as R ^{1 and} the halogen atom selectable as X ^{1 in} the general formula (a).

In addition, the trifunctional silane-based compound represented by the above general formula (b-2) can be used alone or in combination of two or more kinds.

Moreover, as the component (B-2), it is preferable to contain a trifunctional silane-based compound in which s is 3 in the general formula (b-2).

The antifouling composition used in the present invention may contain It is preferable to have (B-1) component and (B-2) component as (B) component. As the (B) component, the combined use of the (B-1) component and (B-2) component has better surface condition and hardenability, and better water repellency and water sliding properties than when used alone. Form an anti-fouling layer with high surface hardness and low friction coefficient.

As the (B) component, when the (B-1) component and (B-2) component are used, the content of the (B-1) component in the antifouling composition is improved by increasing the antifouling composition formed by the antifouling composition. From the viewpoint of hardening of the soil layer, the viewpoint of obtaining a good surface condition, and the viewpoint of obtaining high surface hardness, the total of (A) component, (B-1) component and (B-2) component is 100 mol% In other words, it is preferably 0.30 mol% or more, preferably 0.50 mol% or more, more preferably 1.00 mol% or more, more preferably 2.00 mol% or more, still more preferably 4.00 mol% or more, and It is preferably 36.00 mol% or less, preferably 26.00 mol% or less, more preferably 24.00 mol% or less, and even more preferably 19.00 mol% or less. And the content can be calculated from the blending amount when adding to each component.

When the (B-1) component and (B-2) component are used as the (B) component, the relationship between the aforementioned (A) component and (B-1) component is relative to the molar amount of (B-1) component ( A) The molar ratio [(A)/(B-1)] (molar ratio) of the component is preferably 1.40 or more.

When the [(A)/(B-1)] (molar ratio) is 1.40 or more, the antifouling layer formed of the antifouling composition is excellent in curability and surface hardness. From this point of view, the [(A)/(B-1)] (molar ratio) is preferably 1.50 or more, preferably 1.90 or more, and more preferably 2.10 or more, It is more preferably 2.50 or more, more preferably 5.00 or more, and still more preferably 6.00 or more.

In addition, the [(A)/(B-1)] (mole ratio) is preferably 300.00 or less. When the [(A)/(B-1)] (molar ratio) is 300.00 or less, the presence of the alkyl group represented by R ⁴ in the component (B-1) is formed from an antifouling composition The antifouling layer can have better water repellency. From this point of view, the [(A)/(B-1)] (molar ratio) is preferably 200.00 or less, more preferably 150.00 or less, more preferably 100.00 or less, and still more preferably 90.00 or less, More preferably, it is 50.00 or less, and still more preferably 20.00 or less.

When the (B-1) component and (B-2) component are used as the (B) component, the content of the (B-2) component in the antifouling composition will increase the antifouling formed by the antifouling composition From the viewpoint of hardening of the layer, the viewpoint of obtaining a good surface condition, and the viewpoint of obtaining high surface hardness, the total of (A) component, (B-1) component and (B-2) component is 100 mol% , Preferably 0.50 mol% or more, more preferably 1.00 mol% or more, more preferably 1.30 mol% or more, more preferably 2.00 mol% or more, and more preferably 40.00 mol% or less, more preferably It is 38.00 mol% or less, more preferably 35.00 mol% or less, and even more preferably 20.00 mol% or less. In addition, the content can be calculated from the blending amount when adding to each component.

As (B) component, when using (B-1) component and (B-2) component, the relationship between the aforementioned (A) component and (B-2) component is relative to the molar amount of (B-2) component (A) The molar ratio of the component [(A)/(B-2)] (molar ratio) is not particularly limited, but 1.00 or more is preferred, Preferably it is 4.00 or more. In addition, the [(A)/(B-2)] (mole ratio) is preferably 70.00 or less, preferably 40.00 or less, and more preferably 35.00 or less.

(For condition (II))

The antifouling composition used in the present invention is preferably an antifouling composition that satisfies the following condition (II) for the relationship between the aforementioned (B-1) component and (B-2) component.

Condition (II): For the total molar amount of (B-1) component and (B-2) component, the ratio of the molar amount of (B-1) component [(B-1)/{(B- 1)+(B-2)}] (mole ratio) is 0.020 or more, when the [(B-1)/{(B-1)+(B-2)}] (mole ratio) is 0.020 or more , The static friction coefficient and dynamic friction coefficient of the antifouling layer formed by the antifouling composition will be lower, and its friction characteristics will be excellent. In addition, when the alkyl group represented by R ⁴ in the component (B-1) is appropriately present, the water contact angle of the antifouling layer formed of the antifouling composition can be increased, and the water repellency can be excellent. From this point of view, the [(B-1)/{(B-1)+(B-2)}] (molar ratio) is preferably 0.025 or more, preferably 0.035 or more, and more preferably 0.080 or more , More preferably 0.180 or more, still more preferably 0.220 or more.

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

Moreover, the antifouling composition used in the present invention is When the components (B-1) and (B-2) of the trifunctional silane-based compound meet the above conditions (I) and (II), they can also have an antifouling layer formed by an antifouling composition. The higher surface hardness and lower friction coefficient. In addition, since the component (B-2) is contained, it is also expected that the weather resistance of the antifouling layer formed from the antifouling composition will be improved.

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

((C) component: metal catalyst)

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

In addition, when the antifouling composition does not contain the component (C), the curing reaction cannot sufficiently proceed at a relatively low temperature (130°C or less). Therefore, when the antifouling layer formed of the antifouling composition is formed on a support with low heat resistance such as chlorinated vinyl resin, it is necessary to form an antifouling layer at a low temperature that can suppress the heat shrinkage of the support. When the dirt layer is hardened with the anti-pollution layer Concerns about insufficient sex. On the contrary, in order to fully progress the curing reaction, when curing is to be performed at a relatively high temperature (over 130°C), there is a concern that the support may undergo heat shrinkage.

As the metal catalyst, a metal catalyst that does not require light irradiation when it is desired to perform the catalytic action is preferable.

In addition, in this specification, the "metal catalyst that does not require light irradiation when it is desired to express the catalytic effect" means that for the condensation reaction of the aforementioned (A) component and (B) component, light is not required to express the catalytic effect. Irradiated metal catalyst. For example, when removing the so-called photocatalyst below, when electrons and holes are generated by light irradiation, such as titanium oxide (TiO ₂ ) or zinc oxide (ZnO), it will cause oxidation and reduction reactions. Those who need photocatalyst for light irradiation.

In addition, when the antifouling layer contains the above-mentioned "metal catalyst that does not require light irradiation when it is desired to perform the function of the catalyst", it can avoid the doubt about the bad situation caused by the use of the photocatalyst. The doubts about the problems caused when the photocatalyst is used, for example, when the photocatalyst itself is solid, the surface of the antifouling layer becomes rough and the water repellency is reduced or the hydrophilicity of the photocatalyst is imparted, resulting in a decrease in water repellency, and The problem of promoting the hydrolysis of the polymer of the silane compound and reducing the durability of the antifouling layer can be cited.

As the metal catalyst, at least one selected from the group consisting of titanium-based catalysts, zirconium-based catalysts, palladium-based catalysts, tin-based catalysts, aluminum-based catalysts, and zinc-based catalysts is preferred.

As the above-mentioned titanium-based catalyst, compounds other than the photocatalyst containing titanium atoms are preferred. Examples include titanium alkoxides and titanium chelate It can also be titanium hydroxide, acetate, carbonate, sulfate, nitrate or chloride.

Examples of titanium alkoxides include titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium butoxide dimer, and titanium tetra-2-ethylhexyl oxide.

As the titanium chelate compound, for example, titanium diisopropoxy bis (acetyl pyruvate), titanium acetyl pyruvate such as titanium tetraacetyl pyruvate; titanium diisopropoxy bis (ethyl Acetate) and other titanium ethyl acetate; titanium diisopropoxy bis(triethanolamino acid) and other titanium triethanolamino acid salts; titanium tetraoctyl glycolate, titanium dioctyloxy Bis(octanediolate), titanium bis-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexanoxide) and other titanium octanediolate; titanium lactate, titanium lactic acid Ester ammonium salt and so on.

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

As the above-mentioned zirconium-based catalyst, compounds other than the photocatalyst containing zirconium atoms are preferred, for example, zirconium alkoxides, zirconium chelate compounds, zirconium amides, etc., zirconium hydroxides, acetates, carbonates, Sulfate, nitrate, chloride, etc. are also acceptable.

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

Examples of zirconium chelate compounds include zirconium acetylpyruvate such as zirconium tributoxy monoacetate pyruvate and zirconium tetraacetate pyruvate; zirconium dibutoxy bis(ethyl acetylacetate) Zirconium ethyl acetate; zirconium chloride compound, zirconium lactate ammonium salt, etc.

Examples of zirconium compounds include octyl acid zirconium compounds, stearic acid Zirconium etc.

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).

As the above-mentioned tin-based catalyst, compounds other than the photocatalyst containing tin atoms are preferred. Examples include stannous octoate, dibutyltin diacetate, dibutyltin laurate, dibutyltin mercaptan, and dibutyltin diacetate. Organic tin compounds or inorganic tin compounds such as thiocarboxylate, dibutyltin dimaleate, dioctyltin thiolate, and dioctyltin thiocarboxylate.

As the above-mentioned aluminum-based catalyst, compounds other than the photocatalyst containing aluminum atoms are preferable, and examples include aluminum acetylacetate complexes or aluminum acetylpyruvate complexes.

As the aluminum acetyl acetate complex, for example, diisopropoxy aluminum monooleyl acetyl acetate, monoisopropoxy aluminum dioleyl acetyl acetate, monoisopropoxy Aluminum monooleate monoethyl acetyl acetate, diisopropoxy aluminum monolauryl acetyl acetate, diisopropoxy aluminum monostearyl acetyl acetate, diisopropoxy Aluminum monoisostearyl acetyl acetate, monoisopropoxy aluminum mono-N-lauryl-β-aluminate monolauryl acetyl acetate, aluminum ginseng acetopyruvate, etc.

As the aluminum acetopyruvate complex, for example, monoacetylpyruvate aluminum bis(isobutylacetate) chelate, monoacetylpyruvate aluminum bis(2-ethyl Hexyl Acetyl Acetate) Chelate, Mono Acetyl Pyruvate Aluminum Bis (Dodecyl Acetate) Chelate, Mono Acetyl Pyruvate Aluminum Bis (Oleyl Acetate) ) Chelate etc.

As the above-mentioned zinc-based catalyst, a compound other than the photocatalyst containing a zinc atom is preferable, for example, zinc-chromium oxide, zinc-aluminum oxide, zinc-aluminum-chromium oxide, zinc-chromium-manganese oxide , Zinc-iron oxide, zinc-iron-aluminum oxide, etc.

In addition, as the above-mentioned metal catalyst, it can be used alone or in combination of two or more kinds.

In addition, it is obtained by effectively promoting the condensation reaction of silane-based compounds to improve the curability of the antifouling layer formed from the antifouling composition, and the curing reaction can also proceed at relatively low temperatures (below 130°C) From the viewpoint of the antifouling composition, it is preferable to contain at least the aforementioned titanium-based catalyst.

As the titanium-based catalyst, titanium chelate is preferred, and titanium ethyl acetyl acetate, titanium acetyl pyruvate or titanium octyl glycolate are preferred, and titanium ethyl acetyl acetic acid is preferred. Ester is more preferable, and titanium diisopropoxy bis(ethyl acetate) is more preferable.

The content of component (C) in the antifouling composition is based on the viewpoint of improving the curability of the antifouling layer formed by the antifouling composition, and the curing reaction can also proceed at relatively low temperatures (below 130°C) to obtain protection. From the point of view of the soiling composition, the total 100 mole% of the (A) component and (B) component is preferably 0.010 mol% or more, preferably 0.100 mol% or more, and more preferably 0.150 mol% % Or more, more preferably 0.300 mol% or more, more preferably 0.500 mol% or more, still more preferably 1.000 mol% or more. The content is preferably 50.000 mol% or less, preferably 30.000 mol% or less, more preferably 20.000 mol% or less, more preferably 10.000 mol% or less, and even more preferably 6.000 mol% or less , Preferably 3.000 Mole% or less.

In addition, the content can be calculated from the compounding amount when each component is added.

((D) component: acid catalyst)

From the viewpoint that the antifouling composition used in the present invention can further improve the curability of the antifouling layer formed from the antifouling composition, it is preferable to further contain an acid catalyst as the component (D).

Since the antifouling composition contains an acid catalyst, it can promote the hydrolysis of the reactive functional groups having the components (A) and (B). As a result, the condensation polymerization reaction between silane-based compounds can be further promoted, and an antifouling layer with excellent curability can be formed.

As the above-mentioned acid catalyst, what has the effect of promoting the hydrolysis of the reactive functional groups of the component (A) and the component (B) is not particularly limited. For example, from the viewpoint of further improving the curability of the anti-fouling layer formed by the anti-fouling composition, the content is selected from hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, bromic acid, and p-toluenesulfonic acid. , And one or more types of trifluoroacetic acid are preferred, and those containing hydrochloric acid are preferred.

In addition, as the above-mentioned acid catalyst, it can be used alone or in combination of two or more kinds.

The content of the (D) component in the antifouling composition can further improve the curability of the antifouling layer formed by the antifouling composition, and for the total of the (A) and (B) components For 100 mol%, 0.010 mol% or more is preferable, 0.030 mol% or more is more preferable, 0.050 mol% or more is more preferable, and 0.060 mol% or more is still more preferable. The content is preferably 1.000 mol% or less, preferably 0.500 mol% or less The lower, more preferably 0.100 mol% or less, and still more preferably 0.075 mol% or less. And the content can be calculated from the blending amount when each component is added.

(Other additives)

In the antifouling composition used in the present invention, in addition to the above-mentioned (A) to (D) components, other additives may be contained within a range that does not impair the effects of the present invention.

Examples of other additives include resin components, hardeners, anti-aging agents, light stabilizers, flame retardants, conductive agents, antistatic agents, plasticizers, and the like.

With respect to the total amount of the antifouling composition, the content of each of these additives is preferably 0-20% by mass, preferably 0-10% by mass, more preferably 0-5% by mass, and still more preferably 0-2 quality%.

In addition, the total content of the (A) component, (B) component, (C) component, and optional (D) component contained in the antifouling composition used in the present invention is relative to the total amount of the antifouling composition (Solid content 100% by mass) is preferably 50% by mass or more, more preferably 65% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass Above, more preferably 99% by mass or more, and more preferably 100% by mass or less. Moreover, the content is preferably 100% by mass. Moreover, when the (D) component is not contained in the antifouling composition, the preferable range of these content amounts shows the preferable range of the total content of (A)-(C) component. In addition, the content can be calculated from the blending amount when each component is added.

<<Step (2)>>

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

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

As this solvent, methanol, ethanol, propanol, butanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene, etc. are mentioned, for example.

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

<Support body>

The support used in step (2) is that a coating film made of the antifouling composition described above can be formed on the support, and only in the following steps (3) and (4) will not produce bad conditions It is sufficient, and there is no particular limitation. As the support, it is preferable to use a substrate or release material described later.

In addition, the support may be a support directly contained in the structure of the obtained antifouling sheet, or may be a support removed in the following step (3) and subsequent steps.

(Substrate)

Examples of substrates that can be used for the aforementioned support include paper substrates, resin films, resin sheets, and substrates in which paper substrates are laminated with resin, and can be appropriately selected according to the use of the antifouling sheet.

Examples of paper constituting the paper base material include tissue paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, cellophane, and the like.

Examples of the resin constituting the resin film or the resin sheet include polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-ethylene Alcohol copolymers, etc., ethylene-methacrylic acid copolymer vinyl resins; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Polyester resin; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane, acrylic modified polyurethane and other urethane formic acid Ester resin etc.

As a base material laminated|stacked by resin of a paper base material, the laminated paper etc. which laminated|stacked the said paper base material by thermoplastic resin, such as polyethylene, are mentioned.

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

As a substrate that can be used for the aforementioned support, it can be used for a substrate with a primer layer provided with a primer layer on the surface of the substrate from the viewpoint of improving adhesion to the antifouling layer or the weather resistant layer described later .

Examples of components constituting the primer layer include polyester resins, urethane resins, polyester urethane resins, acrylic resins, etc. These resins can be used alone or in combination of two or more kinds. .

In addition, as a substrate that can be used for the aforementioned support, it can be used on the surface of the substrate or on the surface of a substrate with a primer layer, and a weathering layer with a weathering layer made of a polymer ultraviolet absorber is further provided The substrate (there may be a primer layer between the weathering layer and the substrate). As the polymer ultraviolet absorber, it is a structure in which the ultraviolet absorbing skeleton has a covalent bond in the polymer structure, and the weight average molecular weight is preferably 5,000 or more, preferably 10,000 or more.

In addition, as a substrate that can be used for the aforementioned support, it can be used on the surface of the above-mentioned substrate or on the surface of a substrate with a primer layer, and a substrate with a hard coating layer further provided with a hard coating layer (in hard coating There may be a primer layer between the layer and the substrate). The material for forming the hard coating layer is not particularly limited, and it can be appropriately selected according to the use of the antifouling sheet among known hard coating layer forming materials.

In addition, when the substrate that can be used as the aforementioned support is a resin film or a resin sheet, from the viewpoint of improving the adhesion to the antifouling layer, an oxidation method may be applied to the surface of these resin films or resin sheets as necessary Or surface treatment such as embossing method.

The oxidation method is not particularly limited, and examples include corona discharge treatment, plasma treatment, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone. Ultraviolet radiation treatment, etc.

In addition, there is no particular limitation on the roughening method, and for example, sandblasting Treatment method, solvent treatment method, etc.

These surface treatments can be appropriately selected according to the type of substrate, but from the viewpoint of improving the adhesion to the antifouling layer and the viewpoint of operability, corona discharge treatment is preferred.

Although the thickness of the substrate is appropriately set according to the use of the antifouling sheet, from the viewpoint of handling and economy, it is preferably 10 to 250 μm, preferably 15 to 200 μm, and more preferably 20 to 150 μm.

In addition, the base material that can be used as the aforementioned support may further contain ultraviolet absorbers, light stabilizers, antioxidants, anti-charge agents, slip agents, anti-blocking agents, colorants, etc. other than the above-mentioned polymer ultraviolet absorbers. .

(Peeling material)

As the peeling material that can be used for the support, a peeling sheet subjected to double-sided peeling treatment or a peeling sheet subjected to single-sided peeling treatment, etc. are used, and a release agent is applied to the substrate for the peeling material.

As the substrate for the release material, for example, a substrate having the antifouling sheet of the present invention can be used. Examples include paper substrates, resin films, resin sheets, and paper substrates laminated with resin. Substrate etc.

Examples of release agents include rubber elastomers such as silicone resins, olefin resins, isoprene resins, butadiene resins, long-chain alkyl resins, alkyd resins, and fluorine resins. Resin etc.

The thickness of the release material is not particularly limited, but is preferably 10 to 200 μm, preferably 25 to 150 μm.

In addition, when the antifouling layer has a structure in which two release materials are sandwiched, the two release materials may be the same or different from each other.

In addition, the peeling material may be directly contained in the structure of the obtained antifouling sheet, or it may be used as a peeling material that is removed in the steps after (3) described later. As a case where the peeling material is removed in the steps after step (3), for example, the following examples can be given. First, in step (2), the antifouling composition is applied to the release material, and the antifouling layer is formed through the following steps (3) and (4). After bonding the antifouling layer to the above-mentioned base material, a new release material, or an adhesive layer described later, the case where the release material is removed can be mentioned.

<<Step (3)>>

The step (3) used in the present invention is the process of heating the coating film on the support formed in the above step (2) from the support side, and starting the hardening reaction of the coating film from the support side step.

As mentioned above, the inventors heated the coating film on the support from the support side, and the organic solvent in the coating film on the surface of the coating film on the side opposite to the support side was volatilized and/or evaporated. Before the post-coating film is dried, the focus is to start and promote the hardening reaction of the coating film.

If this step (3) is not introduced, the gelation of the coating film is easier to proceed compared with the case of this step (3). As a result, the surface condition of the antifouling layer is easily deteriorated, the hardenability of the antifouling layer is reduced, and the surface hardness may be reduced. In addition, when an antifouling composition that more easily gels the coating film is used, the coating film will gel, which reduces the curability of the antifouling layer and deteriorates the surface condition of the antifouling layer. And sometimes the antifouling layer cannot be formed.

In addition, the so-called "hardening reaction of the coating film starting from the side of the support" means that for the hardening reaction inside the coating film close to the side opposite to the support side, it is desired that the hardening reaction inside the coating film close to the support side preferentially proceed. At the beginning, to promote the hardening reaction.

From this point of view, for step (3), it is desired to increase the temperature of the support side of the aforementioned coating film more rapidly than the temperature of the opposite side of the support to heat, and start from the support side to promote the coating film The hardening responder is better.

To meet such conditions, apply the coating on the surface opposite to the coating film side of the support on which the coating film is formed (hereinafter also referred to as "coating film forming sheet"), and start from the support side to promote the coating film. Hardening response is better.

When heating the aforementioned coating film, a support tool is usually used to hold the coating film forming sheet forming the coating film or place the coating film forming sheet on the support tool. Examples of this supporting tool include master paper, metal and/or plastic sheets, belt conveyors, and supporting tools called guide rollers.

As this heating method, for example, when heating with hot air, the temperature of the hot air blown from the surface of the support side of the coating film forming sheet is set to be higher than the temperature of the hot air blown from the surface of the coating film forming sheet on the coating film side. The method of higher hot air temperature can be cited. In addition, a method of blowing hot air only from the support side of the coating film forming sheet can also be cited.

From the viewpoint that the effect of the present invention can be obtained more reliably, the method of heating the coating film on the surface of the support on the side opposite to the coating film side of the coating film forming sheet mentioned above by contacting the previously heated support tool Better.

In addition, as the heating mechanism used in this heating method, the drying mechanism described later in the following step (4) can be used.

The heating temperature in step (3) can be set appropriately. As mentioned above, the temperature of the support side of the coating film is to be heated more rapidly than the temperature of the side opposite to the support, starting from the side of the support , It is better to promote the hardening reaction of the coating film. Therefore, it is preferable to heat at least at a temperature higher than the temperature of the side surface opposite to the support side surface of the coating film.

In addition, the antifouling composition used in the present invention is capable of undergoing a curing reaction even at a relatively low temperature below 130°C. When a support with low heat resistance such as a chlorinated vinyl group is used, the heat shrinkage of the support can be suppressed .

Therefore, from the above viewpoint and the viewpoint of productivity, the heating temperature is preferably 40°C or higher, preferably 50°C or higher, more preferably 60°C or higher, and still more preferably 70°C or higher. Preferably, it is below 130°C, preferably below 120°C, more preferably below 110°C, even more preferably below 95°C.

Regarding the heating time in step (3), only the effect of the present invention can be exerted, and it is not particularly limited and can be set appropriately.

In addition, from the point of view that the time between the formation of the coating film in step (2) and step (3), the loss caused by the volatilization or evaporation of the organic solvent in the coating film formed in step (2) can be suppressed as much as possible. It is better to shorten the time as much as possible. It is preferably 20 seconds or less, preferably 10 seconds or less, more preferably 5 seconds or less, and still more preferably 3 seconds or less.

<<Step (4)>>

The step (4) used in the present invention is a step of solidifying the above-mentioned coating film to form an antifouling layer.

The coating film whose curing reaction is promoted in step (3) In step (4), the coating film is cured while the surface on the side opposite to the support side of the coating film forming sheet is dried. In the end, the coating film did not gel and became an antifouling layer after solidification.

As this step, the step of forming an antifouling layer after the coating film whose curing reaction has been promoted in the step (3) is put into a drying mechanism is preferred.

As the drying mechanism, for example, a batch type drying mechanism called an air oven, and a heat roller, hot air passing mechanism (a device that moves the inside of an open drying furnace and passes through the object to be dried for heating and drying. Etc.) continuous drying mechanism. In addition, a device that can be used as a part of these drying mechanisms, for example, a heating medium circulation heater such as an oil heater, and a heater itself such as a far-infrared heater may be used as the drying mechanism.

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

In addition, the antifouling composition used in the present invention can undergo a curing reaction even at a relatively low temperature of 130°C or less, and the support can also be suppressed when a support with low heat resistance such as a chlorinated vinyl group is used. Thermal shrinkage of the body.

Therefore, from the above viewpoints and productivity viewpoints, the temperature is preferably 10°C or higher, preferably 20°C or higher, more preferably 40°C or higher, more preferably 50°C or higher, and still more preferably Above 60°C. It is preferably below 130°C, preferably below 120°C, more preferably below 110°C. More preferably, it is 95°C or less.

Moreover, from the viewpoint of smooth switching from step (3) and the viewpoint that the hardening reaction in step (3) can continue to be promoted, the temperature of this step (4) is set to be the same as the heating temperature in step (3) The same temperature is better.

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

Moreover, the time from step (3) to step (4) can only achieve the effect of the present invention, and there is no particular limitation. However, from the viewpoint of productivity that the solidification of the final antifouling layer can be completed as soon as possible, 60 Seconds or less is preferable, 30 seconds or less is more preferable, 20 seconds or less is more preferable, 10 seconds or less is more preferable, and 5 seconds or less is still more preferable.

And, as step (4), the heating treatment of step (3) may be continued directly, and the coating film is solidified to eventually become an antifouling layer.

And, on the antifouling layer formed by the above-mentioned manufacturing method, a new release material can be further laminated to protect the surface of the antifouling layer during storage.

And, on the formed antifouling layer or substrate, by laminating an adhesive layer formed on the release material, the antifouling sheet 1b as shown in Figure 1(b) or Figure 2(b) can be manufactured The antifouling sheet 2b is an antifouling sheet with an adhesive layer.

Also, when the support used in step (2) is a release material, after the antifouling layer is formed, the antifouling layer is attached to the above-mentioned base material or a new release material, and then the release used as the support can be removed material.

〔Antifouling sheet〕

The antifouling sheet obtained by the production method of the present invention may only be obtained by the above-mentioned antifouling sheet production method of the present invention, and is not particularly limited.

<Construction example of antifouling sheet>

FIG. 1 shows an exemplary cross-sectional view of an antifouling sheet having a base material obtained by an example manufacturing method of this embodiment.

As an antifouling sheet having a substrate, for example, an antifouling sheet 1a having an antifouling layer 11 on a substrate 12 as shown in FIG. 1(a) is mentioned.

In addition, as shown in FIG. 1(b), an antifouling sheet 1b in which an adhesive layer 13 and a release material 14 are further provided on the surface opposite to the surface having the antifouling layer 11 of the base material 12 may be used.

In addition, on the antifouling layer 11 of the antifouling sheets 1a and 1b, a release material can be further provided to protect the antifouling layer during storage.

FIG. 2 shows an exemplary cross-sectional view of an antifouling sheet without a base material obtained by an example manufacturing method of this embodiment.

As an antifouling sheet having no base material, for example, an antifouling sheet 2a having an antifouling layer 11 sandwiched by two release materials 14, 14' as shown in Fig. 2(a) is exemplified.

In addition, as shown in Fig. 2(b), an antifouling sheet 2b in which an adhesive layer 13 is further provided between the antifouling layer 11 and the release material 14' may be configured as shown in Fig. 2(a).

(Antifouling layer)

The antifouling layer having an antifouling sheet obtained by the manufacturing method of the present invention is formed of the above-mentioned antifouling composition.

The thickness of the antifouling layer is preferably 0.001 μm or more, preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and still more preferably 0.10 μm or more. In addition, the thickness is preferably 40 μm or less, more preferably 25 μm or less, more preferably 15 μm or less, still more preferably 5.0 μm or less, still more preferably 1.0 μm or less, and still more preferably 0.80 μm or less.

(Substrate)

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. The substrate used in the method for producing the antifouling sheet of the present invention is as described above. Show.

(Peeling material)

When the antifouling sheet of the present invention has a release material, the release material can be appropriately selected according to the application of the antifouling sheet. The release material used in the method for producing the antifouling sheet of the present invention is as described above Show.

(Adhesive layer)

When the antifouling sheet of the present invention has an adhesive layer, as an adhesive constituting the adhesive layer, it can be suitably selected according to the use of the antifouling sheet select.

Specific adhesives include, for example, acrylic adhesives, urethane-based adhesives, silicone-based adhesives, rubber-based adhesives, polyester-based adhesives, and those cured by energy rays such as ultraviolet rays. Hardening adhesive, etc.

These adhesives can be used individually or in combination of 2 or more types.

The thickness of the adhesive layer is not particularly limited, and is preferably 1 to 100 μm, preferably 5 to 80 μm.

[Example] Examples 1~6

Each antifouling sheet was manufactured through the following steps (1) to (4).

step 1):

The components (A) and (B) were blended with the types and mixing ratios shown in Table 1 (active ingredient ratio and molar %), and ethanol was added and diluted to obtain a solution with an active ingredient concentration of 1.8M. In this solution, the compounding ratio shown in Table 1 (active ingredient ratio and mole %) was further added with hydrochloric acid as component (D) and stirred for 1 minute. After stirring, the solution was allowed to stand for 15 minutes.

Next, add (C) titanium diisopropoxy bis(ethyl acetyl acetate) in the mixing ratio shown in Table 1 (active ingredient ratio and mole %) to prepare a solution of antifouling composition .

Step (2):

As the substrate, a polyethylene terephthalate (PET) film (product name "Cosmo Shine A-4100" manufactured by Toyobo Co., Ltd., thickness 50μm) with a primer layer on one side was used.

On the primer layer of the substrate with the primer layer, the solution of the antifouling composition prepared as described above is coated by the wire method to form a coating film.

Step (3):

Place the coating film on the substrate obtained in step (2) on a master paper (product name "Adebor" manufactured by Fuji Paper Co., Ltd., thickness 1mm) heated to 80°C in advance, so that the substrate side Contact with the master paper to promote the hardening reaction of the coating film.

And, after the coating film is formed on the substrate in step (2), the time to place the substrate on the master paper to form the coating film in step (3) is within 3 seconds.

Step (4):

Next, for each master paper, the coating film was placed in an oven set at 80°C, and dried at 80°C for 2 minutes to produce an antifouling sheet having an antifouling layer having a thickness shown in Table 3. In addition, the time from placing the base material forming a coating film on the master paper in step (3) to the oven in step (4) is within 5 seconds.

Comparative example 1~6

Except that the master paper used in step (3) was not heated to 80°C in advance, and the normal temperature (25°C) was used directly, the same method as in each of Examples 1 to 6 was used to produce each antifouling sheet.

The details of each component described in Table 1 used in the preparation of the antifouling composition of each Example and each Comparative Example are as follows.

<(A) component: tetrafunctional silane compound represented by general formula (a)>

. "TEOS": Tetraethoxysilane, a tetrafunctional silane compound in the aforementioned general formula (a), p=4, R ¹ = ethyl (carbon number: 2).

<(B) component: trifunctional silane compound represented by general formula (b)>

. "Cetyltrimethoxysilane": q=3 in the aforementioned general formula (b), R ² = n-hexadecyl (carbon number: 16), R ³ = methyl (carbon number: 1) The 3-functional silane compound.

. "Octadecyltrimethoxysilane": q=3 in the aforementioned general formula (b), R ² = n-octadecyl (carbon number: 18), R ³ = methyl (carbon number: 1) The 3-functional silane compound.

And, when each R ^{2 is} read as R ⁴ , R ^{3 is} read as R ⁵ , and q is read as r among these compounds, the compound represented by the aforementioned general formula (b-1) is defined as (B -1) The compound shown in the component.

. "Methyltrimethoxysilane": a trifunctional silane compound with q=3, R ² = methyl (carbon number: 1), R ³ = methyl (carbon number: 1) in the aforementioned general formula (b) .

And in this compound, when R ^{2 is} read as R ⁶ , R ^{3 is} read as R ⁷ , and q is read as s, the compound represented by the aforementioned general formula (b-2) is regarded as (B -2) The compound shown in the component.

<(C) Ingredient: Metal-based catalyst>

. "Titanium-based catalyst": Titanium diisopropoxy bis (ethyl acetyl acetate) [product name "Orgatics TC-750" manufactured by Matsumoto Fine Chemical Co., Ltd.].

<(D) Ingredient: 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 according to the following method. The results are shown in Table 2.

<Thickness of Antifouling Layer>

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

<The surface state of the antifouling layer>

After visually observing the surface of the antifouling layer of the antifouling sheet produced in each example and each comparative example, the surface state of the antifouling layer was evaluated based on the following criteria.

A: Transparent.

B: A slightly foggy surface is confirmed.

C: A matte surface is generated and becomes a non-transparent state.

In addition, if the evaluation of the surface condition of the antifouling layer was "C", evaluation other than the evaluation of the curability of the antifouling layer shown below was not performed because it could not be used.

<The hardening of antifouling layer>

The surface of the antifouling layer of the antifouling sheet produced in each example and each comparative example was wiped with fingers 20 times, and the antifouling layer was visually observed, and the curability of the antifouling layer was evaluated based on the following criteria.

. A: No change is seen compared to before wiping with fingers.

. B: The color is slightly changed to white, but it is acceptable.

. C: Discoloration becomes white.

. D: The coating film made of the antifouling composition is not hardened, and the antifouling layer cannot be formed.

In addition, if the evaluation of the curability of the antifouling layer was "C" or "D", the following evaluations were not performed because it was not usable.

<Water contact angle of antifouling layer>

The water contact angle of the antifouling layer uses a fully automatic contact angle measuring device (product name "DM-701") manufactured by Kyowa Interface Science Co., Ltd. to prevent the antifouling sheet produced in each example and each comparative example. On the surface of the soiled layer, measure the contact angle of 2μL to water.

<Water slide angle of antifouling layer>

The antifouling sheet produced in each example and each comparative example was placed on a sample table (glass plate) with an inclination angle of 0° for water expansion. Next, 14 μL of pure water was dropped on the surface of the antifouling layer of the antifouling sheet to form droplets. When the sample table was tilted, the angle of inclination of the sample table when the droplet moved backward was the water slide angle.

<Surface hardness of antifouling layer>

Using Nano Indenter manufactured by MTS Corporation (product name "Nano Indenter SA2"), the depth of 45nm of the surface layer of the antifouling layer (facing the substrate in the vertical direction) of the antifouling sheet produced in each example and each comparative example was measured The hardness of Modulus.

The Modulus value of the hardness is regarded as the surface hardness.

<Friction coefficient of antifouling layer>

According to JIS K7312, the universal tensile testing machine made by A&D Co., Ltd. is used for testing. On a square and smooth metal plate (200g) with a side of 63.5mm, a sample made from the antifouling sheet produced in each example and each comparative example was laminated, and the measurement was performed on the polyethylene produced by Torayi Co., Ltd. The coefficient of static and dynamic friction of ethylene terephthalate film (product name "Lumilar T-60", thickness 50μm).

It can be seen from Table 1 and Table 2 that the antifouling composition of Examples 1 to 4 was used, and the surface state and curability of the antifouling sheet produced by the above-mentioned production method were good. It is confirmed that the water contact angle is large, the water slip angle is small, and the water repellency and water slip are also excellent. Moreover, as shown in Examples 1 and 4, the surface hardness is high, the friction coefficient is also low, and all the characteristics are good.

In addition, using the antifouling compositions of Examples 5 and 6, the surface condition of the antifouling sheet manufactured by the above-mentioned manufacturing method was found to be inferior compared with other Examples 1 to 4, but its It is acceptable for actual use. And the hardenability of its antifouling layer is good. Also, confirm its water contact angle Larger, smaller water slip angle, excellent water repellency and water slip.

On the other hand, since the antifouling layer formed from the antifouling composition of Comparative Examples 1 to 6 used a normal-temperature master paper in step (3), the surface condition and hardenability showed poor results. Therefore, the antifouling sheet having these antifouling layers was judged to be non-user-friendly, and no evaluation other than the evaluation of the surface state and the curability was performed.

Each example and each comparative example were the same as in the actual step (4), and dried under the same temperature condition of 80°C as the master paper used in the step (3) of each example. However, in each embodiment, before the drying in step (4), the heated master paper in step (3) heats the direct substrate. It is assumed that the internal temperature of the coating film on the surface side of the coating film contacting the substrate and near the surface of the coating film is heated in order from the surface side of the coating film in contact with the substrate. The temperature on the side surface rises more rapidly, which promotes the hardening reaction of the coating film more preferentially than the evaporation of the organic solvent from the surface of the coating film. As a result, in the example using the manufacturing method of the present invention, the coating film does not gelate like the comparative example, and an antifouling sheet having an antifouling layer with good surface state and curability can be obtained.

[Industrial availability]

By using the manufacturing method of the present invention, even in the case of an antifouling composition with poor surface state and curability of the antifouling layer, the surface state and curability of the antifouling layer can be improved.

As a result, the antifouling sheet obtained by the manufacturing method of the present invention has a good surface state and curability of the antifouling layer. And the surface state and hardness of the antifouling layer An antifouling composition containing a trifunctional silane-based compound with a larger carbon number of an antifouling composition, which is hardened by the manufacturing method of the present invention, has good water repellency and water sliding properties , And confirmed to have high surface hardness and low friction coefficient.

Therefore, the manufacturing method of the present invention is the following preferred method for manufacturing an antifouling sheet. The antifouling sheet is an antifouling sheet with an antifouling layer, such as window glass for construction, window glass for automobiles, cars, Windshields for aircrafts, ships, etc., water tanks, bottom windows, films for preventing the adhesion of marine organisms to the bottom of ships, flat plates for roads such as sound insulation walls, mirrors, glass containers, glass decorations, etc. installed in bathrooms, etc. It is suitable for the manufacturing method of the antifouling sheet that prevents adhesion of water droplets, scratches, dirt, etc.

Claims (14)

A method for manufacturing an antifouling sheet, which is a method for manufacturing an antifouling sheet with an antifouling layer, characterized by having the following steps (1) to (4) in sequence; step (1): preparing the following steps: The step (A) component of the antifouling composition of the components (A) to (C): the tetrafunctional silane compound 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 exist in plural, the plural R ¹ and X ¹ may be the same or the same as each other Iso; p represents an integer from 0 to 4] (B) component: the trifunctional silane compound represented by the following general formula (b) R ² Si(OR ³ ) _q (X ² ) _3-q (b) [general formula In (b), R ² represents an alkyl group having 1 to 24 carbon atoms, which may have a substituent; R ³ represents an alkyl group having 1 to 6 carbon atoms, X ² represents a halogen atom; R ³ and X ^{2 are} in plural When present, the plural R ³ and X ² may be the same or different from each other; q represents an integer from 0 to 3] (C) component: metal catalyst step (2): the antifouling property prepared in step (1) The step of applying the composition on the support to form a coating film Step (3): The coating film on the support formed in step (2) is heated from the side of the support, and the coating is started from the side of the support. The step of curing reaction of the film Step (4): the step of solidifying the coating film to form an antifouling layer; and for the step (1), as the component (B), at least one of the following components (B-1) is contained ; (B-1) component: the trifunctional silane compound R ⁴ Si(OR ⁵ ) _r (X ³ ) _3-r (b-1) [general formula (b-1) represented by the following general formula (b-1) In 1), R ⁴ represents an alkyl group with 15 to 24 carbons, which may have a substituent; R ⁵ represents an alkyl group with 1 to 6 carbons, X ³ represents a halogen atom; R ⁵ and X ³ exist in plural When, the plural R ⁵ and X ³ may be the same or different from each other; r represents an integer from 0 to 3]. According to the method of manufacturing an antifouling sheet of claim 1, in step (3), the temperature of the support side of the coating film is heated more rapidly than the temperature of the side opposite to the support. The hardening reaction of the coating film begins on the side of the body. According to the method of manufacturing an antifouling sheet of claim 2, in step (3), heating is performed on the surface of the support on the opposite side to the side of the coating film, and the coating film is started from the side of the support Hardening reaction. According to the method for manufacturing an antifouling sheet according to any one of claims 1 to 3, in step (3), by contacting the surface on the side opposite to the coating film side of the aforementioned support with a preheated support, The coating film on the aforementioned support is heated. Such as the manufacturer of the anti-fouling sheet in any of claims 1 to 3 Method, in step (3), the heating temperature is above 40°C. According to the method for manufacturing an antifouling sheet according to any one of claims 1 to 3, the time required for step (2) to step (3) is 20 seconds or less. The method for manufacturing an antifouling sheet according to any one of claims 1 to 3, wherein step (4) is a step of putting it into a drying mechanism to form an antifouling layer. The method for manufacturing an antifouling sheet according to claim 7, wherein the time required for step (3) to step (4) is 60 seconds or less. The method for producing an antifouling sheet according to any one of claims 1 to 3, wherein in step (1), as component (B), at least one of the following components (B-2); (B-2) component : The 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 carbons, which may have substituents; R ⁷ represents an alkyl group having 1 to 6 carbons, X ⁴ represents a halogen atom; when R ⁷ and X ⁴ are present in plural, the plural R ⁷ and X ⁴ may be the same or different from each other; s represents an integer from 0 to 3]. For example, in the method for manufacturing an antifouling sheet according to any one of claims 1 to 3, in step (1), the following condition (I) is further satisfied; condition (I): for the molar amount of component (B) (A) The molar ratio of the component [(A)/(B)] (molar ratio) is 0.01 or more. Such as the method for manufacturing an antifouling sheet of claim 9, wherein in step (1), the following condition (II) is further satisfied; Condition (II): The ratio of the molar amount of (B-1) component to the total molar amount of (B-1) component and (B-2) component [(B-1)/{(B-1) +(B-2)}] (molar ratio) is 0.020 or more. For the method for producing an antifouling sheet according to any one of claims 1 to 3, in step (1), the content of (C) component is 100 mol% of the total of (A) component and (B) component It is said to be above 0.010 mol% and below 50.000 mol%. According to the method for producing an antifouling sheet according to any one of claims 1 to 3, the aforementioned support is a substrate or a release material. Such as the method for producing an antifouling sheet according to any one of claims 1 to 3, wherein in step (1), the acid catalyst of component (D) is further contained, and the content of component (D) is relative to component (A) and (B) The total 100 mol% of the components is 0.010 mol% or more and 1.000 mol% or less.

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