Surface modifier and composition comprising surface modifier

Abstract

To provide a surface modifier containing a polyether-modified organopolysiloxane having water solubility while maintaining the surface characteristics possessed by a polyether-modified organosiloxane.SOLUTION: There is provided a surface modifier comprising a polyether-modified organopolysiloxane having an oxyethylene group and an oxypropylene group, wherein the polyether-modified organopolysiloxane has an oxyethylene group content of 35 mass% or less, the Haze value of a 1 mass% aqueous solution of the polyether-modified organopolysiloxane at 25°C is 5.0 or less and the cloud number is 10 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a surface modifier comprising a polyether-modified organopolysiloxane having oxyethylene groups and oxypropylene groups, and a composition containing said surface modifier. [Background technology]

[0002] Polyether-modified polyorganosiloxanes have excellent surface properties such as leveling, wettability, anti-fogging, anti-fouling, wettability, and antistatic properties. Therefore, they are widely used in agricultural chemicals, paints, and internal additives for films and resins. However, since siloxane chains or oxypropylene chains are hydrophobic, when trying to make a material water-soluble, it is necessary to increase the hydrophilicity in some way. For example, there are methods such as increasing the proportion of oxyethylene groups, which are hydrophilic groups, in the molecule or introducing hydroxyl groups to the ends of polyether chains (Patent Documents 1, 2, 3, 4). However, these methods have the problem that the above advantages of polyether-modified polyorganosiloxanes are weakened as the water solubility is increased. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2000-327787 A [Patent Document 2] JP 2003-253166 A [Patent Document 3] JP 2015-054934 A [Patent Document 4] JP 2015-151480 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in view of the above circumstances, and has an object to provide a surface modifier containing a polyether-modified organopolysiloxane that is water-soluble while maintaining the surface properties of the polyether-modified polyorganosiloxane. [Means for solving the problem]

[0005] As described above, there is a demand for the development of a surface modifier containing a highly water-soluble polyether-modified organopolysiloxane that better retains the properties of siloxane, and a coating composition containing the surface modifier. As a result of intensive research by the present inventors to achieve the above object, the present inventors have found that polyether-modified organopolysiloxanes having oxyethylene groups and oxypropylene groups have good water solubility, and that by incorporating them into a composition as a surface modifier, it is possible to provide a coating composition that maintains the surface properties of siloxane, and have thus completed the present invention.

[0006] That is, the present invention provides [1] Provided is a surface modifier comprising a polyether-modified organopolysiloxane having an oxyethylene group and an oxypropylene group, the polyether-modified organopolysiloxane having an oxyethylene group content of 35% by mass or less, and characterized in that a 1% by mass aqueous solution of the polyether-modified organopolysiloxane has a haze value of 5.0 or less at 25°C and a haze number of 10 or more.

[0007] The present invention further provides the surface modifier having at least one of the following configurations [2] and [3]: [2] The surface modifier is a polyether-modified organopolysiloxane represented by the following formula (1): [ka] (In the formula, R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; x is an integer of 2 to 100; R 1are each independently a group represented by the following formula (2): [ka] (In the formula, R 2 is an alkyl group or an acetyl group having 1 to 12 carbon atoms, a is an integer of 2 to 40, b is an integer of 1 to 40, n is an integer of 2 to 10, and (a+1) / (a+b+1) is in the range of 0.30 to 0.65. However, the linking state of the oxyalkylene groups bracketed by a and b may be block or random. [3] In the above formula (1), R is a methyl group, x is an integer of 5 to 60, and R 2 is an alkyl group having 1 to 4 carbon atoms or an acetyl group; and n is 3.

[0008] [4] The present invention further provides a composition containing the surface modifier according to any one of the above [1] to [3] and one or more curable compounds. [5] The present invention further provides a method for using the surface modifier according to any one of the above items [1] to [3] in a coating composition. [6] The present invention further provides a method for using the surface modifier according to any one of the above items [1] to [3] in combination with a curable resin. [7] The present invention further provides a method for imparting leveling property to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of the above items [1] to [3] to the curable composition. [8] The present invention further provides a method for imparting antifouling properties to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of the above items [1] to [3] to the curable composition. [9] The present invention further provides a method for imparting wettability to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of the above items [1] to [3] to the curable composition.

[10] The present invention further provides a method for imparting antistatic properties to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of the above items [1] to [3] to the curable composition.

[0009] The present invention also provides a method for using the surface modifier described below.

[11] Use of the surface modifier according to any one of the above [1] to [3] for imparting leveling properties to a coating surface.

[12] Use of the surface modifier according to any one of the above [1] to [3] for imparting antifouling properties to a coating surface.

[13] Use of the surface modifier according to any one of the above [1] to [3] for imparting wettability to a coating surface.

[14] Use of the surface modifier according to any one of the above [1] to [3] for imparting antistatic properties to a coating surface. Effect of the Invention

[0010] The surface modifiers of the present invention containing polyether-modified organopolysiloxanes having oxyethylene groups and oxypropylene groups retain the properties of siloxanes better and are effective in many applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in more detail below, but the present invention is not limited thereto.

[0012] The surface modifier of the present invention is a polyether-modified organopolysiloxane having an oxyethylene group and an oxypropylene group, characterized in that the content of oxyethylene groups in the polyether-modified organopolysiloxane is 35 mass% or less, and a 1 mass% aqueous solution of the polyether-modified organopolysiloxane at 25°C has a haze value of 5.0 or less and a haze number of 10 or more.

[0013] The content of the oxyethylene group is preferably from 18% by mass to 35% by mass, more preferably from 20% by mass to 33% by mass, and most preferably from 21% by mass to 32% by mass.

[0014] The above Haze value is preferably from 0 to 3.0, and most preferably from 0 to 2.0.

[0015] The above-mentioned haze number is preferably from 10.3 to 18, more preferably from 10.6 to 17, and most preferably from 11.0 to 15.

[0016] The haze number of a surface modifier is a measure of hydrophilicity / hydrophobicity determined by titration, and was calculated using the following formula. Cloud number: The number of mL of phenol solution required when ethanol is added to 0.5 g of polyether-modified organopolysiloxane to make a 5 mL solution, and then the solution is titrated with a 2% phenol solution at 25°C. In general, the higher the haze number, the higher the hydrophilicity, and a haze number of 10 or more is considered to have sufficient hydrophilicity.

[0017] The polyether-modified organopolysiloxane is preferably a polyether-modified organopolysiloxane represented by the following formula (1). [ka]

[0018] In the above (1), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, and a decyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a tolyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group.

[0019] Among these, R is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, more preferably a methyl group or a phenyl group, and most preferably a methyl group.

[0020] In the above formula (1), x is an integer of 2 to 100, preferably 3 to 80, more preferably 5 to 60, and most preferably 5 to 50.

[0021] If x is less than 2, the characteristics of the siloxane are not fully exhibited, whereas if it is more than 100, water solubility may be impaired.

[0022] In the above formula (1), R 1 are each independently a group represented by the following formula (2): [ka] In the above formula (2), R 2 is an alkyl group having 1 to 12 carbon atoms or an acetyl group. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, and a lauryl group. Among these, R 2 As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and an acetyl group are preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and an acetyl group are more preferable, and in view of ease of availability, a methyl group, a butyl group, and an acetyl group are most preferable.

[0023] In the above formula (2), n is an integer of 2 to 10, preferably an integer of 3 to 8, and most preferably 3 in terms of availability.

[0024] In the above formula (2), a is an integer of 2 to 40, preferably an integer of 3 to 30, more preferably an integer of 4 to 25, and most preferably an integer of 5 to 20. If a is less than 2, water solubility is insufficient, and if it is more than 40, the characteristics of the siloxane are not fully exhibited.

[0025] In the above formula (2), b is an integer of 1 to 40, preferably an integer of 2 to 30, more preferably an integer of 4 to 25, and most preferably an integer of 5 to 20. If b is smaller than 1, compatibility with other materials may be affected, and if it is larger than 40, water solubility and the effect of siloxane may be impaired.

[0026] In the above formula (2), (a+1) / (a+b+1) is in the range of 0.30 to 0.65, preferably 0.32 to 0.60, more preferably 0.34 to 0.55, and most preferably 0.36 to 0.52. If (a+1) / (a+b+1) is less than the lower limit, water solubility is insufficient, and if it is more than the upper limit, the characteristics of the siloxane are not fully exhibited.

[0027] In the above formula (2), the linking state of the oxyalkylene groups bounded by a and b may be block or random.

[0028] The present invention is a surface modifier comprising the polyether-modified polyorganosiloxane. By adding the surface modifier to a curable composition, it is possible to impart excellent defoaming properties, leveling properties, antifouling properties, wettability, and antistatic properties to the surface of the cured product (particularly coating) obtained by curing the curable composition. The surface modifier of the present invention can be added to any curable composition as long as it can be mixed with the surface modifier and cured. In particular, it is preferable to add it to a thermosetting resin and use it, and it is particularly suitable as a surface modifier for thermosetting resins.

[0029] The present invention further provides a curable composition containing the above-mentioned surface modifier and one or more curable compounds. The content of the surface modifier in the curable composition may be adjusted appropriately depending on the type of resin, but may be, for example, 0.005 to 10% by mass, preferably 0.01 to 5% by mass. In particular, for surfactant-like applications such as leveling agents and defoamers, it is preferable to add a relatively small amount within this range, and for applications that utilize the silicone properties of the surface modifier, such as antifouling and slip properties, it is preferable to add a relatively large amount within this range. In addition, when the surface modifier is added to a thermosetting resin, it is preferable to add it after preparing a master pellet, since the surface modifier is uniformly dispersed in the thermosetting resin. In this case, the content of the surface modifier in the master pellet, which is the curable composition, may be adjusted appropriately depending on the type of resin, but may be, for example, 1 to 50% by mass, preferably 3 to 40% by mass. The curable compound is preferably a thermosetting compound, such as a compound having a hydroxyl group, a compound having a carboxyl group, a compound having an amino group, a compound having an epoxy group, a compound having a mercapto group, a compound having an isocyanate group, a compound having a hydrolyzable silyl group, a compound having a silanol group, a compound having a carboxylic anhydride group, an acrylic resin, a urethane resin, an epoxy resin, a melamine resin, and a silicone resin.

[0030] The method for preparing the curable composition containing the surface modifier of the present invention is not particularly limited, and can be obtained by mixing the surface modifier with a curable compound, and any additives and solvents as necessary, according to a conventionally known method. The curing conditions may be appropriately selected according to a conventionally known method depending on the type of curable compound used. The curable composition containing the surface modifier of the present invention provides a cured product (coating) having excellent defoaming properties, leveling properties, antifouling properties, wettability, and antistatic properties on the surface by applying it to the surface of a substrate and curing it. EXAMPLES

[0031] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0032] [Haze value] In the following, the haze value of a 1% by mass aqueous solution of polyether-modified polyorganosiloxane at 25°C was measured using a cell with a cell length of 1 cm with the following device, and the haze value of each material was measured at 25°C after a blank (air) measurement. Device name: Nippon Denshoku Industries Co., Ltd. Haze Meter NDH-4000

[0033] Synthesis Example 1 692 g of the polyether of the following formula (3) and 220 g of the siloxane of the following formula (4) were placed in a reaction vessel, and then 76 mg of a 3 mass % solution of chloroplatinic acid in isopropyl alcohol was added and reacted at 90° C. for 2 hours. [ka] (However, the linking state of the oxyalkylene groups has a block structure in the above order.) [ka] After the reaction, the volatile matter was removed at 100°C / 3 torr for 1 hour, and the mixture was filtered to obtain 862 g of the desired polyether-modified siloxane of the following formula (A). [ka] (However, the linking state of the oxyalkylene groups has a block structure in the above order.) The content of oxyethylene groups in the obtained polyether-modified siloxane was 28% by mass, and the haze value of a 1% by mass aqueous solution at 25°C was 0.18, and the cloud number was 12.9. The value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0034] Synthesis Example 2 In the same manner as in Synthesis Example 1, except that 440 g of siloxane of the following formula (6) was used instead of 220 g of siloxane of the above formula (4), 1072 g of polyether-modified siloxane of the following formula (B) was obtained. [ka] [ka] (However, the linking state of the oxyalkylene groups has a block structure in the above order.) The content of oxyethylene groups in the obtained polyether-modified siloxane was 21% by mass, and the haze value of a 1% by mass aqueous solution at 25° C. was 2.8, and the cloud number was 10.3. In addition, the value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0035] Synthesis Example 3 In the same manner as in Synthesis Example 1, except that 687 g of the polyether of the following formula (7) was used instead of 692 g of the polyether of the above formula (3), 859 g of a polyether-modified siloxane of the following formula (C) was obtained. [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) The content of oxyethylene groups in the obtained polyether-modified siloxane was 29% by mass, and the haze value of a 1% by mass aqueous solution at 25° C. was 0.15, and the cloud number was 11.3. In addition, the value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0036] Synthesis Example 4 In the same manner as in Synthesis Example 1, except that 692 g of the polyether of the above formula (3) was replaced with 692 g of the polyether of the following formula (8), 859 g of a polyether-modified siloxane of the following formula (D) was obtained. [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) The content of oxyethylene groups in the obtained polyether-modified siloxane was 28% by mass, and the haze value of a 1% by mass aqueous solution at 25° C. was 0.18, and the cloud number was 11.1. The value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0037] Synthesis Example 5 In the same manner as in Synthesis Example 1, except that 578 g of the polyether of the following formula (9) was used instead of 692 g of the polyether of the above formula (3), 751 g of a polyether-modified siloxane of the following formula (E) was obtained. [ka] (However, the linking state of the oxyalkylene groups has a block structure in the above order.) [ka] (However, the linking state of the oxyalkylene groups has a block structure in the above order.) The content of oxyethylene groups in the obtained polyether-modified siloxane was 21% by mass, and the haze value of a 1% by mass aqueous solution at 25° C. was 1.1, and the cloud number was 11.9. In addition, the value of (a+1) / (a+b+1) in the above formula (2) was 0.4.

[0038] Comparative Synthesis Example 6 In the same manner as in Synthesis Example 1, except that 856 g of the polyether of the following formula (10) was used instead of 692 g of the polyether of the above formula (3), 1,018 g of a polyether-modified siloxane of the following formula (F) was obtained. [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.)

[0039] The content of oxyethylene groups in the obtained polyether-modified siloxane was 30% by mass, and a 1% by mass aqueous solution was cloudy at 25° C., with a Haze value of 98 and a cloudiness of 10.1 at 25° C. The value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0040] Comparative Synthesis Example 7 In the same manner as in Example 1, except that 692 g of the polyether of the above formula (3) was replaced with 692 g of the polyether of the following formula (11), 858 g of a polyether-modified siloxane of the following formula (G) was obtained. [ka] [ka] (However, the connection state of each oxyalkylene group in the part enclosed in square brackets is a random structure, -(C3H6O) 10 The bond between the - portion and the oxyalkylene group is a block structure. [ka] (However, the connection state of each oxyalkylene group in the part enclosed in square brackets is a random structure, -(C3H6O) 10The bond between the - portion and the oxyalkylene group is a block structure. The content of oxyethylene groups in the obtained polyether-modified siloxane was 28% by mass, and a 1% by mass aqueous solution was cloudy at 25° C., with a Haze value of 99 and a cloudiness of 8.9 at 25° C. The value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0041] Comparative Synthesis Example 8 In the same manner as in Example 1, except that 1,036 g of the polyether of the following formula (12) was used instead of 692 g of the polyether of the above formula (3), 1,178 g of a polyether-modified siloxane of the following formula (H) was obtained. [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.)

[0042] The content of oxyethylene groups in the obtained polyether-modified siloxane was 31.5% by mass, and the haze value of a 1% by mass aqueous solution at 25° C. was 0.31, and the cloud number was 9.6. In addition, the value of (a+1) / (a+b+1) in the above formula (2) was 0.5.

[0043] Comparative Synthesis Example 9 In the same manner as in Example 1, except that 600 g of the polyether of the following formula (13) was used instead of 692 g of the polyether of the above formula (3), 769 g of a polyether-modified siloxane of the following formula (I) was obtained. [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.) [ka] (However, the connection state of the oxyalkylene groups enclosed by the two parentheses is a random structure.)

[0044] The content of oxyethylene groups in the obtained polyether-modified siloxane was 37% by mass, and the haze value of a 1% by mass aqueous solution at 25° C. was 0.69, and the cloud number was 13.6. The value of (a+1) / (a+b+1) in the above formula (2) was 0.67.

[0045] The physical properties of the polyether-modified siloxanes (surface modifiers) obtained in the above Synthesis Examples and Comparative Synthesis Examples are summarized in Table 1 below.

[0046] [Table 1]

[0047] Water-based coating compositions were produced by adding the various polyether-modified siloxanes synthesized above as surface modifiers, and the following evaluations were carried out.

[0048] Example 1 115 g of Bayhydrol A 2651 (Covestro, 41% aqueous dispersion of acrylic resin), 10 g of water, 20 g of Bayhydur XP 2655 (Covestro, water-based curing agent, isocyanate-based) and 2.0 g of the compound (A) obtained in Synthesis Example 1 were mixed until uniform to prepare an aqueous coating composition. After leaving it to stand for 30 minutes, the obtained coating composition was coated on glass using an applicator to a thickness of 30 μm, and the coating layer (1) was formed by heating and curing at 80 ° C for 90 minutes. The obtained coating layer (1) was subjected to various evaluations according to the following.

[0049] Examples 2 to 5 Coating layers (2) to (5) were formed by repeating the steps of Example 1, except that compounds (B) to (E) were used instead of compound (A) in Example 1, and various properties were evaluated.

[0050] Comparative Example 1 The process of Example 1 was repeated except that the compound (A) was not added, to form a coating layer (6), and various properties were evaluated.

[0051] Comparative Examples 2 to 5 Coating layers (7) to (10) were formed by repeating the steps of Example 1, except that compounds (F) to (I) were used instead of compound (A) in Example 1, and various properties were evaluated.

[0052] ·Defoaming property The coating composition was mixed uniformly and allowed to stand for 10 minutes, after which the state of defoaming of the coating composition was observed. ○: No bubbles. △: Some fine bubbles. ×: Many bubbles present.

[0053] Leveling ability The surface condition of the coating layer on the glass was visually observed. ○: smooth surface condition. △: There are small pockmarks on the surface in various places. ×: There is separation of color shades and large pockmarks / waviness on the surface.

[0054] ·Stain resistance A line was drawn on the coating layer on the glass with an oil-based pen, and the ease with which the line could be wiped off with tissue was evaluated. ○: Lines disappear easily. △: The lines disappear when you wipe forcefully and repeatedly. ×: The lines do not disappear.

[0055] The results of Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 2 below.

[0056] [Table 2]

[0057] As shown in Table 2, the coating layers (1) to (5) formed using the water-based paint additive containing the surface modifier of the present invention had good defoaming properties, leveling properties and antifouling properties.

[0058] On the other hand, in Comparative Example 1, which used a water-based paint additive that did not contain polyether-modified siloxane, good results were not obtained in any of the defoaming, leveling, and antifouling properties. In Comparative Examples 2 to 4, color separation was observed on the coating layer surface, there was a problem with smoothness, and the antifouling properties were insufficient. In Comparative Example 5, color separation was not observed on the coating layer surface, but there was room for improvement in the leveling and defoaming properties, and there was also a problem with the antifouling properties.

[0059] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A surface modifier comprising a polyether-modified organopolysiloxane having an oxyethylene group and an oxypropylene group, the polyether-modified organopolysiloxane having an oxyethylene group content of 35% by mass or less, and a 1% by mass aqueous solution of the polyether-modified organopolysiloxane having a haze value of 5.0 or less at 25°C and a haze number of 10 or more.

2. The surface modifier according to claim 1, which is a polyether-modified organopolysiloxane represented by the following formula (1): 【Chemistry 1】 (In the formula, R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; x is an integer of 2 to 100; R １ are each independently a group represented by the following formula (2): 【Chemistry 2】 (In the formula, R ２ is an alkyl group or an acetyl group having 1 to 12 carbon atoms, a is an integer from 2 to 40, b is an integer from 1 to 40, n is an integer from 2 to 10, and (a+1) / (a+b+1) is in the range of 0.30 to 0.

65. However, the linking state of the oxyalkylene groups bracketed by a and b may be block or random.

3. In the formula (1), R is a methyl group, x is an integer of 5 to 60, and R ２ The surface modifier according to claim 2, wherein is an alkyl group having 1 to 4 carbon atoms or an acetyl group, and n is 3.

4. A composition comprising the surface modifier according to any one of claims 1 to 3 and one or more curable compounds.

5. A method for using the surface modifier according to any one of claims 1 to 3 by adding it to a coating composition.

6. A method for using the surface modifier according to any one of claims 1 to 3 by mixing it with a curable resin.

7. A method for imparting leveling properties to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of claims 1 to 3 to the curable composition.

8. A method for imparting antifouling properties to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of claims 1 to 3 to the curable composition.

9. A method for imparting wettability to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of claims 1 to 3 to the curable composition.

10. A method for imparting antistatic properties to a coating surface obtained by curing a curable composition by adding the surface modifier according to any one of claims 1 to 3 to the curable composition.

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