KR20190133610A - Active energy ray-curable composition - Google Patents

Abstract

Provided by the present invention is an active energy ray curable composition capable of supplying a cured product having excellent water and oil repellency, antifouling properties, and anti-finger printing properties on the surface. The present invention includes a compound (A) and a photopolymerization initiator (B), represented by formula 1. In formula 1, Rf is a specific monovalent or divalent group of a number average molecular weight of 400-40,000 having a fluoropolyether structure independently of each other; Q^1 is a specific group of (a+b) valence having at least (a+b) Si atoms independently of each other; Q^2 is a divalent hydrocarbon group of 1 to 20 carbon atoms independently; and X is a group represented by a, b, c wherein R^2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms or hydrogen atoms. Moreover, a′ is 1 and a is an integer of 1 to 6 when Rf is a monovalent group; a′ is 2 and a is 1 when Rf is a divalent group; b is an integer of 1 to 20; and a+b is an integer of 3 to 21.

Description

ACTIVE ENERGY RAY-CURABLE COMPOSITION}

The present invention relates to an active energy ray curable composition. Specifically, it is applicable also to the use as an active energy ray curable composition containing a photocationic curable resin, especially a photocationic type hard coat agent, and relates to the active energy ray curable composition useful as an ultraviolet curable antifouling surface imparting agent.

A hard coat agent (or a paint having a role as a hard coat) is a material that can be applied to the surface of various articles represented by plastic resins and harden, thereby protecting the surface of the article and giving a new function to the surface of the article. Widely used.

These hard coat agents include, in addition to hardness, abrasion resistance, chemical resistance, durability, and the like, which have been conventionally required according to the expansion of their use, water and oil repellent, antifouling, anti-fingerprint, weather resistance, slipperiness, antistatic property, antifogging property, Further high functions such as orchid and antireflection are required. In particular, in recent years, there has been a demand for improvement of antifouling properties and dirt wiping properties.

Examples of the active energy ray-curable hard coat agent include an ultraviolet ray and an electron beam-curable hard coat agent and a thermosetting hard coat agent. As an ultraviolet-ray electron beam hardening type hard coat agent, the acrylic group containing hard coat agent hardened | cured by radical polymerization by an ultraviolet-ray is mentioned, for example. In recent years, in addition to the characteristic which the hard coat agent before addition has, by adding a very small amount to an ultraviolet curable hard coat agent, the fluorine-containing compound which can provide water- and oil-repellent property, antifouling property, anti-fingerprint, etc. to the hardened surface obtained is examined.

MEANS TO SOLVE THE PROBLEM This patent proposes the fluorine-containing compound which can use suitably as an additive for an ultraviolet-ray or electron beam hardening type hard coat agent, and can provide favorable water- and oil-repellent property, antifouling property, and fingerprint property to the hardened | cured material obtained by patent document 1-4. It was.

Japanese Patent Application Laid-Open No. 2010-053114 Japanese Patent Application Laid-Open No. 2010-138112 Japanese Patent Application Laid-Open No. 2010-285501 Japanese Patent Application Laid-Open No. 2011-241190

The ultraviolet (UV) curable acrylic hard coat agent which is cured by radical polymerization used for the above-mentioned purposes is quick to cure, and is rich in kinds of acrylic compounds and initiators that can be used as components, and it is easy to adjust the composition for the purpose. There is an advantage. On the other hand, there is an inherent problem due to the characteristics of radical polymerization of acrylic groups such as large curing shrinkage, which are affected by curing inhibition by oxygen.

In particular, the inhibition of curing by oxygen is more likely to be affected as the air interface, i.e., the side closer to the outermost surface of the coating film by the hard coat composition, becomes a major obstacle in providing antifouling properties to the outermost surface. In addition, the curing shrinkage due to the polymerization of the acrylic group is likely to have a large effect of curling and cracking due to the curing shrinkage when the polyfunctionalization is performed for increasing the hardness, and further increases the demand for higher hardness for the recent hard coat agent. About acrylic polymerization type, it became difficult to respond.

On the other hand, in the ultraviolet curable cationic polymerization system hard coat agent by the compound which has an epoxy group, an oxetane group, a vinyl ether group, etc., since there is no polymerization inhibition by oxygen, it is excellent in surface hardenability and the volume shrinkage at the time of hardening is also acrylic type It has the big feature of being small compared with (radical polymerization type).

For this reason, the development of a UV cation hardening type hard coat agent is progressing in recent years, and the demand for providing antifouling property also increased in the cation hardening type hard coat agent.

This invention is made | formed in view of the said situation, and is applicable also to the use as a photocationic type hard-coat agent which can supply the hardened | cured material which has the excellent water-oil repellency, antifouling property, and fingerprint-proof, and provides UV-curable antifouling surface It is an object to provide an active energy ray curable composition useful as an agent.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the active energy ray curable composition containing the specific fluorine-containing epoxy-modified organosilicon compound (A) and photoinitiator (B) represented by following General formula (1) ( The hardened | cured material of the photocationic polymerization type composition) discovered that the surface may have the outstanding water / oil repellency, antifouling property, and fingerprint resistance, and came to this invention.

(Rf, Q1, Q2, X, a, a ', b and a + b are as follows.)

That is, the present invention provides the following active energy ray curable composition.

[One]

General formula (1)

(In Formula (1), Rf is a monovalent or divalent group having a number average molecular weight of 400 to 40,000 having a fluoropolyether structure independently of each other, and when Rf is a monovalent group,

또는

or

(Wherein j is an integer of 1 to 3, k is an integer of 0 to 200, k 'is an integer of 1 to 200, and l and m are each an integer of 1 to 100).

Is indicated by

When Rf is a divalent group, the following formula

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.),

(In formula, j is an integer of 1-3 independently, h and i are each an integer of 0-200, and h + i is 2-300. Each repeating unit may be combined at random.) ,

(Wherein r is an integer of 2 to 6, k and t are each an integer of 0 to 200, provided that k + t is 2 to 200. s is an integer of 0 to 6), or

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.)

Is displayed.

When Rf is a monovalent group, a 'is 1 and a is an integer of 1-6. When Rf is a divalent group, a 'is 2, a is 1, b is an integer of 1-20, a + b is an integer of 3-21.

Q ¹ is, independently of each other, a group of (a + b) values having at least (a + b) Si atoms,

(Wherein a and b are as described above, the dashed line represents a bond and each silicon atom of the unit represented in parentheses having a repeat is bonded to Rf in the formula (1), and b repeats) Each silicon atom of the unit represented in parentheses having the above bond with Q ² in the above formula (1), and the sequence of units represented in the parentheses may be random.)

Is displayed.

Q ² is a C1-C20 divalent hydrocarbon group which may include an ether bond or an ester bond independently of one another and may have a cyclic structure.

X independently of each other, the following formula (I) or (II)

(In formula (I), R <^1> is a hydrogen atom or a C1-C20 unsubstituted or substituted monovalent hydrocarbon group independently, may contain an ether bond or an ester bond, and may have a cyclic structure. )

(In formula (II), R <^2> is a hydrogen atom or a C1-C20 unsubstituted or substituted monovalent hydrocarbon group each independently.)

Is represented by.)

Fluorine-containing epoxy-modified organosilicon compound (A) represented by

It is an active energy ray curable composition containing a photoinitiator (B), The active energy ray curable composition which supplies hardened | cured material whose surface water contact angle is 100 degrees or more.

[2]

The formula (1), to the structure represented by the formula -X ² -Q (2) to an active energy ray curable composition according to [1] is selected from a group represented by (5).

In the above formula, f is an integer of 1 to 10, e is an integer of 0 to 5, g is an integer of 0 to 10, f + 2g + e is in the range of 1 to 20, and n is 1 to 1 It is an integer of 20. R <^2> is a hydrogen atom or a C1-C20 unsubstituted or substituted monovalent hydrocarbon group each independently.).

[3]

In the formula (1), the active energy ray curable composition according to [1] or [2], wherein Q ² is independently selected from the group represented by the following formula.

-CH ₂ CH _2- ,

-CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ OCH _2- ,

-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , or

-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2-

[4]

In the formula (1), the structure represented by -Q ² -X is

The active energy ray curable composition as described in phosphorus [2] or [3].

[5]

The active energy ray curable composition in any one of [1]-[4] whose photoinitiator (B) is a photo-acid generator.

[6]

The active energy ray curable composition as described in any one of [1]-[5] whose photoinitiator (B) is either a diazonium salt, an iodonium salt, or a sulfonium salt.

[7]

When the compound which has cation curability is only (A) component, the active energy in any one of [1]-[6] containing 0.01-20 mass parts of (B) component with respect to 100 mass parts of (A) component. Precurable compositions.

[8]

(C) component which consists of a compound which has one or more types of cation curability other than (A) component further, and 0.01-20 mass of (B) component with respect to a total of 100 mass parts of (A) component and (C) component. The active energy ray curable composition in any one of [1]-[6] which contains a part.

[9]

(C) The compound has any one or more of an epoxy group, a vinyl ether group, an oxane group, and a carbonyl group in 1 molecule, an aliphatic unsaturated hydrocarbon compound, a styrene derivative, a bicyclo ortho ester, a spiro orthocarbonate, and a spy The active energy ray curable composition as described in [8] which is a rooso ester or a cationically polymerizable nitrogen containing compound.

[10]

0.01-10 mass parts of (A) component are contained with respect to 100 mass parts of (C) component, and the active energy ray curable composition as described in [8] or [9] whose water contact angle of the hardened | cured material surface after hardening is 100 degrees or more.

The active energy ray curable composition of the present invention can impart excellent water / oil repellency, antifouling property, and anti-fingerprint to the surface of the cured product. Therefore, this active energy ray curable composition is applicable also to a use as a photocationic type hard coat agent, and is useful as an ultraviolet curable antifouling surface imparting agent which can be hardened by a photocationic polymerization reaction.

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The active energy ray curable composition which concerns on this invention contains a fluorine-containing epoxy modified organosilicon compound (A) shown below, and a photoinitiator (B).

A fluorine-containing epoxy modified organosilicon compound (A) which is a 1st component of this invention is a cation curable compound represented by following General formula (1).

(In formula (1), Rf is a monovalent or divalent later-described specific group having a number average molecular weight of 400 to 40,000 having a fluoropolyether structure independently of each other, and Q ¹ is independently of each other at least (a + b). (A + b) which has (a) Si atom is a specific group mentioned later, Q <^2> is a C1-C20 divalent hydrocarbon group which may contain an ether bond or an ester bond independently, and may have a cyclic structure. X is a group represented by formula (I) or (II) described later, and when Rf is a monovalent group, a 'is 1 and a is an integer of 1 to 6. When Rf is a divalent group, a' Is 2, a is 1, b is an integer of 1 to 20, and a + b is an integer of 3 to 21.)

In formula (1), X is group represented by following formula (I) or (II) independently of each other.

In formula (I), R <^1> is a hydrogen atom or C1-C20, Preferably it is C1-C10, More preferably, it is a C1-C8 unsubstituted or substituted monovalent hydrocarbon group, It is an ether bond Or it may contain the ester bond and may have a cyclic structure. Examples of the monovalent hydrocarbon group include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group and decyl group, vinyl group and allyl. Alkenyl groups, such as group, a propenyl group, butenyl group, and a hexenyl group, cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group, etc. are mentioned. Moreover, halogen substituted monovalent hydrocarbon groups, such as a fluoromethyl group, bromoethyl group, and a trifluoropropyl group, which substituted part or all of the hydrogen atoms of these hydrocarbon groups by halogen atoms, such as chlorine, fluorine, and bromine, may be sufficient.

Preferably, R ¹ is a hydrogen atom.

In formula (II), R <^2> is a hydrogen atom or C1-C20, Preferably it is C1-C10, More preferably, it is a C1-C8 unsubstituted or substituted monovalent hydrocarbon group mutually. Examples of the monovalent hydrocarbon group include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group and decyl group, vinyl group and allyl. Alkenyl groups, such as group, a propenyl group, butenyl group, and a hexenyl group, etc. are mentioned. Moreover, halogen substituted monovalent hydrocarbon groups, such as a fluoromethyl group, bromoethyl group, and a trifluoropropyl group, which substituted part or all of the hydrogen atoms of these hydrocarbon groups by halogen atoms, such as chlorine, fluorine, and bromine, may be sufficient. Preferably, R ² is a hydrogen atom or a methyl group.

Examples of the structure represented by the formula (I) or (II) include the following ones.

(Wherein R ² is as described above.)

In said formula (1), Q <^2> is a C1-C20, preferably C2-C15 bivalent hydrocarbon group independently of each other, may form the cyclic structure, and it may be an ether bond (-O-) or an ester bond. (-COO-) may be included.

In said formula (1), Q <^2> can mention the following, for example.

In the above formula, f is an integer of 1 to 10, e is an integer of 0 to 5, g is an integer of 0 to 10, and f + 2g + e is in the range of 1 to 20. Preferably f Is an integer of 1 to 6, e is 1 or 2, g is an integer of 0 to 4, and f + 2g + e is in the range of 3 to 10. n is an integer of 1 to 20, preferably 2 It is an integer of -15.)

As this Q <^2> , the thing of the following structure is mentioned, for example.

-CH ₂ CH _2- ,

-CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ OCH _2- ,

-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- ,

-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2-

In the formula (1), as the structure represented by -Q ² -X, for example, there may be mentioned a structure represented by the following formula (2) to (5).

In said formula, f, e, g, f + 2g + e, n are as above-mentioned. R <^2> is as above-mentioned, Preferably it is a hydrogen atom or a methyl group.

In the formula (1), the structure represented by -Q ² -X is

or

Is particularly preferred.

In said formula (1), Q <^1> is a (a + b) valent group which has at least (a + b) Si atom independently of each other.

When Rf is monovalent in said Formula (1), a 'is 1, a is an integer of 1-6, Preferably it is an integer of 1-4, More preferably, it is 1. When Rf is bivalent, a 'is 2 and a is 1. b is an integer of 1-20, Preferably it is an integer of 1-6, More preferably, it is an integer of 2-4. Moreover, a + b is an integer of 3-21, the integer of a + b = 3-10 is preferable, the integer of a + b = 3-6 is more preferable, and a + b = 4 or 5 is still more preferable. Do.

Q <^1> has a (a + b) valent cyclic siloxane structure represented by the following formula | equation.

In the above formula, a and b are as described above, and the dashed line represents a bonding hand, and each silicon atom of the unit represented in parentheses having a repetition is bonded to Rf in the formula (1), and b repetitions Each silicon atom of the unit represented in parentheses having the above bonds with Q ² in the formula (1). Arrangement of each unit shown in parentheses may be random.

In said formula (1), Rf is a monovalent or divalent group of the number average molecular weights 400-40,000 which have a fluoropolyether structure independently of each other. The number average molecular weight of Rf is preferably in the range of 500 to 20,000. In a number average molecular weight in the invention is a value calculated from the ratio of the terminal structure and the main chain structure based on the ¹ H-NMR and ¹⁹ F-NMR.

Rf which is monovalent is represented by a following formula.

(Wherein j is an integer of 1 to 3, k is an integer of 0 to 200, preferably an integer of 0 to 100, k 'is an integer of 1 to 200, preferably an integer of 1 to 60) , l and m are each an integer of 1 to 100.)

Especially, it is preferable to represent with the following formula | equation.

(In said formula, j is an integer of 1-3, k is an integer of 0-200, Preferably it is an integer of 0-100, and l and m are integers of 1-100, respectively.)

Rf which is bivalent is represented by a following formula.

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.)

(In formula, j is an integer of 1-3 independently, h and i are each an integer of 0-200, and h + i is 2-300. Each repeating unit may be combined at random.)

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.)

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.)

Especially, it is preferable to represent with the following formula especially.

(In formula, j is an integer of 1-3, h and i are integers of 0-200, respectively, except h + i is 2-300. Each repeating unit may be combined at random.)

The compound (fluorine-containing epoxy-modified organosilicon compound) represented by the said General formula (1) can be manufactured by the following method, for example.

First of all, with respect to the fluorine-containing compound (a) having an olefin group at its terminal, an organosilicon compound (b) having two or more, preferably three or more SiH groups, in combination with siloxane or two or more thereof The organosilicon compound) is reacted by addition under the condition that the SiH group becomes excessive. By this reaction, a fluorine-containing compound (c) having a plurality of SiH groups is synthesized.

In particular, the compound (a) can be represented by the following formula (6).

Rf ^0- (CH = CH ₂ ) _x (6)

(In Formula (6), x is 1 when Rf ⁰ is monovalent and 2 when divalent.)

Rf ⁰ is a monovalent group represented by the following formula (7) or a divalent group represented by the following formula (8).

Rf ² -Q ^6- (7)

-Q ⁶ -Rf ¹ -Q ^6- (8)

In the formula (7), Rf ² is the formula

(Wherein j is an integer of 1 to 3, k is an integer of 0 to 200, preferably an integer of 0 to 100, k 'is an integer of 1 to 200, preferably an integer of 1 to 60) , l and m are each an integer of 1 to 100.)

Is displayed.

In addition, the expression (8), Rf ¹ has the formula

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.),

(In formula, j is an integer of 1-3, h and i are integers of 0-200, respectively, except h + i is 2-300.)

Is displayed.

In addition, in said Formula (7) and (8), Q <^6> is C2-C10, Preferably it is a C2 bivalent organic group which may contain the oxygen atom, the nitrogen atom, or the silicon atom independently of each other.

As said Q <^6> , what is represented by a following formula is mentioned.

Examples of monovalent Rf ⁰ The compound (a), for example, there may be mentioned the following.

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(In formula, j is an integer of 1-3, k 'is an integer of 1-200, Preferably it is an integer of 1-60.)

(In said formula, j is an integer of 1-3, l and m are integers of 1-100, respectively.)

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

Divalent Rf ⁰ As the compound (a), for example, there may be mentioned the following.

(Wherein r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with k + t being 2 to 200, preferably 3 to 150 S is an integer of 0 to 6)

(Wherein j is an integer of 1 to 3 independently, h and i are each an integer of 0 to 200, preferably an integer of 2 to 100, except that h + i is 2 to 300, preferably 4 To 200. Each repeating unit may be combined at random.)

(Wherein r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with k + t being 2 to 200, preferably 3 to 150 S is an integer of 0 to 6)

(Wherein r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with k + t being 2 to 200, preferably 3 to 150 S is an integer of 0 to 6)

In particular, the compound (b) can be represented by the following formula (9).

Q ^1- (H) _{a + b} (9)

(Q <^1> , a, and b are as above-mentioned in Formula (9). H shown in parentheses is a hydrogen atom couple | bonded with Si atom in Q <^1> structure directly.)

As this compound (b), the following are mentioned, for example.

(In the above formula, a and b are as described above.)

In particular, the following are preferable.

When Rf ⁰ in the compound (a) is a monovalent group, the number of olefin groups in the compound (a) is (a + b) relative to the number (a + b) of SiH groups in the compound (b) in one molecule. The reaction is preferably carried out in an amount of less than + b), preferably a. The structure of obtained compound (c) can be represented by following formula (10).

(Rf ⁰ -C ₂ H ₄ ) _a -Q ^1- (H) _b (10)

(Wherein, Rf ⁰ , Q ¹ , a and b are as described above.)

As a compound (c) represented by Formula (10), the following are mentioned, for example.

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

When Rf ⁰ in the compound (a) is a divalent group, it is preferable to react at a molar ratio of the compound (a): compound (b) = 1: 2, and the structure of the compound (c) obtained is, for example, It can be represented by the following formula (11). That is, it becomes a structure in which the compound (b) of each molecule was introduce | transduced into the both ends of compound (a).

(Wherein, Q ¹ , Rf ⁰ and b are as described above. H in parentheses is a hydrogen atom directly bonded to the Si atom in the Q ¹ structure.)

As a compound (c) represented by Formula (11), the following are mentioned, for example.

(Wherein j is an integer of 1 to 3 independently, h and i are each an integer of 0 to 200, preferably an integer of 2 to 100, except that h + i is 2 to 300, preferably 4 To 200. Each repeating unit may be combined at random.)

Although the said addition reaction can be performed in absence of solvent, you may carry out in presence of a solvent as needed. What is necessary is just to use the organic solvent widely used, such as toluene, xylene, and isooctane. However, it is preferable that a boiling point is more than the target reaction temperature, and does not inhibit reaction, and the fluorine-containing compound (c) produced after reaction is soluble at reaction temperature. For example, partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are preferable. In particular, m-xylene hexafluoride is preferable.

The addition reaction catalyst may use a conventionally well-known thing. For example, compounds containing platinum, rhodium or palladium can be used. Among them, compounds containing platinum are preferred, hexachloroplatinum (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octyl Aldehyde / octanol complexes or platinum supported on activated carbon can be used. The compounding quantity of a catalyst should just be an effective amount. In particular, the amount of metal contained in the compound (a) is preferably 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 mass ppm.

In addition reaction, the loading order of each component is not specifically limited. For example, a method of heating a mixture of compound (a), compound (b) and catalyst gradually from room temperature to addition reaction temperature, to a desired reaction temperature of a mixture of compound (a), compound (b) and dilution solvent Method of adding a catalyst after heating, dropping compound (a) into a mixture of compound (b) and catalyst heated to the target reaction temperature, compound (b) heated to target reaction temperature (b) The method of dripping the mixture of a) and a catalyst is mentioned. Among them, compound (a) to a method of adding a catalyst after heating the mixture of compound (a), compound (b) and dilution solvent to the target reaction temperature, or heated to the target reaction temperature (b) Particularly preferred is a method of dropping a mixture of and a catalyst. The addition reaction conditions may be in accordance with a conventionally known method. In particular, it is 0.5 to 96 hours, preferably 1 to 48 hours at a reaction temperature of 50 to 150 ° C, preferably 70 to 120 ° C in air or an inert gas (N ₂ , Ar, etc.) in a dry atmosphere. desirable.

The compounding quantity of the compound (a) is less than (a + b) the number of olefin groups which the compound (a) has with respect to 1 molecule of the compound (b) which has (a + b) SiH groups, Preferably a is It is good to be quantity. In particular, when Rf ⁰ in the compound (a) is a divalent group, the reaction is preferably carried out at a molar ratio of compound (a): compound (b) = 1: 2. In particular, in order to prevent three-dimensional crosslinking, it is preferable to remove the unreacted compound (b) by vacuum distillation or the like after carrying out the addition reaction using the excess amount of the compound (b) with respect to the terminal olefin group of the compound (a). desirable.

Subsequently, addition reaction of the SiH group of the fluorine-containing compound (c) obtained above and the compound (d) which has a terminal olefin group and an epoxy group in 1 molecule is performed, and the fluorine-containing epoxy modified organosilicon compound represented by said Formula (1) is made into You can get it.

As a compound (d), the compound represented by following formula (2a)-(5a) is mentioned, for example.

In said formula, f 'is an integer of 0-8, e is an integer of 0-5, g is an integer of 0-10, f' + 2g + e is in the range of 2-18. Preferably, f is an integer of 0-6, e is 1 or 2, g is an integer of 0-4, and f '+ 2g + e is in the range of 2-8. n 'is an integer of 0-18, Preferably it is an integer of 0-13. R <^2> is as above-mentioned, Preferably it is a hydrogen atom or a methyl group.

As a compound (d), the following are illustrated. You may use this compound individually by 1 type or in combination of 2 or more types.

The addition reaction of the compound (c) and the compound (d) may be performed according to a conventionally known method. Preferably, in the presence of the above-described addition reaction catalyst, in a dry atmosphere, in the air or an inert gas (N ₂ , Ar, etc.), the reaction temperature is 50 to 150 ° C, preferably 0.5 to 96 hours at 50 to 120 ° C, preferably It is good to carry out in 1 to 48 hours. This reaction may use a solvent as needed.

Although the compounding quantity of a compound (d) with respect to a compound (c) can use arbitrary values, with respect to the number of SiH groups which a compound (c) has, the number of terminal olefin groups which a compound (d) has is the same, or Or it is preferable to carry out using the quantity by which the number of terminal olefin groups becomes excess, and after addition reaction is performed, it is preferable to remove unreacted compound (d) by distillation under reduced pressure etc. In particular, the ratio of the number of terminal olefin groups of the compound (d) to one of the SiH groups of the compound (c) is preferably 1.0 to 5.0, preferably in an amount of 1.0 to 2.0.

As a compound (A) represented by the said General formula (1), Especially preferably, the compound shown below is mentioned.

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(In formula, k is an integer of 0-200, Preferably it is an integer of 0-100.)

(Wherein j is independently an integer of 1 to 3, h and i are each an integer of 0 to 200, preferably an integer of 2 to 100, with h + i being 2 to 300, preferably 4 To 200. Each repeating unit may be combined at random.)

(Wherein j is an integer of 1 to 3 independently, h and i are each an integer of 0 to 200, preferably an integer of 2 to 100, except that h + i is 2 to 300, preferably 4 To 200. Each repeating unit may be combined at random.)

(Wherein j is an integer of 1 to 3 independently, h and i are each an integer of 0 to 200, preferably an integer of 2 to 100, except that h + i is 2 to 300, preferably 4 To 200. Each repeating unit may be combined at random.)

These compounds (A) may be individual types, or may mix and use different compound (A) in multiple types.

This invention is an active energy ray curable composition containing the compound (A) mentioned above and at least 1 photoinitiator (B). The photopolymerization initiator (B) is not particularly limited as long as it is a compound capable of initiating the polymerization of the epoxy group of the compound (A) by light (particularly, ultraviolet rays). Onium salt is mentioned.

These examples as the counter anion _{^{SbF 6 -, AsF 6 -,}} BF 4 -, B (C 6 F 5) 4 -, PF 6 -, (Rf '''') x PF 6-x - ( wherein, Rf ''''Is, independently of each other, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and at least 80 mol% of hydrogen atoms bonded to carbon atoms of the respective groups by fluorine atoms; X is an integer of 1 to 5), and an allyl diazonium salt (diazonium salt), a diallyl iodonium salt (iodonium salt), a triallyl sulfonium salt (sulfonium salt), etc. are mentioned. In view of toxicity, however, onium salts having a counter anion of boron and phosphorus are particularly preferred.

As a photoinitiator (B), many kinds of compounds and their mixture are marketed including the example shown above. As a specific brand name, San Afro Corporation "CPI series" (for example, CPI-100P, CPI-101A8, CPI-200K, CPI-210S, CPI-310B, CPI-400PG), ADEKA `` ADEKA OPTO '' Merc SP series "(for example, SP150, SP152, SP170, Adekao SP172), Sanshin Kagaku" San-Eido SI series "(for example, SI-60L, SI-80L, SI-100L), FUJIFILM Wako Pure Chemical Industries, Ltd. "light WPI series" (for example, PI-169, WPI-170, WPI-124, WPI-116, WPI-113), BASF Corporation `` IRGACURE 250, IRGACURE 270, IRGACURE 290 '' Etc. can be presented and these can also be used individually and in mixture. Moreover, in recent years, the polymerization initiator which has the function of photo cation generation and thermal cation generation is also marketed, These can also be used. For example, TA-100 of San Afro Co., Ltd. can be mentioned.

In addition to (A) component and (B) component, this invention may further contain (C) component which consists of a compound which has one or more types of cation curability other than (A) component.

Examples of the compound having cation-curable properties include compounds having one or more epoxy groups and cyclic ethers such as oxetane groups, compounds having vinyl ether groups, and aliphatic unsaturated hydrocarbon compounds such as isobutylene (IB), styrene derivatives, and lactones. And cationically polymerizable nitrogen-containing compounds (monomers) such as compounds having a carbonyl group such as cyclic carbonate, bicyclo ortho ester, spiro ortho carbonate, spiro ortho ester, and N-vinyl carbazole.

Among these, the compound which has an epoxy group contains aromatic epoxide, alicyclic epoxide, and aliphatic epoxide.

Examples of the aromatic epoxide include monovalent or polyvalent phenol derivatives having at least one aromatic ring, for example, phenol, bisphenol A, bisphenol F, bisphenol AF, and glycidyl ether of phenol novolac. Moreover, the compound which introduce | transduced the alkyl ether and the ester structure into a part of structure of these glycidyl ether can also be used.

As an alicyclic epoxide, it is a compound obtained by epoxidizing the compound which has at least 1 cyclohexene ring and a cyclopentene ring, The structure of an alkyl ether, an alkyl ether oligomer, an ester structure, and an epsilon caprolactone oligomer The compound introduced in the middle can also be used. Specifically, vinylcyclohexene dioxide, 3, 4- epoxycyclohexyl methyl-3, 4- epoxy cyclohexane carboxylate, limonene dioxide, bis (3, 4- epoxy cyclohexyl methyl) adipate, dicyclopentadiene Ended diepoxide 1, 4- cyclohexane dimethanol bis (3, 4- epoxy cyclocarboxylate) etc. are mentioned.

Examples of the aliphatic epoxide include aliphatic polyhydric alcohols or polyglycidyl ethers (1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl) of the alkylene oxide adduct. ), Polyglycidyl esters of aliphatic polybasic acids (such as diglycidyl tetrahydrophthalate), and epoxides of long-chain unsaturated compounds (epoxidized polybutadienes, epoxides of plant-derived unsaturated hydrocarbon compounds). .

As a compound which has an oxetane group, a well-known thing etc. can be used, For example, 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl (3-ethyl-3- oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3 -Oxetanyl methoxy) methyl] benzene, an oxetanyl silsesquioxane, a phenol novolak oxetane, etc. are mentioned. As a specific brand name, "Aron oxetane series" by Toagose Co., Ltd., etc. are mentioned.

Examples of the compound having a vinyl ether group include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether, 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p- Aromatic vinyl ethers such as methoxyphenyl vinyl ether. Moreover, bifunctional vinyl ether, such as butanediol- 1, 4- vinyl ether, triethylene glycol vinyl ether, and dipropylene glycol vinyl ether, is mentioned.

Examples of the styrene derivatives include derivatives such as α-methyl styrene, p-methoxy styrene and p-tert-butoxy styrene in addition to styrene.

Examples of the aliphatic unsaturated hydrocarbon compound include isobutylene, cyclopentadiene, norbornadiene, indene and tetrahydroindene.

Examples of the cationic polymerizable nitrogen-containing monomer include cyclic amines such as ethyleneimine, oxazoline, N-vinylcarbazole and N-vinylpyrrolidone.

As bicycloorthoester, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabi Cyclo- [2.2.2] octane and the like.

Examples of spiroocarbonate include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane Can be.

Particularly, those having an epoxy group, an oxetane group, and a vinyl ether group are suitable. Among these polymerizable reactors, in addition to the above-described monomers, those in the form introduced into the terminal and side chain of the siloxane polymer (oligomer) may be used. .

The ratio of each component of the active energy ray-curable composition of the present invention is determined by considering various factors such as the nature of the cationic polymerizable compound, the type and amount of energy ray, irradiation amount, temperature, curing time, humidity, and thickness of the coating film, and is not particularly limited. When the compound having cation curability is only the component (A), the component (B) is preferably 0.01 to 20 parts by mass, and particularly preferably 0.05 to 10 parts by mass based on 100 parts by mass of the component (A). If the amount of the component (B) is too small, curing concentration tends to occur because the concentration of the initiator component is low, and the reaction rate is lowered. When too much, the quantity of the initiator fragment which does not participate in the crosslinked structure contained in hardened | cured material after hardening may become too large, and may have an unintended effect on the physical property of hardened | cured material.

Moreover, when it further contains the said (C) component as an active energy ray curable composition of this invention, 0.01-20 mass of (B) components are preferable with respect to a total of 100 mass parts of (A) component and (C) component. Part, particularly preferably 0.05 to 10 parts by mass. Also in this case, when the quantity of (B) component is too small, since the density | concentration of an initiator component is light, hardening defect will arise easily and reaction rate will fall. When too much, the quantity of the initiator fragment which does not participate in the crosslinked structure contained in hardened | cured material after hardening may become too large, and may have an unintended effect on the physical property of hardened | cured material.

Moreover, in the active energy ray curable composition of this invention, when it contains (C) component, it is preferable to contain 0.01-10 mass parts of (A) component with respect to 100 mass parts of (C) component, and especially 0.05- It is more preferable to contain 5 mass parts.

The active energy ray curable composition of this invention complements sclerosis | hardenability, and can also contain a sensitizer as needed. As such a sensitizer, the sensitizer disclosed in Unexamined-Japanese-Patent No. 11-279212, Unexamined-Japanese-Patent No. 09-183960, etc. can be used, For example, anthracene {anthracene, 9, 10- dibutoxy anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxycanthracene, etc .; Pyrene; 1,2-benzanthracene; Perylene; Tetracene; Coronene; Thioxanthones {thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2-isopropyl thioxanthone and 2,4-diethyl thioxanthone]; Phenothiazines {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine and the like}; Xanthone; Naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxy naphthalene, 4-methoxy-1-naphthol and the like}; Ketones {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone and 4-benzoyl-4'-methyldiphenylsulfide and the like}; Carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole and the like}; Chrysene {1,4-dimethoxycrysene and 1,4-di-α-methylbenzyloxycrysen and the like}; Phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene and the like} and the like. When it contains a sensitizer, 1-300 mass parts is preferable with respect to 100 mass parts of (B) component, More preferably, it is 5-200 mass parts.

In addition to the curable composition of this invention, if necessary, well-known additives (pigment, filler, antistatic agent, flame retardant, antifoamer, flow regulator, light stabilizer, antioxidant, adhesiveness imparting agent, ion supplement, coloring inhibitor, solvent, non Reactive resins, oils, oligomers, and the like).

About the above-mentioned (B) component, (C) component, and the other arbitrary additives which can be mix | blended arbitrarily, for example, Technonet company "Photocuring technology databook material edition" (2000, Technonet company), photo `` Photopolymer handbook '' in `` Polymer polymer meeting '' (1989), Beef Juice Center `` UV and EB Curing Technology '' (in 1982, Comprehensive Technology Center), `` UV and EB Curing Materials '' (1992, CMC), Kijutsu Chohokyokai `` Cure failure and inhibition causes and UV countermeasures in UV curing '' (2003, Kijutsu Johokyokai), color materials, 68, (5), 286-293 (1995 ), Fine Chemical, 29, (19), 5-14 (2000), "Network Polymer" Vol. 30 No. 5 (2009), "Network Polymer" Vol. 30 No. 5 (2009), "Network Polymer" Vol. 31 No. 4 (2010), Kijutsu Johokyokai `` Combination Design, Characterization and New Application of UV Curable Resin '' (2017, Kijutsu Johokyokai), CMC Edition Edition `` Market Status of UV, EB Cured Materials and Products and Many publications are disclosed in "Prospect" (2007, CMC Edition), Science & Technology Edition "Optimizing UV Curing Process" (2008, Science & Technology), and these can be used in any combination.

Moreover, the active energy ray curable composition of this invention may contain a solvent as needed. Preferred solvents include alcohols such as isopropanol and butanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ethyl acetate and ethyl lactate. And esters of glycol ethers such as propylene glycol monomethyl ether acetate, and the like. Although the compounding quantity of a solvent in particular is not restrict | limited, Preferably, when it contains a total of 100 mass parts ((C) component of the said (A) component and (B) component, of (A), (B), (C) component It is good that it is 20-900 mass parts with respect to 100 mass parts in total), especially 50-400 mass parts.

The preparation method of the active energy ray curable composition of this invention is not specifically limited. The curable composition of this invention can be obtained by mixing the said (A) component, (B) component, (C) component, other arbitrary additives, and a solvent as needed according to a conventionally well-known method.

Moreover, as a general use form of the active energy ray curable composition of this invention, if the active energy ray curable composition layer of this invention adheres or adheres after hardening, it can apply on any base material, Especially a resin base material, for example, polyethylene tere Phthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride , Polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, Fluorine Resin, Nile , There may be mentioned a resin such as acrylic resin. These can be used for the surface about what takes arbitrary forms, such as a film, a plate shape, and a shaping | molding member.

Moreover, when coating to a film base material, you may take the structure which apply | coated the adhesive to the surface opposite to what apply | coated and formed the fluorine-containing active-energy-ray-curable composition layer, and may further arrange | position the release film for protecting an adhesive.

Moreover, although the said film base material may be a base material which consists only of the resin film mentioned above, in order to improve adhesiveness with the active energy ray curable composition of this invention, the film base material which provided the primer layer in the said resin film may be sufficient. As said primer layer, what consists of polyester resin, urethane resin, acrylic resin etc. is mentioned, for example.

Moreover, you may coat-harden the active energy ray curable composition of this invention on the curable composition layer which does not correspond to this invention of hardening and uncuring. For example, the active-energy-ray-curable composition of this invention can be apply | coated on the hardened | cured material layer with higher deformation prevention properties, such as hardness, durability, antistatic property, and curl.

Moreover, in order to improve the adhesiveness with the active energy ray curable composition of this invention, the surface of a resin film is uneven | corrugated, the corona discharge treatment, the chromic acid treatment, the flame treatment, the hot wind treatment by the sandblasting method, the solvent treatment method, etc. The treatment may be carried out by ozone / ultraviolet irradiation treatment, oxidation treatment or the like.

Although it does not restrict | limit especially as a method of apply | coating the active energy ray curable composition of this invention to the said base material or article, For example, roll coat, gravure coat, flow coat, curtain coat, dip coat, spray coat, spin coat, bar Known coating methods such as coating, inkjet printing and screen printing can be used.

After coating, an active energy ray is irradiated to a coating film, and this is hardened | cured. Here, as an active energy ray, arbitrary things, such as an electron beam and an ultraviolet-ray, can be used, but an ultraviolet-ray is especially preferable. As an ultraviolet source, a mercury lamp, a metal halide lamp, and an LED lamp are suitable. As the ultraviolet ray irradiation quantity is too small, since the possibility of uncured components remain, and the degradation is too large, the coating film and the base material is preferably in the range of 10~10,000mJ / cm ^2, in particular 100~4,000mJ / cm ² .

In addition, in order to prevent the inhibition of curing by moisture, at the time of ultraviolet irradiation, the irradiation atmosphere is replaced with a gas such as air, nitrogen, carbon dioxide or argon in which the amount of moisture in the gas is controlled, or the surface of the coating film has ultraviolet permeability having releasability. It may be covered with a protective layer and irradiated with ultraviolet rays thereon, or when the substrate has ultraviolet permeability, the surface of the coating film may be covered with a protective layer having releasability and then irradiated with ultraviolet rays from the opposite side to the coated surface of the substrate. Moreover, in order to perform the leveling of a coating film or reaction of a cationically polymerizable group in a coating film effectively, you may heat a coating film and a base material by arbitrary methods, such as an infrared rays or hot air drying furnace, before and during ultraviolet irradiation.

Although it does not restrict | limit especially as thickness of the hardened | cured material layer of the active energy ray curable composition obtained in this way, It is preferable that it is 0.01-5,000 micrometers, especially 0.05-200 micrometers.

In addition, the cured product layer of the active energy ray-curable composition of the present invention thus obtained has a static water contact angle (also referred to as a water contact angle) measured by the angle between the liquid and solid surfaces of 1 μL of droplets of ion-exchanged water 1 second after contact with the liquid. ) Becomes a surface of 100 ° or more, particularly 105 ° or more. In addition, a 4 μL drop of oleic acid may be a water and oil repellent surface having a static oleic acid contact angle (also referred to as oleic acid contact angle) measured by the angle between the liquid and solid surfaces one second after the contact liquid is 60 ° or more, in particular 65 ° or more. It is desirable to have. In addition, in order to set it as said contact angle, it is preferable that the hardened | cured material layer of the fluorine-containing active-energy-ray-curable composition of this invention forms an average layer 10 nm or more in thickness with respect to the total surface area of this hardened | cured material layer. In addition, the more unreacted cationically polymerizable groups remain on the surface of the cured product layer, the more preferable. For this reason, the active energy ray curing treatment in an atmosphere where water is managed or under heating conditions, the adjustment of the amount of the photopolymerization initiator (B) adjusted, and the active energy ray Oil and the like for advancing the cancer reaction in a clean environment after irradiation can be arbitrarily performed.

As described above, the active energy ray-curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and forms a cured resin layer having excellent water / oil repellency, antifouling property, anti-fingerprint property, slip resistance, and wear resistance on the surface of the article. can do.

Moreover, in this invention, the article which has a cured film which apply | coated and hardened the active energy ray curable composition of this invention mentioned above to the surface is provided. As mentioned above, when the active energy ray curable composition of this invention is used, it becomes possible to form the cured film (cured resin layer) which has the surface characteristic excellent in the surface of a base material (article). In particular, it is useful also in providing water repellency, oil repellency, and antifouling property to the surface of a cation hardening type hard coat. As a result, contamination of human oil such as fingerprint, sebum, sweat, cosmetics, etc., hardly adhere to the machine oil, and the surface of the hard coat excellent in wiping property can be supplied to the substrate. For this reason, the active energy ray-curable composition of the present invention is used in substrates (articles) that may be contaminated by human oil, cosmetics, etc. by human contact, and inside the machine that may be contaminated with human body oil or machine oil of an operator. An antifouling coating film or a protective film on the surface of a process material film or the like can be provided.

The cured coating film (cured resin layer) formed by using the active energy ray curable composition of the present invention may be a tablet computer, a notebook computer, a mobile (communication) information terminal such as a mobile phone or a smartphone, a digital media player, an electronic book reader, or the like. Casing of the device, watch-type glasses type wearable computer; Various flat panel displays such as liquid crystal displays, plasma displays, organic electroluminescent (EL) displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays, CRTs, toner-based displays, and TV screens. Surface of display operation equipment and various optical films used in them, exterior of automobile, polished surface of piano or furniture, building stone surface such as marble, decorative building material around water such as toilet, bathroom, washroom, and protective glass for artwork display Display window, showcase, cover for photo frame, watch, glass for car window, window glass such as train, aircraft, transparent glass or transparent plastic member such as car headlight, tail lamp, etc. It is useful as a coating film and surface protection film, such as a mirror member.

Among them, in particular, various devices having a display input device for performing on-screen operation with a human finger or a palm, such as a touch panel display, for example, a tablet-type computer, a notebook, a smartphone, a mobile phone, and other portable (communication) information terminals. Smart watch, digital media player, electronic book reader, digital photo frame, game machine, digital camera, digital video camera, GPS display recording device, navigation device such as car, control panel such as car, automatic cash withdrawal device, It is useful as surface protection films, such as a cash dispenser, a vending machine, a digital signage (electronic sign), a security system terminal, a POS terminal, various controllers, such as a remote controller, and display input devices, such as a panel switch for in-vehicle devices.

Further, the cured coating film formed by the active energy ray curable composition of the present invention may include optical recording media such as magneto-optical disks and optical disks; Optical components such as spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, fresnel lenses, antireflection films, lenses for various cameras, protective filters for various lenses, optical fibers, optical couplers, etc. It is also useful as a surface protective film.

As described above, the active energy ray-curable composition of the present invention is water-repellent and oil-repellent by disposing a perfluoropolyether structure of the fluorine-containing epoxy-modified organosilicon compound (A) according to the present invention on the surface of the article of interest. Its essence is to provide excellent properties such as slipperiness, antifouling property, hard adhesion of fingerprint, fingerprint wiping resistance, abrasion resistance, low refractive index property, solvent resistance, and chemical resistance.

When using such a fluorine-containing active energy ray-curable composition of the present invention, an appropriate method of use may be selected based on known techniques for each use, depending on the combination, composition ratio, and characteristics of the compound. Such known techniques can be included in the scope of the study, including not only those for fluorine-containing compositions, but also techniques used in existing active energy ray-curable compositions.

For example, when blending and preparing the active energy ray-curable composition of the present invention, in addition to the fluorine-containing epoxy-modified organosilicon compound (A) according to the present invention, when combining various blends in the present curable composition, In the case of focusing on low refractive index characteristics and low reflection characteristics using the same, use of various types of multifunctional compounds as reactive hollow silica, hollow silica not having a reactive group, and compound (C), and when improving film strength and scratch resistance In the compound (C), various polyfunctional compounds are blended in a suitable amount, and in the case of using an epoxy group-containing compound having a low curing rate as the compound (C), by compounding an oxetane group-containing compound or a vinyl ether-containing compound A number that can be easily inferred from the knowledge of known cationically curable composition formulations, such as improving the curing rate. A.

(Example)

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited to the following Example.

Synthesis Example 1

Preparation of Compound (A-1)

In a dry nitrogen atmosphere, the following formula was added to a 100 ml three-necked flask equipped with a reflux device and a stirring device.

(Wherein Rf '' is the following group. The number of repeating units has a distribution and 5.2 is an average value.

)

)

30.0 g of fluorine-containing cyclic siloxane and 30.0 g of m-xylene hexafluoride represented by were charged and heated to 90 ° C while stirring. To this was added dropwise a mixed solution of 8.0 g of allylglycidyl ether and 0.010 g of a toluene solution (2.49 × 10 ⁻⁸ mol in terms of platinum) of a platinum / 1,3-divinyl-tetramethyldisiloxane complex over 30 minutes. And it stirred at 90 degreeC for 8 hours. In this case, the ratio of the number of terminal olefin groups which allyl glycidyl ether has with respect to one SiH group which the said fluorine-containing cyclic siloxane has is 1.02. After confirming that Si-H of the raw material was lost by ¹ H-NMR, activated carbon treatment was performed. Thereafter, the solvent and the excess allyl glycidyl ether were distilled off under reduced pressure to obtain 34.2 g of the compound (A-1) represented by the following formula.

Synthesis Example 2

Preparation of Compound (A-2)

In a dry nitrogen atmosphere, to a 2000 ml three-necked flask equipped with a reflux device and a stirring device, the following formula

CH ₂ = CH-CH ₂ -O-CH ₂ -Rf'-CH ₂ -O-CH ₂ -CH = CH ₂

Rf ': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-

(p / q = 0.9, p + q ≒ 45)

500 g of perfluoropolyethers having an α-unsaturated bond, 700 g of m-xylene hexafluoride, and 361 g of tetramethylcyclotetrasiloxane were added to both terminals indicated by, and heated to 90 ° C. while stirring. 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was added thereto, and the internal temperature was maintained at 90 ° C. or higher. The stirring was continued for hours. After confirming that the allyl group of the raw material disappeared by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was carried out to obtain 498 g of a colorless transparent liquid compound (P-1) represented by the following formula.

Rf ': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-

(p / q = 0.9, p + q ≒ 45)

60.0 g of the compound (P-1), 10.0 g of allyl glycidyl ether and 60.0 g of m-xylene hexafluoride were mixed and heated to 80 ° C. under a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups which allyl glycidyl ether has with respect to one SiH group which the said compound (P-1) has is 1.15. To this was added 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 ^-8 mol as Pt alone), and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming that Si-H of the raw material was lost by ¹ H-NMR, activated carbon treatment was performed. Thereafter, the solvent and the excess allyl glycidyl ether were distilled off under reduced pressure to obtain 66.2 g of the compound (A-2) represented by the following formula having a translucent grease shape.

Rf ': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-

(p / q = 0.9, p + q ≒ 45)

Synthesis Example 3

Preparation of Compound (A-3)

60.0 g of the compound (P-1), 10.9 g of 3-vinylcyclohexene oxide, and 60.0 g of m-xylene hexafluoride were mixed and heated to 80 ° C. under a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups which 3-vinyl cyclohexene oxide has with respect to one SiH group which the said compound (P-1) has is 1.14. To this was added 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 ^-8 mol as Pt alone), and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming that Si-H of the raw material was lost by ¹ H-NMR, activated carbon treatment was performed. Thereafter, the solvent and excess 3-vinylcyclohexene oxide were distilled off under reduced pressure to obtain 66.1 g of the compound (A-3) represented by the following formula having a translucent grease shape.

Rf ': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-

(p / q = 0.9, p + q ≒ 45)

Synthesis Example 4

Preparation of Compound (A-4)

In a dry nitrogen atmosphere, to a 2000 ml three-necked flask equipped with a reflux device and a stirring device, the following formula

CH ₂ = CH-CH ₂ -O-CH ₂ -Rf '''-CH ₂ -O-CH ₂ -CH = CH ₂

Rf ''': -CF ₂ (OCF ₂ CF ₂ ) _h' (OCF ₂ ) _{i '} OCF _2-

(h '= 6.8, i' = 5.7, h 'and i' are the average of each)

500 g of perfluoropolyethers having an α-unsaturated bond, 700 g of m-xylenehexafluoride, and 865 g of pentamethylcychloropentasiloxane were added to both ends of the terminal, and heated to 90 ° C. while stirring. . 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was added thereto, and the internal temperature was maintained at 90 ° C. or higher. The stirring was continued for hours. After confirming that the allyl group of the raw material disappeared by ¹ H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 538 g of a colorless transparent liquid compound (P-2) represented by the following formula.

Rf ''': -CF ₂ (OCF ₂ CF ₂ ) _h' (OCF ₂ ) _{i '} OCF _2-

(h '= 6.8, i' = 5.7, h 'and i' are the average of each)

100.0 g of the compound (P-2), 41.0 g of allyl glycidyl ether, and 100.0 g of m-xylene hexafluoride were mixed and heated to 80 ° C. under a nitrogen atmosphere while stirring. In this case, the ratio of the number of terminal olefin groups which allyl glycidyl ether has with respect to one SiH group which the said compound (P-2) has is 1.2. To this was added 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 ^-8 mol as Pt alone), and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming that Si-H of the raw material disappeared by ¹ H-NMR, activated carbon treatment was performed. Then, the solvent and excess allyl glycidyl ether were distilled off under reduced pressure, and 134 g of compounds (A-4) represented by a following formula which is a colorless transparent liquid were obtained.

Rf ''': -CF ₂ (OCF ₂ CF ₂ ) _h' (OCF ₂ ) _{i '} OCF _2-

(h '= 6.8, i' = 5.7, h 'and i' are the average of each)

[Examples and Comparative Examples]

(Preparation of active energy ray curable composition)

Each component was mixed by the composition of following Table 1, and the active energy ray curable composition was prepared.

B-1: Photocationic polymerization initiator CPI-200K (phosphorus anion type triarylsulfonium salt, a solvent dilution product, the San Afro Corporation make)

B-2: Photocationic polymerization initiator CPI-210S (phosphorus anion type triarylsulfonium salt, powder, a San Afro Corporation make)

B-3: Photo-thermal cationic polymerization initiator TA-100 (sulfonium salt, powder, a San Afro Corporation make)

C-1: liquid epoxy resin epot ZZ-1059 (bisphenol A, bisphenol F monomer mixture of the following formula, Shinnitetsu Sumikin Kagaku Co., Ltd.)

C-2: tetrafunctional epoxy compound of the following formula

D-1: methyl ethyl ketone

D-2: Butyl Acetate

(Formation of Curing Film)

Each composition of the compounding examples 1-14 was coated on the polycarbonate board of thickness 2mm so that it might become about 12 micrometers (wet film thickness), with a spin coater, and it dried with the hot air dryer. The dry film thickness after drying became about 5 micrometers. Thereafter, a conveyor metal halide UV irradiation device (manufactured by Panasonic Denco Co., Ltd., 80w / cm) was used, and ultraviolet rays of a predetermined amount of accumulated light were irradiated and cured in a nitrogen atmosphere under the conditions shown in Table 2 to obtain a cured film.

Moreover, each composition of the compounding examples 6-8 and 12-14 was coated on the polycarbonate plate of thickness 2mm so that it might become about 12 micrometers (wet film thickness), with a spin coater, and it dried with the hot air dryer. The dry film thickness after drying became about 5 micrometers. Thereafter, using a conveyor metal halide UV irradiation device (manufactured by Panasonic Denko Co., Ltd., 80w / cm), ultraviolet rays having a predetermined amount of accumulated light were irradiated and cured in air under the conditions shown in Table 3 to obtain a cured film.

(Assessment Methods)

[Evaluation of Water and Oil Repellency]

The contact angle (water contact angle) with respect to the water of the cured film surface obtained above, and the contact angle at 25 degreeC (oleic acid contact angle) with respect to oleic acid were measured using the contact angle meter DropMaster (made by Kyowa Chemical Co., Ltd.). The measurement was performed after 30 minutes from UV irradiation.

In addition, the water contact angle was measured by the angle which a 2 microliter droplet of ion-exchange water makes with a liquid surface and a cured film surface after 1 second from a contact liquid. In addition, the contact angle of oleic acid was measured by the angle which a liquid surface and a cured film surface make after 1 second of 4 microliters of oleic acid droplets from contact liquid.

[Magic Ink Repellency]

Oily magic (made by Zebra Corporation, bold-faced bold letters) was apply | coated to the hardened | cured material surface, and the ink repellency was evaluated by visual observation using the following index. The measurement was performed 45 minutes after UV irradiation.

A: Reject quickly.

B: Exclude.

C: No rejection at all.

[Fingerprint wipes]

Five panelists evaluated the wiping property at the time of transferring the sebum of the forehead to the hardened | cured material surface with a finger, and wiping off with Bencote (made by Asahi Kasei Co., Ltd.) by the following evaluation criteria.

Evaluation was performed between 1 hour and 2 hours after UV irradiation.

A: A fingerprint can be wiped off easily.

B: You can wipe your fingerprint.

C: I can't wipe my fingerprints.

The above evaluation results are shown in Tables 2 and 3, respectively.

Claims (10)

General formula (1)

(In formula (1), Rf is a monovalent or divalent group having a number average molecular weight of 400 to 40,000 having a fluoropolyether structure independently of each other,
When Rf is a monovalent group, the following formula

or

(Wherein j is an integer of 1 to 3, k is an integer of 0 to 200, k 'is an integer of 1 to 200, and l and m are each an integer of 1 to 100).
Displayed as
When Rf is a divalent group, the following formula

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.),

(In formula, j is an integer of 1-3 independently, h and i are each an integer of 0-200, and h + i is 2-300. Each repeating unit may be combined at random.) ,

(Wherein r is an integer of 2 to 6, k and t are each an integer of 0 to 200, provided that k + t is 2 to 200. s is an integer of 0 to 6), or

(In formula, r is an integer of 2-6, k and t are integers of 0-200, respectively, except k + t is 2-200. S is an integer of 0-6.)
Is displayed.
When Rf is a monovalent group, a 'is 1 and a is an integer of 1-6. When Rf is a divalent group, a 'is 2, a is 1, b is an integer of 1-20, a + b is an integer of 3-21.
Q ¹ is, independently of each other, a (a + b) valent group having at least (a + b) Si atoms,

(Wherein a and b are as described above, the dashed line represents a bond and each silicon atom of the unit represented in parentheses having a repeat is bonded to Rf in the formula (1), and b repeats) Each silicon atom of the unit represented in parentheses having the above bond with Q ² in the above formula (1), and the sequence of units represented in the parentheses may be random.)
Is displayed.
Q ² is a C1-C20 divalent hydrocarbon group which may include an ether bond or an ester bond independently of one another and may have a cyclic structure.
X independently of each other, the following formula (I) or (II)

(In formula (I), R <^1> is a hydrogen atom or a C1-C20 unsubstituted or substituted monovalent hydrocarbon group independently, may contain an ether bond or an ester bond, and may have a cyclic structure. )

(In formula (II), R <^2> is a hydrogen atom or a C1-C20 unsubstituted or substituted monovalent hydrocarbon group each independently.)
Is represented by.)
Fluorine-containing epoxy-modified organosilicon compound (A) represented by
It is an active energy ray curable composition containing a photoinitiator (B), Comprising: The active energy ray curable composition characterized by providing the hardened | cured material whose surface water contact angle is 100 degrees or more. The active energy ray curable composition according to claim 1, wherein in the formula (1), the structure represented by -Q ² -X is selected from the group represented by the following formulas (2) to (5).

In the above formula, f is an integer of 1 to 10, e is an integer of 0 to 5, g is an integer of 0 to 10, f + 2g + e is in the range of 1 to 20, and n is 1 to 1 It is an integer of 20. R <^2> is a hydrogen atom or a C1-C20 unsubstituted or substituted monovalent hydrocarbon group each independently.). The active energy ray curable composition according to claim 1 or 2, wherein in formula (1), Q ² is independently selected from the group represented by the following formula.
-CH ₂ CH _2- ,
-CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ OCH _2- ,
-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH _2- , or
-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2- The structure represented by -Q ² -X in claim 2 or 3, wherein in formula (1):

An active energy ray curable composition, characterized by the above-mentioned. The active energy ray curable composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (B) is a photoacid generator. The active energy ray curable composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (B) is any one of a diazonium salt, an iodonium salt, and a sulfonium salt. When the compound which has cation curability is only (A) component, 0.01-20 mass parts of (B) component are included with respect to 100 mass parts of (A) component, The compound in any one of Claims 1-6. An active energy ray curable composition. The component (C) which consists of a compound which further has one or more types of cation curability other than (A) component is contained, The sum total of (A) component and (C) component in any one of Claims 1-6. 0.01-20 mass parts of (B) component with respect to 100 mass parts, The active energy ray curable composition characterized by the above-mentioned. The compound according to claim 8, wherein the component (C) has at least one of an epoxy group, a vinyl ether group, an oxetane group, and a carbonyl group in one molecule, an aliphatic unsaturated hydrocarbon compound, a styrene derivative, a bicycloorthoester, An active energy ray curable composition, characterized in that it is a spiro orthocarbonate, a spiro ortho ester or a cationically polymerizable nitrogen-containing compound. The activity according to claim 8 or 9, wherein 0.01 to 10 parts by mass of the component (A) is contained with respect to 100 parts by mass of the component (C), and the water contact angle on the surface of the cured product after curing is 100 ° or more. Energy ray curable composition.