KR20220009347A - Fluorine-containing acryl composition, activation energy radiation-curable fluorine-containing composition and article - Google Patents

Abstract

(assignment)
A fluorinated acrylic composition capable of imparting excellent liquid repellency, antifouling properties and abrasion resistance without increasing (non-reactive) volatile organic compounds that do not have (non-reactive) groups reactive with acrylic groups as a whole of the curable composition when added to the curable composition, including this composition It provides a fluorine-containing active energy ray-curable composition, and an article having a cured product layer of the composition on the surface of a substrate.
(Solution)
(A) a fluorine-containing acrylic compound having a perfluoropolyether group, an acryl group or an α-substituted acryl group, and having a specific structure that does not contain a urethane bond in the molecule;
(B) An acrylic compound having a viscosity of 100 mPa·s or less at 25°C and containing one or two (meth)acrylic groups in one molecule
A fluorinated acrylic composition in which a volatile organic compound having no group reactive with an acryl group is not incorporated, wherein the mass ratio of component (A) and component (B) is 0.01<(A)/(B)<10.

Description

Fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition and article

The present invention relates to a fluorinated acrylic composition capable of imparting excellent liquid repellency, antifouling property and abrasion resistance by adding to an active energy ray curable composition such as ultraviolet rays or electron beam, a fluorinated active energy ray curable composition comprising the fluorinated acrylic composition, and the It relates to an article having a cured product layer of the composition on the surface of the substrate.

BACKGROUND ART Conventionally, a hard coat treatment has been widely and generally used as a means for protecting the surface of a resin molded body or the like. This forms a hard cured resin layer (hard-coat layer) on the surface of a molded object, and makes it hard to get hurt. As a material which comprises a hard-coat layer, the curable composition by active energy rays, such as a thermosetting resin and an ultraviolet-ray or electron beam curable resin, is used many.

With the expansion of the field of use of resin molded products and the flow of high added value, the demand for high functionalization of the cured resin layer (hard coat layer) is increasing, and as one of them, provision of antifouling properties to the hard coat layer is required. This is to impart properties such as water repellency and oil repellency to the surface of the hard coat layer so that it is difficult to be contaminated or can be easily removed even if it is contaminated.

As a method of imparting antifouling properties to the hard coat layer, a method of coating and/or fixing a fluorine-containing antifouling agent on the surface of the hard coat layer once formed is widely used. A fluorine-containing curable component is added to the cured resin composition before curing, and this The method of simultaneously performing formation of a hard-coat layer and provision of antifouling property by coating hardening has also been examined. For example, in Unexamined-Japanese-Patent No. 6-211945 (patent document 1), manufacture of the hard-coat layer which provided antifouling property by adding and hardening a fluoroalkyl acrylate to an acrylic curable resin composition is shown.

Moreover, the present inventors are advancing various development as a fluorine compound which can provide antifouling property to such curable resin composition, For example, Unexamined-Japanese-Patent No. 2010-53114 (patent document 2), Unexamined-Japanese-Patent No. 2010-138112. The photocurable fluorine compound shown in the publication (patent document 3), JP 2010-285501 A (patent document 4), etc. is proposed.

By having a fluoropolyether structure and a structure having a plurality of acrylic groups in one molecule, they can impart high antifouling properties to the curable resin composition. In order to improve the compatibility with the composition, it was necessary to handle it as a solution diluted with a highly volatile organic solvent. For this reason, there existed a problem that it could not mix|blend as it is with a solvent-free type hard-coat agent or a paint.

On the other hand, handling with the coating liquid diluted with the organic solvent for the coating property and film performance improvement of a hard-coat process is performed widely. However, in recent years, the movement to suppress the use of volatile organic compounds (VOCs) such as volatile organic solvents is increasing out of concerns about the effects on the environment and the human body, and high solidification and solvent-free formation are strongly demanded also for the coating liquid of the hard coat. Accordingly, also for the additive composition added to impart liquid repellency and antifouling properties to the coating liquid of the hard coat as described above, a composition that does not contain a volatile organic compound without a reactive group such as a volatile organic solvent has been demanded. .

In addition, the conventional hard coat composition containing a volatile organic compound without a reactive group such as a volatile organic solvent has a particularly large dimensional change between coating and curing. For example, it becomes especially unsuitable in uses, such as a curable composition for nanoimprints, and a curable composition for 3D printers.

The present inventors are conducting various developments as a fluorinated acrylic composition capable of imparting liquid repellency and antifouling properties to a curable resin composition without including a volatile organic compound without a reactive group such as a volatile organic solvent, for example, in Japan In Japanese Patent Application Laid-Open No. 2017-190429 (Patent Document 5), by suppressing the content of a volatile organic compound without a reactive group, when added to the curable composition, the curable composition as a whole does not have a group that reacts with an acrylic group (non-reactive) volatile organic compound A fluorinated acrylic composition capable of imparting liquid repellency and antifouling properties without increasing it is proposed.

However, in recent years, there is a tendency that the use of a hard coat containing a fluorine-containing composition for items that are easily touched by a human finger, such as a touch panel, tends to increase. Since the surface is worn out by abrasion by a person's fingers and the antifouling property is deteriorated, it does not have practically satisfactory wear resistance.

Japanese Patent Application Laid-Open No. 6-211945 Japanese Patent Laid-Open No. 2010-53114 Japanese Patent Laid-Open No. 2010-138112 Japanese Patent Laid-Open No. 2010-285501 Japanese Patent Laid-Open No. 2017-190429

The present invention has been made in view of the above circumstances. A fluorinated acrylic composition capable of imparting excellent liquid repellency, antifouling properties and abrasion resistance by adding to an active energy ray-curable composition such as ultraviolet rays or electron beams, and a fluorinated acrylic composition comprising the fluorinated acrylic composition An object of the present invention is to provide an active energy ray-curable composition and an article having a cured product layer of the composition on the surface of a substrate.

As a result of repeated studies of the present inventors to achieve the above object,

(A) a fluorinated acrylic compound represented by the following general formula (1)

[In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Z ¹ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or two or more selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may contain a cyclic structure in the middle, provided that the structure It does not contain a urethane bond in it. Q ¹ is independently an (a+1) valent coupling group containing at least (a+1) silicon atoms, may form a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom, It may exist, however, it does not contain a urethane bond in structure. Z ² is independently the formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l are in the range where the molecular weight ^{of Z 2 is 58 to 748,} Each independently represents an integer from 0 to 10, i+j+k+l=1 to 10. o is an integer from 2 to 10) is a divalent alkylene ether group. X is independently a hydrogen atom, or an acryl group which may contain at least one selected from an oxygen atom and a nitrogen atom, or a monovalent organic group containing an α-substituted acryl group, and is an average of at least one acryl group per molecule It contains a monovalent organic group containing a group or an α-substituted acryl group, provided that it does not contain a urethane bond in its structure. a is independently an integer from 1 to 10; Y is a fluorine atom or _a monovalent group represented by ^{-Z 1} -Q ¹ -[Z ² -X] a . ^{Z 1} in Formula (1) ^{and a Z 2} bounded by [ ] are each bonded to a silicon atom in the ^{Q 1 structure], and}

(B) An acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acryl groups in one molecule

contains as an essential component, the mass ratio of component (A) and component (B) is within the range of 0.01 < (A) / (B) < 10, and does not contain a volatile organic compound having no group reactive with an acryl group The non-fluorinated acrylic composition can be added to the active energy ray-curable composition without increasing the content of the volatile organic compound that does not have a group reactive with the acrylic group, has good compatibility with the active energy ray-curable composition, and has good liquid repellency , found that a fluorine-containing active energy ray-curable composition that has antifouling properties, suppresses the content of volatile organic compounds, and exhibits high abrasion resistance can be obtained, leading to the achievement of the present invention.

Accordingly, the present invention provides the following fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition, and article.

[One]

(A) a fluorinated acrylic compound represented by the following general formula (1)

[In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Z ¹ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or two or more selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may contain a cyclic structure in the middle, provided that the structure It does not contain a urethane bond in it. Q ¹ is independently an (a+1) valent coupling group containing at least (a+1) silicon atoms, may form a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom, It may exist, however, it does not contain a urethane bond in structure. Z ² is independently the formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l are in the range where the molecular weight ^{of Z 2 is 58 to 748,} Each independently represents an integer from 0 to 10, i+j+k+l=1 to 10. o is an integer from 2 to 10) is a divalent alkylene ether group. X is independently a hydrogen atom, or an acryl group which may contain at least one selected from an oxygen atom and a nitrogen atom, or a monovalent organic group containing an α-substituted acryl group, and is an average of at least one acryl group per molecule It contains a monovalent organic group containing a group or an α-substituted acryl group, provided that it does not contain a urethane bond in its structure. a is independently an integer from 1 to 10; Y is a fluorine atom or _a monovalent group represented by ^{-Z 1} -Q ¹ -[Z ² -X] a . ^{Z 1} in Formula (1) ^{and a Z 2} bounded by [ ] are each bonded to a silicon atom in the ^{Q 1 structure], and}

(B) An acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acryl groups in one molecule

contains as an essential component, the mass ratio of component (A) and component (B) is within the range of 0.01 < (A) / (B) < 10, and does not contain a volatile organic compound having no group reactive with an acryl group A fluorine-containing acrylic composition that is not.

[2]

In general formula (1), Rf ¹ is the following formula

(Wherein, b is an integer from 1 to 3 independently for each unit. c, d, e, f, g, and h are each an integer from 0 to 200, and c+d+e+f+g+h=3 ~ 200. Each of these units may be linear or branched, and each repeating unit indicated in parentheses marked with c, d, e, f, g, h may be randomly bonded.)

The fluorinated acrylic composition according to [1], which is a divalent perfluoropolyether group represented by

[3]

In the general formula (1), Rf ¹ is the following structural formula

(However, the arrangement of repeating units enclosed in ( ) is random, p is an integer from 1 to 199, q is an integer from 1 to 170, and p+q is from 6 to 200. s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120, s+t+u is an integer from 3 to 126, v is an integer from 4 to 120)

The fluorinated acrylic composition according to [1] or [2], which is any of the divalent perfluoropolyether groups represented by

[4]

In the general formula (1), Z ¹ is the following formula

The fluorinated acrylic composition according to any one of [1] to [3], wherein the structure is represented by

[5]

In the general formula (1), Q ¹ is the following formula

(Wherein, a' is an integer from 2 to 10.)

The fluorinated acrylic composition according to any one of [1] to [4], wherein (a'+1) is a linking group represented by

[6]

In the general formula (1), X is the following formula

(Wherein, R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and Z ³ is a single bond or 2 that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms. It is a valent or trivalent hydrocarbon group, and n is 1 or 2.)

The fluorinated acrylic composition according to any one of [1] to [5], which is a structure represented by

[7]

The fluorinated acrylic composition according to any one of [1] to [6], wherein the component (A) is a fluorinated acrylic compound represented by the following general formula (2) or (3).

(Wherein, Rf ¹ , Z ¹ , Z ² , Q ¹ , and a are as described above. R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[8]

The fluorinated acrylic composition according to any one of [1] to [7], wherein the component (A) is a fluorinated acrylic compound represented by the following general formula (4) or (5).

[wherein, Rf ¹ , Z ¹ , Q ¹ , and a are as described above. Z ⁴ is the following formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and j', k', and l' are each independently an integer of 0 to 4, and j'+k '+l' = 1 to 10, and o is an integer from 2 to 10.) is a divalent alkylene ether group.]

[9]

The fluorinated acrylic composition according to any one of [1] to [8], wherein the component (A) is one or more selected from the group consisting of fluorinated acrylic compounds represented by the following formula.

[wherein, Rf ² is -CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF ₂ -, p is an integer from 1 to 199, q is an integer from 1 to 170, p+ q is 6~200, and the arrangement of repeating units enclosed in ( ) is random. v is an integer from 4 to 120; R ² is independently a hydrogen atom or a methyl group, and R ³ is independently a hydrogen atom, a methyl group or a phenyl group. Z ⁴ is the following formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and j', k', and l' are each independently an integer of 0 to 4, and j'+k '+l' = 1 to 10, and o is an integer from 2 to 10.)

is a divalent alkylene ether group represented by , and m is an integer of 2 to 5.]

[10]

(B) As a part or all of a component, following General formula (6)

(Wherein, R ⁴ is a urethane bond, an ether bond, an isocyanate group, or contains a hydroxyl group and a monovalent hydrocarbon group of 1 to 20 carbon atoms group which may. R ⁵ represents a hydrogen atom, a methyl group, a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms It is a roalkyl group.)

The fluorinated acrylic composition according to any one of [1] to [9], comprising an acrylic compound represented by

[11]

(B) As a part or all of a component, following General formula (7)

(Wherein, R ⁶ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group. R ⁷ is each independently a hydrogen atom, a methyl group, a fluorine atom, or a carbon number 1 to 6 is a fluoroalkyl group.)

The fluorinated acrylic composition according to any one of [1] to [10], comprising an acrylic compound represented by

[12]

The fluorine-containing acrylic composition according to any one of [1] to [11], wherein the acrylic compound as component (B) does not contain an alkyl group substituted with a fluorine atom.

[13]

A fluorinated active energy ray-curable composition comprising 0.005 to 40 parts by mass of the fluorinated acrylic composition according to any one of [1] to [12] with respect to 100 parts by mass of the active energy ray-curable composition (E).

[14]

The active energy ray-curable composition (E),

(Ea) Acrylic compound: 100 parts by mass;

(Eb) Photoinitiator: 0.1-15 mass parts

The fluorine-containing active energy ray-curable composition according to [13], comprising:

[15]

The fluorine-containing active energy ray-curable composition according to [13] or [14], which provides a cured product having a water contact angle of 90° or more at 25°C and 40% relative humidity.

[16]

An article having on its surface a layer of a cured product of the fluorine-containing active energy ray-curable composition according to any one of [13] to [15].

According to the fluorinated acrylic composition of the present invention, the active energy ray-curable composition does not increase the content of a volatile organic compound having no group reactive with an acryl group (especially a non-reactive volatile organic compound that does not contain a (meth)acryl group in the molecule). It is possible to provide a fluorine-containing active energy ray-curable composition capable of imparting liquid repellency and antifouling properties by adding to the composition. Further, since the fluorinated acrylic compound contained in the fluorinated acrylic composition of the present invention does not contain a urethane bond in its molecule, the antifouling property is hardly lowered even by abrasion. Therefore, this fluorinated acrylic composition is useful as an antifouling additive for imparting liquid repellency, antifouling properties and abrasion resistance to ultraviolet curable or thermosetting hard coat agents, paints, resins, antireflection coating compositions, and the like.

The fluorinated acrylic composition of the present invention comprises:

(A) a fluorinated acrylic compound represented by the following general formula (1)

[In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Z ¹ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or two or more selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may contain a cyclic structure in the middle, provided that the structure It does not contain a urethane bond in it. Q ¹ is independently an (a+1) valent coupling group containing at least (a+1) silicon atoms, may form a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom, It may exist, however, it does not contain a urethane bond in structure. Z ² is independently the formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l are in the range where the molecular weight ^{of Z 2 is 58 to 748,} Each independently represents an integer from 0 to 10, i+j+k+l=1 to 10. o is an integer from 2 to 10) is a divalent alkylene ether group. X is independently a hydrogen atom, or an acryl group which may contain at least one selected from an oxygen atom and a nitrogen atom, or a monovalent organic group containing an α-substituted acryl group, and is an average of at least one acryl group per molecule It contains a monovalent organic group containing a group or an α-substituted acryl group, provided that it does not contain a urethane bond in its structure. a is independently an integer from 1 to 10; Y is a fluorine atom or _a monovalent group represented by ^{-Z 1} -Q ¹ -[Z ² -X] a . ^{Z 1} in Formula (1) ^{and a Z 2} bounded by [ ] are each bonded to a silicon atom in the ^{Q 1 structure], and}

(B) An acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acryl groups in one molecule

contains as an essential component, the mass ratio of component (A) and component (B) is within the range of 0.01 < (A) / (B) < 10, and does not contain a volatile organic compound having no group reactive with an acryl group characterized as not being.

In the fluorinated acrylic composition of the present invention, the fluorinated acrylic compound of component (A) has a perfluoropolyether group as a water and oil repellency group, an acryl group or an α-substituted acryl group, and does not contain a urethane bond in the molecule When added to the active energy ray-curable composition, excellent liquid repellency, antifouling properties, and abrasion resistance can be imparted.

The fluorinated acrylic compound of component (A), which is the first essential component in the fluorinated acrylic composition of the present invention, is represented by the following general formula (1). In the present invention, "acrylic compound" is a generic term for compounds having an acrylic group or an α-substituted acrylic group, and includes compounds in which two or more acrylic groups or α-substituted acrylic groups are introduced into the side chains or terminals of various polymers by any method. . Moreover, in this invention, "(meth)acrylate" shows one or both of an acrylate and a methacrylate.

In the formula (1), Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group ^{having 1 to 6 carbon atoms and an oxygen atom, Rf 1} is a perfluoropolyether group having 1 to 6 carbon atoms, In particular, those having the following perfluorooxyalkylene structures having 1 to 3 carbon atoms as the main repeating unit are suitable.

Any of these structures may be a homopolymer or a random or block polymer comprising a plurality of structures.

^{As an example of Rf 1} which has such a structure, the following structures are mentioned, for example.

(Wherein, b is an integer from 1 to 3 independently for each unit. c, d, e, f, g, and h are each an integer from 0 to 200, and c+d+e+f+g+h=3 ~ 200. Each of these units may be linear or branched, and each repeating unit indicated in parentheses marked with c, d, e, f, g, h may be randomly bonded.)

In the above formula, b is an integer of 1 to 3 each independently for each unit.

In addition, c, d, e, f, g, and h are each an integer of 0 to 200, preferably c is an integer of 5 to 100, d is an integer of 5 to 100, e is an integer of 0 to 100, and f is 0 An integer of ~100, g is an integer of 0-100, h is an integer of 0-100, c+d+e+f+g+h=3-200, preferably 10-105, more preferably c+d is an integer from 10 to 105, particularly from 15 to 60, e=f=g=h=0. When c+d+e+f+g+h is smaller than the above upper limit, adhesiveness and curability are good, and when c+d+e+f+g+h is larger than the above lower limit, it is preferable because the characteristics of the fluoropolyether group can be sufficiently exhibited.

In the above formula, each unit may be linear or branched. Moreover, each repeating unit shown in the parenthesis to which c, d, e, f, g, and h is attached may be couple|bonded at random.

^{Suitable examples of Rf 1} having such a structure include, for example, the following structures.

(Wherein, the arrangement of the repeating units enclosed in ( ) is random, p is an integer from 1 to 199, preferably an integer from 1 to 99, q is an integer from 1 to 170, preferably an integer from 1 to 99, p+q is 6 to 200, preferably an integer of 10 to 100.)

(Wherein, the arrangement of the repeating units enclosed in ( ) is random, s is an integer from 0 to 6, t is an integer from 1 to 100, u is an integer from 1 to 100, t+u is from 2 to 120, preferably is an integer from 4 to 100, s+t+u is an integer from 3 to 126, preferably from 4 to 100. v is an integer from 4 to 120, preferably from 4 to 80.)

As for ^{the molecular weight of Rf 1} , the number average molecular weight of the corresponding structural moiety may be in the range of 400 to 20,000, preferably 800 to 10,000, respectively, and the molecular weight distribution (or polymerization degree distribution) is not particularly limited. In addition, in the present invention, the molecular weight (or the degree of polymerization or the number of repeating units) can be obtained as a number average molecular weight (or number average polymerization degree) in terms of polystyrene by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. However, it is preferably a number average molecular weight (or number average degree of polymerization) calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluorinated acrylic compound based on ¹ H-NMR analysis and ^{19 F-NMR analysis (hereinafter referred to as the number average degree of polymerization).} , same).

In said formula (1), Z<^1> is a C1-C20 divalent hydrocarbon group which may contain 1 type(s) or 2 or more types independently selected from an oxygen atom, a nitrogen atom, and a silicon atom, and a cyclic structure in the middle may be included, provided that it does not contain a urethane bond in the structure. The following are mentioned as a especially preferable structure of ^Z<1>. In addition, in the following structure, it is preferable that the ^{left hand bond with Rf 1} and the right hand bond with Q ^{1 .}

What is shown below as Z<^{1> is more preferable.}

In said Formula (1), a is independently an integer of 1-10, Preferably it is an integer of 2-8.

In the formula (1), Q ¹ is independently an (a+1) valent coupling group containing at least (a+1) silicon atoms, and may form a cyclic structure, and is selected from an oxygen atom, a nitrogen atom, and a fluorine atom. It may contain at least 1 sort(s) chosen, provided that it does not contain a urethane bond in a structure. As a preferable thing of such Q ¹ , each of (a+1) a siloxane structure having (a+1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof (a+1) ) is a linking group. As an especially preferable structure, the following structure is specifically shown.

However, in the following formula, a is the same as a in the formula (1), independently an integer of 1 to 10, preferably an integer of 2 to 8. a' is an integer of 2-10, Preferably it is an integer of 2-7. r is an integer of 1-5, Preferably it is an integer of 3-5. The arrangement of each unit is random, and (a+1) and (a'+1) bonds (silicon atoms) of each unit are a Z ² and Z ^{1 bound by [ ] in the above formula (1).} combine with any one group of

Here, T is a (a+1) valent coupling group, for example, the following are illustrated.

^{Among these, Q 1} in the formula (1) is

(Wherein, a' is the same as described above.)

A (a'+1) valent linking group represented by

In the formula (1), Z ² is independently the following formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l have ^{a molecular weight of Z 2} of 58 to 748, preferably 72 to In the range set to 300, each independently an integer of 0 to 10 (that is, the sum of i, j, k, and l is 1 to 10), preferably i is an integer of 0 to 5, j is 0 to An integer of 5, k is an integer of 0-5, l is an integer of 0-5, and i+j+k+l=1-10. o is an integer of 2-10, preferably an integer of 2-8 is a divalent alkylene ether group represented by Further, in the above structure, ^{it is preferable that the left hand bond is Q 1} and the right hand bond is X.

As Z ² as the preferred structures include the following.

Here, k1 is an integer from 0 to 10, j1 is an integer from 0 to 10, i1 is an integer from 0 to 10, and Z ² may have a molecular weight of 86 to 330. The arrangement of the repeating units is random regardless of the type. In addition, each repeating unit may be a mixture of structural isomers instead of a single unit. If the molecular weight of Z ² less than 58 (B) becomes difficult to mix with an acrylic compound of the component, when it exceeds 748 becomes insufficient antifouling capability is also given of the fluorine-acryl compound.

As a structure especially preferable as Z<^2> , the following are mentioned, Among these, a thing whose k1 is 1-4 and j1 is 1-4 is suitable.

In the formula (1), X is independently a hydrogen atom, or an acryl group which may contain at least one selected from an oxygen atom and a nitrogen atom, or a monovalent organic group containing an α-substituted acryl group, and one molecule It contains, on average, at least one monovalent organic group containing the above-mentioned acryl group or an α-substituted acryl group, provided that it does not contain a urethane bond in the structure.

As X, a structure represented by the following formula is preferable.

(Wherein, R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and Z ³ is a single bond or a C1-C18 ether bond and/or an ester bond. It is a divalent or trivalent hydrocarbon group, and n is 1 or 2.)

Here, R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, preferably a hydrogen atom and a methyl group.

Moreover, here, n is 1 or 2, Preferably it is 1.

Here, Z ³ is a single bond or a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms, which may contain an ether bond and/or an ester bond. Preferably, it is a single bond or the following structure.

As X, a group represented by the following formula is preferable.

(Wherein, R ⁸ is a hydrogen atom or a methyl group, and Z' is a single bond, a methylene group, an ethylene group, or a propylene group.)

As the fluorine-containing acrylic compound represented by the formula (1), those represented by the following general formula (2) or (3) are preferable.

(Wherein, Rf ¹ , Z ¹ , Z ² , Q ¹ , R ¹ , and a are as described above.)

As the fluorine-containing acrylic compound represented by the formula (1), those represented by the following general formula (4) or (5) are more preferable.

[wherein, Rf ¹ , Z ¹ , Q ¹ , and a are as described above. Z ⁴ is the following formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and j', k', and l' are each independently an integer of 0 to 4, and j'+k '+l' = 1 to 10, and o is an integer from 2 to 10.) is a divalent alkylene ether group.]

As the fluorine-containing acrylic compound represented by the formula (1), more specifically, those shown below can be exemplified.

(Wherein, Rf ² is -CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF ₂ -, the arrangement of the repeating units enclosed in ( ) is random, and R ² is independently hydrogen atom or a methyl group, and R ³ is independently a hydrogen atom, a methyl group, or a phenyl group. m is an integer of 2 to 5. p, q, p+q, Z ⁴ , and v are as described above.)

Among these, those shown below are particularly preferable.

(Wherein, Rf ² , m, R ² , R ³ , Z ⁴ , and v are as described above.)

The fluorinated acrylic compound represented by the general formula (1) is not particularly limited in its synthesis method. For example, as one of the embodiments of the fluorinated acrylic compound represented by the general formula (2) or (3), first, The following general formula (8) or (9)

(Wherein, Rf ¹ , Z ¹ , Q ¹ , and a are as described above, and a number of hydrogen atoms (H) bounded by [ ] in Formulas (8) and (9) are each Q ¹ structure It is bonded to the silicon atom in it.)

A fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (10)

(Wherein, R ¹ , i, j, k, and l are as described above. w is an integer of 0 to 8.)

A terminal aliphatic unsaturated group having (adjacent to) an alkylene ether group represented by It can be obtained by carrying out a hydrosilylation addition reaction of the compound containing.

Here, as a fluoropolyether compound which has a polyfunctional Si-H group represented by said Formula (8), (9), what is shown below can be illustrated.

(Wherein, Rf ² and v are the same as above.)

In addition, a terminal aliphatic unsaturated group having (adjacent to) an alkylene ether group represented by the formula (10) (for example, an alkyl group containing an aliphatic unsaturated double bond such as an alkenyl group at the terminal, that is, represented by _{CH 2 =CH-} The following can be illustrated as a compound containing the alkyl group which the terminal was blocked with the external olefin (vinyl group) used, or this external olefin (vinyl group), and an acryl group or an alpha-substituted acryl group.

(wherein k2 is an integer from 0 to 10, j2 is an integer from 0 to 10, i2 is an integer from 0 to 10, i2+j2+k2=1 to 16, and CH ₂ =CH-C in formula (10) _{The molecular weight of the moiety corresponding to w} H _2w -(OC ₄ H ₈ ) _i (OC ₃ H ₆ ) _j (OC ₂ H ₄ ) _k (OCH ₂ ) _l - should be 57 to 747. The arrangement of repeating units is It is random regardless of the type, and each repeating unit may be a mixture of structural isomers rather than a single unit.)

Among them, the following ones are particularly suitable.

(Wherein, k3 is an integer from 1 to 4, and j3 is an integer from 1 to 4.)

Conventionally, when an acryl group or an α-substituted acryl group is introduced into a fluorinated compound by a hydrosilylation addition reaction, allyl methacrylate has been mainly used, but the allyl group (terminal aliphatic unsaturated group) in allyl methacrylate is hydrosilyl. Since the reactivity in the chemical addition reaction is low, the hydrosilylation addition reaction proceeds not only with the target allyl group (terminal unsaturated group) as a reaction site but also with the methacryl group as a side reaction, it is unsuitable. In the present invention, by using a compound containing a terminal aliphatic unsaturated group having (adjacent to) an alkylene ether group, and an acryl group or an α-substituted acryl group, the reactivity of the terminal aliphatic unsaturated group is sufficiently ensured. The progress of the hydrosilyl addition of the α-substituted acryl group is effectively suppressed.

A fluoropolyether compound having a polyfunctional Si-H group represented by the formulas (8) and (9), a terminal aliphatic unsaturated group represented by the formula (10), and a compound containing an acryl group or an α-substituted acryl group , these are mixed and stirred, and in the presence of a platinum group metal-based addition reaction catalyst, the reaction is preferably performed at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 72 hours, particularly 5 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without progressing sufficiently. If the reaction temperature is too high, the reaction becomes impossible to control due to the temperature rise due to the reaction heat of hydrosilylation, resulting in burrs and decomposition of raw materials. sometimes it happens

In this case, a fluoropolyether compound having a polyfunctional Si-H group represented by formulas (8) and (9), a terminal aliphatic unsaturated group represented by formula (10), and an acryl group or an α-substituted acryl group containing The introduction ratio of the compound is the terminal aliphatic represented by the formula (10) with respect to the total number of moles of H bound with [ ] of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9). It is preferable to react by using 0.8 to 5 moles, particularly 1 to 2 moles of unsaturated groups and unsaturated groups of the compound containing an acryl group or an α-substituted acryl group. When the compound containing the terminal aliphatic unsaturated group represented by the formula (10) and the acrylic group or the α-substituted acryl group is too small, the fluoropoly having polyfunctional Si-H groups represented by the formulas (8) and (9) In the ether compound, many Si-H groups remain|survive, and the possibility that the target effect cannot be acquired arises. When the amount exceeds this amount, the uniformity of the reaction solution decreases, the reaction rate becomes unstable, and the compound containing the terminal aliphatic unsaturated group represented by the formula (10) and the acryl group or the α-substituted acryl group is removed after the reaction. It becomes necessary to make conditions such as heating, depressurization, and extraction as severe as the amount of excess unreacted components increases.

As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium may be used. Among these, compounds containing platinum are preferable, hexachloroplatinum (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde /octanol complex, a complex of chloroplatinic acid and olefin, aldehyde, vinylsiloxane or acetylene alcohol, or platinum supported on activated carbon can be used.

The amount of the addition reaction catalyst is preferably 0.1 to 5,000 ppm by mass, more preferably 0.1 to 5,000 ppm by mass of the metal contained relative to the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (8) or (9). is 0.1 to 1,000 mass ppm.

Although the above-mentioned addition reaction can be performed even if a solvent does not exist, you may dilute with a solvent as needed. In this case, as the diluting solvent, widely used organic solvents such as toluene, xylene, isooctane and the like can be used. As such an organic solvent, a fluorinated acrylic compound represented by Formula (2) or (3) produced after the reaction has a boiling point equal to or higher than the target reaction temperature, does not inhibit the reaction, and is soluble at the reaction temperature. desirable. For example, fluorine-modified aromatic hydrocarbon-based solvents such as m-xylenehexafluoride and benzotrifluoride, and partially fluorine-modified solvents such as fluorine-modified ether-based solvents such as methylperfluorobutyl ether are preferable, and particularly m -Xylenehexafluoride is preferable.

When using a solvent, the usage-amount becomes like this with respect to 100 mass parts of fluoropolyether compounds which have a polyfunctional Si-H group represented by Formula (8) or (9), Preferably it is 5-2,000 mass parts, More preferably It is usually 50 to 500 parts by mass. When it is less than this, the effect of the dilution by a solvent is light, and when more, the dilution degree becomes high too much, and the fall of the reaction rate may be caused.

After completion of the reaction, the compound or diluent solvent containing the unreacted terminal aliphatic unsaturated group represented by the formula (10) and an acryl group or an α-substituted acryl group is removed by a known method such as vacuum distillation, extraction and adsorption, The fluorinated acrylic compound represented by Formula (2) or (3) can be obtained.

The fluorinated acrylic compound represented by the general formula (1) obtained by the above reaction is used by performing purification and isolation operations such as concentration, column purification, distillation, and extraction.

The fluorinated acrylic compound thus obtained does not contain a volatile organic compound (volatile organic solvent). In addition, (A) fluorine-containing acrylic compound may be used individually by 1 type, or may use 2 or more types together.

The second essential component in the fluorinated acrylic composition of the present invention is (B) an acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acryl groups in one molecule. (B) The acrylic compound of component may contain oxygen atoms other than an acrylic structure, and a nitrogen atom, and may contain an ether bond, a urethane bond, an isocyanate group, and a hydroxyl group specifically.

(B) component is 100 mPa*s or less in viscosity in 25 degreeC from solubility with (A) component, Preferably it is 0.4-20 mPa*s. When the viscosity in 25 degreeC exceeds 100 mPa*s, it will become difficult to mix with (A) component, and it is inferior to handling property. In the present invention, the viscosity can be measured with a rotational viscometer (eg, BL type, GH type, BS type, cone plate type, rheometer, etc.) (hereinafter the same).

As a preferable example of the compound which has one (meth)acryl group in a molecule|numerator among such (B) component, what is specifically represented by the following general formula (6) is shown.

(Wherein, R ⁴ is a urethane bond, an ether bond, an isocyanate group, or contains a hydroxyl group and a monovalent hydrocarbon group of 1 to 20 carbon atoms group which may. R ⁵ represents a hydrogen atom, a methyl group, a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms It is a roalkyl group.)

In the formula (6), R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. , it is preferably an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, and these may be branched or cyclic, and aliphatic unsaturated (double ) a bond, a urethane bond, an ether bond, an isocyanate group, and a hydroxyl group may be included. Specifically as R ⁴ , for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethyl-hexyl group, an isodecyl group, a tridecyl group, an iso Stearyl group, phenyl group, benzyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, furfuryl group, tetrahydrofurfuryl group, tetrahydropyranyl group, 2-(2-ethoxyethoxy)ethyl group, -CH ₂ CH ₂ -OH, -CH ₂ CH(CH ₃ )-OH, -CH ₂ CH ₂ CH ₂ -OH, -CH ₂ CH ₂ CH ₂ CH ₂ -OH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -OH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -OH, 4-hydroxycyclohexyl group, -CH ₂ CH ₂ -NCO, and the like.

R ⁵ is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, such as a trifluoromethyl group, trifluoropropyl group, or nonafluorobutyl group, in particular, a hydrogen atom, a methyl group, a fluorine atom; A trifluoromethyl group is preferred.

As such a compound, more specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) ) acrylate, n-octyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isostearyl (meth) acrylate, 2 -(2-ethoxyethoxy)ethyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate , tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, neopentyl glycol-(meth)acrylic acid-benzoic acid ester, and the like.

In addition, compounds not corresponding to formula (6), for example, methoxy polyethylene, such as acrylate compounds having a repeating unit structure such as ethylene oxide, propylene oxide, tetramethylene oxide, and lactone, and having various alkoxy termini Glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, nonylphenol EO adduct acrylate, etc. (meth) acrylic compound commercially available under the name of 25 ° C. It can be used if the viscosity in is 100 mPa*s or less.

Moreover, as a preferable example of the compound which has two (meth)acryl groups in a molecule|numerator among (B)component, what is specifically represented by the following general formula (7) is shown.

(Wherein, R ⁶ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group. R ⁷ is each independently a hydrogen atom, a methyl group, a fluorine atom, or a carbon number 1 to 6 is a fluoroalkyl group.)

In said formula (7), R<^6> is a C1-C20 divalent hydrocarbon group which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group, C1-C20, Preferably it is a C1-C20 alkyl. It is preferable that they are a lene group, a C6-C20, preferably 6-10 arylene group, or a C7-20, preferably 7-10 aralkylene group, These may be branched or may form a cyclic|annular form, and aliphatic unsaturated group A (double) bond, a urethane bond, an ether bond, an isocyanate group, and a hydroxyl group may be included. Specifically as R ⁶ , for example, a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a hexylene group (hexamethylene group), cyclo Hexylene group, octamethylene group, nonamethylene group, decamethylene group, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -C ₃ H ₆ -OC ₃ H ₆ -, phenylene group, dicyclopentanylene group, Dicyclopentenylene group, furfurylene group, tetrahydrofurfurylene group, tetrahydropyranylene group, etc. are mentioned.

R ⁷ is each independently a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a trifluoropropyl group, or a fluoroalkyl group having 1 to 6 carbon atoms, such as a nonafluorobutyl group, in particular a hydrogen atom, a methyl group, A fluorine atom and a trifluoromethyl group are preferable.

As such a compound, more specifically, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth) Acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, nonanediol di (meth) acrylate, 1,10-decanediol di(meth)acrylate, and the like.

(B) As an acrylic compound of component, you may use the thing containing the alkyl group substituted by the fluorine atom. However, the acrylic compound containing an alkyl group substituted with a fluorine atom has a strong concern about environmental impact compared to the acrylic compound which does not contain a fluorine atom. From the viewpoint of VOC emission regulation, as the acrylic compound of component (B), it is preferable that the content of the acrylic compound containing an alkyl group substituted with a fluorine atom is small, and especially those that do not contain an acrylic compound containing an alkyl group substituted with a fluorine atom desirable.

(B) A component may be single, or the mixture of the some compound which fits the said definition may be sufficient, and in the case of a mixture, what is necessary is just to calculate the sum total of content of the compound corresponding to (B) component as content of (B) component. (B) Although the compound applicable to component can be synthesize|combined by a well-known method as needed, various things are marketed from reagent manufacturers etc., This can also be used as it is.

In the fluorine-containing acrylic composition according to the first embodiment of the present invention, the components (A) and (B) are essential components, and the mass ratio of the component (A) to the component (B) is 0.01<(A)/(B) <10, preferably 0.015≤(A)/(B)≤8, more preferably 0.02≤(A)/(B)≤5.

As another embodiment of the present invention, this fluorine-containing acrylic composition is mixed with an active energy ray-curable composition (E) to be described later to obtain a fluorinated active energy ray-curable composition, which, when coated and cured, exhibits liquid repellency on a substrate , antifouling properties can be provided, but the liquid repellency and antifouling properties are expressed by the presence of the component (A) dispersed in the component of the active energy ray-curable composition (E) on the surface of the cured material layer. For this reason, when the said mass ratio (A)/(B) is 0.01 or less, content of (A) component in a fluorine-containing acrylic composition becomes small too much, and finally expression of liquid repellency and antifouling property becomes difficult. On the other hand, when the said mass ratio (A)/(B) becomes 10 or more, workability|operativity falls by the height of the viscosity of (A) component, and also compatibility and miscibility with (E) component fall. .

The viscosity at 25°C of the fluorinated acrylic composition when (A)/(B) is within the above range is preferably 0.1 to 10,000 mPa·s, more preferably 0.5 to 5,000 mPa·s, More preferably, it is 1-1,000 mPa*s. When it has such a viscosity, a curable composition with favorable handling property is obtained.

The fluorine-containing acrylic composition of the present invention does not contain a volatile organic compound (especially, a non-reactive volatile organic compound (or volatile organic solvent) that does not contain a (meth)acrylic group in the molecule) that does not have a group that reacts with an acrylic group. (that is, a solvent-free fluorinated acrylic composition).

The fluorinated acrylic composition of the present invention can be added to an active energy ray-curable composition (E) described later to form a fluorinated active energy ray-curable composition.

The amount of the fluorinated acrylic composition to be added is 0.005 to 40 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the active energy ray-curable composition (E) to be described later. If the compounding amount of this compound is less than this, the expected liquid repellency and antifouling properties cannot be exhibited because this compound cannot be sufficiently disposed on the surface when the cured product is formed. The influence of the fluorine-containing acrylic compound becomes too large, and the properties of the cured product of the original active energy ray-curable composition are lost.

The active energy ray-curable composition (E) is not particularly limited as long as a cured product is provided by irradiation with active energy rays such as ultraviolet rays or electron beams. In particular, those containing an acrylic compound (Ea) and a photopolymerization initiator (Eb) desirable.

As the acrylic compound (Ea), it can be used regardless of monofunctionality or polyfunctionality. For example, although the monofunctional and bifunctional acrylic compounds which are the above-mentioned (B) component can also be used, it is preferable that the non-fluorinated acrylic compound which has two or more acryl groups in 1 molecule especially as (Ea) component is included.

As such a non-fluorinated acrylic compound, any one having two or more acrylic groups or α-substituted acrylic groups per molecule is sufficient, for example, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate , Ethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaeryth Ritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl; Glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , sorbitol hexa (meth) acrylate 2-6 functional (meth) acrylic compounds, these (meth) acrylic compounds ethylene oxide, propylene oxide, epichlorhydrin, fatty acid, alkyl modified product, epoxy resin Epoxy acrylates obtained by adding acrylic acid to the acrylic acid ester, and those containing a copolymer in which a (meth)acryloyl group is introduced into the side chain of the acrylic acid ester copolymer are preferably mentioned.

In addition, urethane acrylates, those obtained by reacting (meth)acrylate having a hydroxyl group with polyisocyanate, those obtained by reacting (meth)acrylate having a hydroxyl group with polyester of polyisocyanate and terminal diol, those obtained by reacting polyol with excess The thing obtained by making the polyisocyanate obtained by making diisocyanate react with the (meth)acrylate which has a hydroxyl group react, etc. can also be used. Among them, (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate; Hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylene bis (4-cyclohexyl isocyanate), 2-methyl Urethane acrylates in which a polyisocyanate selected from -1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate is reacted, etc. are suitably mentioned.

In addition, 3 in 1 molecule obtained by reacting a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having a urethane bond, or this polyfunctional acrylic compound, and an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group A mixture of at least two types of acrylic compounds including those made of polyfunctional urethane acrylates having two or more acrylic groups or α-substituted acrylic groups may be used.

In this case, as the polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having a urethane bond, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Sorbitol hexa(meth)acrylate and the compound which modified|denatured these with ethylene oxide or propylene oxide are mentioned.

In addition, as polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group, hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate And trimethylolpropanedi (trimethylolpropanedi()) meth) acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylol propane tri ( Meth) acrylate, dipentaerythritol penta (meth) acrylate and ethylene oxide and propylene oxide modified products thereof, aliphatic polyols, polyacrylates having a hydroxyl group in the side chain, and 2-isocyanato What made to react with the acrylic compound which has isocyanate groups, such as ethyl (meth)acrylate and 1, 1- (bisacryloyloxymethyl) ethyl isocyanate, can be shown.

Moreover, as (Ea) component, not only the liquid component, but what modified the surface of the fine particle-form high molecular weight body or the surface of inorganic filler microparticles|fine-particles may be included.

Although the above (Ea) component can be used individually by 1 type, in order to improve coatability and the characteristic of a film after hardening, it can also mix|blend and use the corresponding some compound.

Moreover, it can be set as the curable composition which improved sclerosis|hardenability at the time of using an ultraviolet-ray as an active energy ray by containing a photoinitiator as (Eb) component.

Although the photoinitiator of (Eb) component will not be specifically limited if it can harden an acrylic compound by ultraviolet irradiation, Preferably, For example, For example, acetophenone, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4 -(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanon-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-one [4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide , 1,2-Octanedione-1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-car bazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane -1-one etc. are mentioned, 1 type may be used individually, or 2 or more types may be used together.

Although content of (Eb) component can be suitably determined according to hardening conditions and the physical property of the hardened|cured material by the active energy ray-curable composition (E) made into the objective, For example, 0.1-15 with respect to a total of 100 mass parts of (Ea) component. It is preferable that it is an amount used as a mass part, especially 1-10 mass parts. When the amount added is less than this, the curability may decrease, and when the amount is greater than this, there is a fear that the influence on the physical properties after curing may be increased.

In addition to the active energy ray-curable composition (E), active energy ray-reactive compounds other than acrylic groups, such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light-resistant stabilizers, heat-resistant stabilizers , antioxidants, surfactants, colorants, and fillers of polymers or inorganic substances may also be blended. These structures do not restrict|limit especially the structure, A well-known thing can be used in the range which does not impair the objective of this invention.

Moreover, as an active energy ray-curable composition (E), it is an active-energy-ray-curable composition in which (Ea), (Eb) component and various additives were blended, and it is marketed by each company in the classification of paint, ink, hard-coat agent, etc. You may use the composition of (E) as a part or the whole of component. Even when a commercially available hard coat agent is used as described above, depending on the purpose, organic solvents, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light-resistant stabilizers, heat-resistant stabilizers, It can be formulated by adding antioxidants, surfactants, colorants and fillers.

The fluorine-containing active energy ray-curable composition of the present invention obtained as described above can suppress the inclusion of volatile organic compounds that cannot be incorporated into the structure of the cured product, and contains a perfluoropolyether group as a water and oil repellency group and an active energy A cured product excellent in water repellency, oil repellency, slipperiness, antifouling property, fingerprint wiping property, low refractive index property, solvent resistance, chemical resistance, etc. Since this fluorinated acrylic compound does not contain a urethane bond in its molecule, a cured product excellent in abrasion resistance is obtained.

In addition, the present invention provides an article (an article having a cured product layer (also referred to as a cured film or cured resin layer) on the surface) obtained by applying the above-described fluorine-containing active energy ray-curable composition of the present invention to the surface of a substrate and curing it. . As described above, when the fluorine-containing active energy ray-curable composition of the present invention is used, it becomes possible to form a cured film (cured resin layer) having excellent surface properties on the surface of the substrate. In particular, it is useful for imparting water repellency, oil repellency, and antifouling properties to the surface of the acrylic hard coat. Thereby, it becomes difficult to adhere to the recognition of fingerprints, sebum, sweat, etc., contamination by cosmetics, etc., and can provide the hard-coat surface excellent in wiping property to a base material (article). For this reason, the fluorine-containing active energy ray-curable composition of the present invention can provide a coating film or a protective film for the surface of a base material (article) that may be contaminated by cognition, cosmetics, etc. in contact with the human body.

The cured film (cured resin layer) formed by using the fluorine-containing active energy ray-curable composition of the present invention is cured by coating directly on the surface of the article to which properties are imparted, or various base films (e.g., polyethylene, poly Film of the present invention on propylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyether ether ketone, polyether sulfone, aramid, polyimide, etc.) By coating a fluorine active energy ray-curable composition, preparing a cured film, and sticking this film on the surface of the object made into object, a characteristic can be provided to various goods.

Here, the coating method of the fluorinated active energy ray-curable composition of the present invention is not particularly limited, and for example, roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating, screen printing, etc. of well-known coating method can be used. After coating, an active energy ray is irradiated to a coating film, and this is hardened. Here, as an active energy ray, although arbitrary things, such as an electron beam and an ultraviolet-ray, can be used, an ultraviolet-ray is especially preferable. As the ultraviolet source, a mercury lamp, a metal halide lamp, and an LED lamp are suitable. As the ultraviolet ray irradiation quantity is too small, because there is possibility that the remaining uncured component, and the degradation is too large, the coating film and the substrate, to be in the range of 10 ~ 10,000mJ / cm ^2, particularly 20 ~ 4,000mJ / cm ² is preferred. In addition, in order to prevent inhibition of curing by oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, or argon when irradiated with ultraviolet rays, or the surface of the coating film is replaced with a protective layer having releasability and UV transmittance. It may be covered and irradiated with ultraviolet rays from above, or if the substrate has ultraviolet ray transmittance, the surface of the coating film may be covered with a releasable protective layer and then irradiated with ultraviolet ray from the side opposite to the coated surface of the substrate. Further, in order to effectively level the coating film or to polymerize the acrylic groups in the coating film, the coating film and the substrate may be heated by any method such as a hot air drying furnace before and during UV irradiation.

In addition, the thickness of the cured film (cured resin layer) formed using the fluorinated active energy ray-curable composition of the present invention is not particularly limited, but when the resulting film thickness is too thin, sufficient surface hardness cannot be obtained, and When it is thick, the mechanical strength of a hard-coat film falls and it becomes easy to produce a crack, Usually, it is 5 nm - 100 micrometers, It is preferable that they are especially 1 micrometer - 20 micrometers.

In addition, the cured film (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention has a water contact angle at 25°C and 40% relative humidity of 90° or more, preferably 95° or more. do. In addition, in this invention, the water contact angle is the value measured under the conditions of droplet: 2 microliters using the contact angle meter Drop Master (made by Kyowa Kaimen Chemical Co., Ltd.). Moreover, in order to set it as the said water contact angle, it is preferable that this fluorine-containing active energy ray-curable composition is mixed uniformly.

Examples of such articles include tablet-type computers, portable (communications) information terminals such as mobile phones and smartphones, note PCs, digital media players, watch-type and glasses-type wearable computers, digital cameras, digital video cameras, electronic book readers, and the like. Casings of various devices carried by human hands; Various flat panel displays such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, toner-based displays, and display operation equipment surfaces such as TV screens, automobiles exterior of furniture, polished surfaces of pianos and furniture, marble and other architectural stone surfaces, decorative building materials around drains in toilets, bathrooms and washrooms, protective glass for art display, show windows, showcases, cover for photo frames, wrist watches, automobiles It is useful as a coating film and a surface protective film for a member made of transparent glass or transparent plastic (acrylic resin, polycarbonate, etc.), various mirror members, etc.

In particular, various devices having a display input device for performing operations on the screen with a human finger or palm, such as a touch panel display, for example, a tablet computer, a note PC, a watch-type wearable computer, an activity meter, a mobile phone, a smart phone, etc. (Communications) Information terminals, digital media players, e-book readers, digital photo frames, game machines and game machine controllers, digital cameras, digital video cameras, navigation devices for automobiles, etc., automatic teller machines, automatic teller machines, automatic It is useful as a surface protection film of various controllers, such as a vending machine, digital signage (electronic signage), a security system terminal, a POS terminal, a remote controller, and display input devices, such as a panel switch for in-vehicle devices.

Further, the cured film formed of the fluorine-containing active energy ray-curable composition of the present invention may include optical recording media such as magneto-optical disks and optical disks; Spectacle lenses, camera lenses, projector lens prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, antireflection films, optical fibers and optical couplers, etc. It is useful also as a surface protective film of various protective parts of an apparatus.

In addition, the cured film formed by the fluorine-containing active energy ray-curable composition of the present invention has a small dimensional change between coating and curing compared to a cured film formed by a conventional hard coat composition containing a volatile organic compound. , it is also useful as a surface protective film for applications requiring high dimensional accuracy for cured products, for example, curable compositions for nanoimprints and curable compositions for 3D printers.

(Example)

Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1] Synthesis of fluorinated acrylic compound (A-1)

In a dry nitrogen atmosphere, in a 2,000 mL three-necked flask equipped with a reflux device and a stirring device, the following formula

(q1/p1=0.9, p1+q1 ≒45, number average molecular weight calculated from ^{19 F-NMR ≒4,300)}

500 g (0.12 mol) of a perfluoropolyether represented by , 700 g of m-xylenehexafluoride and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added, and heated to 90° C. while stirring. To this was added 0.442 g of a platinum/1,3-divinyl-tetramethyldisiloxane complex toluene solution ( ^{containing 1.1 × 10 -6} moles as a single Pt), and stirred for 4 hours while maintaining the internal temperature at 90°C or higher continued After it was confirmed that the ¹ H-NMR to allyl groups of the raw material disappeared, and the tetramethyl cyclotetrasiloxane in the solvent and the excess was evaporated under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 498 g of a colorless and transparent liquid compound (a) represented by the following formula.

(q1/p1=0.9, p1+q1 ≒45, number average molecular weight calculated from ^{19 F-NMR ≒4,800)}

In a dry air atmosphere, 3.2 g (1.88×10 ^-2 mol) of allyloxyethyl methacrylate, m-xylenehexa, per 10.0 g of compound (a) obtained above (1.3×10 ^{−2 mol of Si-H groups) 10.0 g of fluoride and 1.0×10 −2} g of a toluene solution of chloroplatinic acid/vinylsiloxane complex ^{(containing 0.3×10 −7} mol as a single Pt) were mixed, and the mixture was stirred at 80° C. for 4 hours. ^{After confirming that the Si-H group has disappeared by 1} H-NMR and IR, the solvent and excess allyloxyethyl methacrylate are distilled off under reduced pressure, treated with activated carbon, and a colorless and transparent fluorinated acrylic compound represented by the following formula (A-1) 10.4 g was obtained.

(q1/p1=0.9, p1+q1≒45)

[Synthesis Example 2] Synthesis of fluorinated acrylic compound (A-2)

In a dry nitrogen atmosphere, in a 1,000 mL three-necked flask equipped with a reflux device and a stirring device, the following formula

(q2/p2=1.3, p2+q2≈16, ¹⁹ Number average molecular weight ≈1,800 calculated from F-NMR)

188 g (0.10 mol) of a perfluoropolyether represented by , 188 g of m-xylenehexafluoride and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added, and heated to 90° C. while stirring. To this, 0.442 g of a platinum/1,3-divinyl-tetramethyldisiloxane complex toluene solution ( ^{containing 1.1 × 10 -6} moles as a single Pt) was added, and stirred for 4 hours while maintaining the internal temperature at 90°C or higher continued ^{After confirming that the allyl group of the raw material had disappeared by 1} H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 192 g of a colorless and transparent liquid compound (b) represented by the following formula.

(q2/p2=1.3, p2+q2≈16, ¹⁹ Number average molecular weight ≈2,300 calculated from F-NMR)

In dry air atmosphere, based on the compound (b) 10.0g (Si-H amount 2.6 × 10 ^-2 mol) obtained above, allyloxy methacrylate 5.1g (2.60 × 10 ^-2 mol), m- xylene hexafluoro ^{10.0 g of fluoride and 2.0 x 10 -2} g of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (0.6 x 10 ^-7 mol as a single Pt) were mixed, and the mixture was stirred at 80°C for 4 hours. ^{After confirming that the Si-H group has disappeared by 1} H-NMR and IR, the solvent and excess allyloxyethyl methacrylate are distilled off under reduced pressure, treated with activated carbon, and a colorless and transparent fluorinated acrylic compound represented by the following formula (A-2) 11.6 g was obtained.

(q2/p2=1.3, p2+q2≒16)

[Synthesis Example 3] Synthesis of fluorinated acrylic compound (A-3)

In a dry nitrogen atmosphere, in a 2,000 mL three-necked flask equipped with a reflux device and a stirring device, the following formula

(q1/p1=0.9, p1+q1 ≒45, number average molecular weight calculated from ^{19 F-NMR ≒4,300)}

500 g (0.12 mol) of a perfluoropolyether represented by , 700 g of m-xylenehexafluoride and 451 g (1.50 mol) of pentamethylcyclopentasiloxane were added, and the mixture was heated to 90° C. while stirring. To this, 0.442 g of a platinum/1,3-divinyl-tetramethyldisiloxane complex toluene solution ( ^{containing 1.1 × 10 -6} moles as a single Pt) was added, and stirred for 4 hours while maintaining the internal temperature at 90°C or higher continued ^{After confirming that the allyl group of a raw material lose|disappeared by <1>} H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 511 g of a colorless and transparent liquid compound (c) represented by the following formula.

(q1/p1=0.9, p1+q1 ≒45, number average molecular weight calculated from ^{19 F-NMR ≒4,900)}

In a dry air atmosphere, 4.2 g (2.44 x 10 ^-2 mol) of allyloxyethyl methacrylate, m-xylenehexa, per 10.0 g (Si-H group amount: 1.6 x 10 ^{-2 mol) of compound (c) obtained above 10.0 g of fluoride and 1.0×10 −2} g of a toluene solution of chloroplatinic acid/vinylsiloxane complex ^{(containing 0.3×10 −7} mol as a single Pt) were mixed, and the mixture was stirred at 80° C. for 4 hours. ^{After confirming that the Si-H group has disappeared by 1} H-NMR and IR, the solvent and excess allyloxyethyl methacrylate are distilled off under reduced pressure, treated with activated carbon, and a colorless and transparent fluorinated acrylic compound represented by the following formula (A-3) 10.1 g was obtained.

(q1/p1=0.9, p1+q1≒45)

[Synthesis Example 4] Synthesis of fluorinated acrylic compound (A-4)

In a dry nitrogen atmosphere, in a 1,000 mL three-necked flask equipped with a reflux device and a stirring device, the following formula

(q2/p2=1.3, p2+q2≈16, ¹⁹ Number average molecular weight ≈1,800 calculated from F-NMR)

188 g (0.10 mol) of a perfluoropolyether represented by , 188 g of m-xylenehexafluoride and 451 g (1.50 mol) of pentamethylcyclopentasiloxane were added, and heated to 90° C. while stirring. To this, 0.442 g of a platinum/1,3-divinyl-tetramethyldisiloxane complex toluene solution ( ^{containing 1.1 × 10 -6} moles as a single Pt) was added, and stirred for 4 hours while maintaining the internal temperature at 90°C or higher continued ^{After confirming that the allyl group of a raw material lose|disappeared by <1>} H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 199 g of a colorless and transparent liquid compound (d) represented by the following formula.

(q2/p2=1.3, p2+q2≈16, ¹⁹ F-NMR number average molecular weight ≈2,400)

In a dry air atmosphere, 8.7 g (5.11 x 10 ^-2 mol) of allyloxyethyl methacrylate, m-xylenehexa, per 10.0 g of compound (d) obtained above (the amount of Si-H ^{groups of 3.3 x 10 -2 mol) 10.0 g of fluoride and 2.0 x 10 -2} g of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (0.6 x 10 ^-7 mol as a single Pt) were mixed, and the mixture was stirred at 80°C for 4 hours. ^{After confirming that the Si-H group has disappeared by 1} H-NMR and IR, the solvent and excess allyloxyethyl methacrylate are distilled off under reduced pressure, treated with activated carbon, and a colorless and transparent fluorinated acrylic compound represented by the following formula (A-4) 11.6 g was obtained.

(q2/p2=1.3, p2+q2≒16)

[Synthesis Example 5] Synthesis of fluorinated acrylic compound (A-5)

In a 100 mL four-necked flask equipped with a reflux device and a stirring device, the following formula

10.0 g of the compound (e) represented by (Si-H group weight: 8.65 × 10 ^-3 mol), 2.2 g (1.30 × 10 ^-2 mol) of allyloxyethyl methacrylate, and 10.0 g of m-xylene hexafluoride were introduced , and stirred under a nitrogen atmosphere to 90°C. ^{To this, 2.0 x 10 -2} g of a toluene solution of a chloroplatinic acid/vinyl siloxane complex ^{(which contains 0.6 x 10 -7} mol as a single Pt) was added, and the mixture was stirred at 80°C for 4 hours. ^{After confirming that the Si-H group has disappeared by 1} H-NMR and IR, the solvent and excess allyloxyethyl methacrylate are distilled off under reduced pressure and treated with activated carbon to form a translucent white highly viscous liquid represented by the following formula 8.9 g of a fluorine acryl compound (A-5) was obtained.

[Synthesis Example 6] Synthesis of fluorinated acrylic compound (A-6)

In a 100 mL four-necked flask equipped with a reflux device and a stirring device, the following formula

10.0 g of the compound (f) represented by (Si-H group weight: 8.88 × 10 ^-3 mol), 2.3 g of allyloxyethyl methacrylate (1.33 × 10 ^-2 mol), and 10.0 g of m-xylene hexafluoride were introduced , and stirred under a nitrogen atmosphere to 90°C. ^{To this, 2.0 x 10 -2} g of a toluene solution of a chloroplatinic acid/vinyl siloxane complex ^{(which contains 0.6 x 10 -7} mol as a single Pt) was added, and the mixture was stirred at 80°C for 4 hours. ^{After confirming that the Si-H group has disappeared by 1} H-NMR and IR, the solvent and excess allyloxyethyl methacrylate are distilled off under reduced pressure and treated with activated carbon to form a translucent white highly viscous liquid represented by the following formula 8.9 g of a fluorine acryl compound (A-6) was obtained.

In addition, the fluorinated acrylic compounds (A-1) to (A-6) obtained in Synthesis Examples 1 to 6 do not contain volatile organic compounds.

Using the fluorinated acrylic compounds (A-1) to (A-6) obtained in Synthesis Examples 1 to 6 above and the following acrylic compounds (B-1) to (B-3), the following fluorinated acrylic compositions (F -1) to (F-6) were prepared.

(B-1) isobutyl acrylate

(B-2) tetrahydrofurfuryl acrylate

(B-3) 1,6-hexanediol diacrylate

Fluorinated acrylic composition (F-1):

(A-1) 20 parts by mass

(B-1) 80 parts by mass

Fluorinated acrylic composition (F-2):

(A-2) 20 parts by mass

(B-3) 80 parts by mass

Fluorinated acrylic composition (F-3):

(A-3) 20 parts by mass

(B-1) 80 parts by mass

Fluorinated acrylic composition (F-4):

(A-4) 20 parts by mass

(B-3) 80 parts by mass

Fluorinated acrylic composition (F-5):

(A-5) 20 parts by mass

(B-2) 80 parts by mass

Fluorinated acrylic composition (F-6):

(A-6) 20 parts by mass

(B-2) 80 parts by mass

[Examples 1 to 6, Comparative Examples 1 and 2]

fluoride activation energy line Preparation of curable composition

The prepared fluorinated acrylic compositions (F-1) to (F-6) or the fluorinated acrylic compounds (A-1) and (A-2) were each blended in the proportions shown in Table 1 below. An active energy ray-curable composition was prepared.

A-9550: dipentaerythritol penta/hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

A-TMM-3: pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

IBA: isobutyl acrylate

THF-A: tetrahydrofurfuryl acrylate

HDDA: 1,6-hexanediol diacrylate

O-1173: 2-hydroxy-2-methylpropiophenone (Omnirad-1173, manufactured by BASF Japan)

potter's department of cured film produce

Each of the fluorine-containing active energy ray-curable compositions of Examples and Comparative Examples was coated on a polycarbonate substrate by spin coating. After coating, after leveling at room temperature (25° C.) for 10 minutes, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Denko Co., Ltd.), in a nitrogen atmosphere, ^{ultraviolet rays with an accumulated irradiation amount of 1,600 mJ/cm 2} were applied to the coated surface. was irradiated to harden the composition, and a cured film having a thickness of about 9 µm was obtained.

The appearance (transparency) of the cured film obtained above was visually measured, and the water contact angle was measured as an evaluation of antifouling property by the method shown below, and the water contact angle was measured after a wear test as an evaluation of magic ink resistance and abrasion resistance. . These results are shown in Table 2.

Evaluation of antifouling properties

[Measurement of water contact angle]

About the cured film produced above, the contact angle with respect to the water of the cured film was measured using the contact angle meter Drop Master (made by Kyowa Kaimen Chemical Co., Ltd.) (droplet: 2 microliters, temperature: 25 degreeC, humidity (RH) ):40%).

[Evaluation of magic ink resistance (magic bounce)]

About the cured film produced above, a straight line was drawn with a magic pen (Magic Ink large size made by Teranishi Chemical Co., Ltd.), and what repelled ink was made into (circle) and what does not repel it was made into x.

Assessment of wear resistance

[Measurement of water contact angle after wear test]

The surface of the cured film was subjected to an abrasion test using a rubbing tester (manufactured by Shinto Chemical Co., Ltd.), and the water contact angle after the test was measured. The average value of the measured values of N=8 was calculated|required.

The test conditions are shown below.

An eraser: RUBBER STICK (product made in Minoan company)

Travel distance (one way): 40mm

Travel speed: 3,200mm/min

Load: 500 g/6 mm ² φ

Number of wear: 1,000 times

Fluorinated acrylic compounds (A-1) to (A-6) that do not contain a urethane bond in the molecular structure as a water/oil repellency and antifouling agent, and acryl containing 1-2 (meth)acrylic groups per molecule Examples 1 to 6 using the fluorinated acrylic compositions (F-1) to (F-6) prepared by blending the compound (B) in a specific ratio showed excellent antifouling properties and high abrasion resistance was confirmed. On the other hand, without mixing the fluorinated acrylic compound (A-1) or (A-2) that does not contain a urethane bond in the molecular structure with the acrylic compound (B) containing 1-2 (meth)acrylic groups in one molecule In Comparative Example 1 and Comparative Example 2 directly added, the cured film appearance was cloudy and low antifouling properties were shown.

Claims (16)

(A) a fluorinated acrylic compound represented by the following general formula (1)

[In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Z ¹ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or two or more selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may contain a cyclic structure in the middle, provided that the structure It does not contain a urethane bond in it. Q ¹ is independently an (a+1) valent coupling group containing at least (a+1) silicon atoms, may form a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom, It may exist, however, it does not contain a urethane bond in structure. Z ² is independently the formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l are in the range where the molecular weight ^{of Z 2 is 58 to 748,} Each independently represents an integer from 0 to 10, i+j+k+l=1 to 10. o is an integer from 2 to 10) is a divalent alkylene ether group. X is independently a hydrogen atom, or an acryl group which may contain at least one selected from an oxygen atom and a nitrogen atom, or a monovalent organic group containing an α-substituted acryl group, and is an average of at least one acryl group per molecule It contains a monovalent organic group containing a group or an α-substituted acryl group, provided that it does not contain a urethane bond in its structure. a is independently an integer from 1 to 10; Y is a fluorine atom or _a monovalent group represented by ^{-Z 1} -Q ¹ -[Z ² -X] a . ^{Z 1} in Formula (1) ^{and a Z 2} bounded by [ ] are each bonded to a silicon atom in the ^{Q 1 structure], and}
(B) An acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acryl groups in one molecule
contains as an essential component, the mass ratio of component (A) and component (B) is within the range of 0.01 < (A) / (B) < 10, and does not contain a volatile organic compound having no group reactive with an acryl group A fluorine-containing acrylic composition that is not. The method according to claim 1, wherein in the general formula (1), Rf ¹ is

(Wherein, b is an integer from 1 to 3 independently for each unit. c, d, e, f, g, and h are each an integer from 0 to 200, and c+d+e+f+g+h=3 ~ 200. Each of these units may be linear or branched, and each repeating unit indicated in parentheses marked with c, d, e, f, g, h may be randomly bonded.)
A fluorinated acrylic composition, characterized in that it is a divalent perfluoropolyether group represented by The method according to claim 1, wherein in the general formula (1), Rf ¹ is

(However, the arrangement of repeating units enclosed in ( ) is random, p is an integer from 1 to 199, q is an integer from 1 to 170, and p+q is from 6 to 200. s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120, s+t+u is an integer from 3 to 126, v is an integer from 4 to 120)
A fluorinated acrylic composition, characterized in that it is any one of the divalent perfluoropolyether groups represented by The method according to claim 1, wherein in the general formula (1), Z ¹ is

A fluorinated acrylic composition, characterized in that it has any one structure represented by The method according to claim 1, wherein in the general formula (1), Q ¹ is

(Wherein, a' is an integer from 2 to 10.)
A fluorinated acrylic composition, characterized in that (a'+1) is a linking group represented by The method according to claim 1, wherein in the general formula (1), X is

(Wherein, R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and Z ³ is a single bond or 2 that may contain an ether bond and/or an ester bond having 1 to 18 carbon atoms. It is a valent or trivalent hydrocarbon group, and n is 1 or 2.)
Fluorine-containing acrylic composition, characterized in that the structure represented by. The fluorinated acrylic composition according to claim 1, wherein the component (A) is a fluorinated acrylic compound represented by the following general formula (2) or (3).

(Wherein, Rf ¹ , Z ¹ , Z ² , Q ¹ , and a are as described above. R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.) The fluorinated acrylic composition according to claim 1, wherein the component (A) is a fluorinated acrylic compound represented by the following general formula (4) or (5).

[wherein, Rf ¹ , Z ¹ , Q ¹ , and a are as described above. Z ⁴ is the following formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and j', k', and l' are each independently an integer of 0 to 4, and j'+k '+l' = 1 to 10, and o is an integer from 2 to 10.) is a divalent alkylene ether group.] The fluorinated acrylic composition according to claim 1, wherein the component (A) is one or two or more selected from fluorinated acrylic compounds represented by the following formulas.

[wherein, Rf ² is -CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF ₂ -, p is an integer from 1 to 199, q is an integer from 1 to 170, p+ q is 6~200, and the arrangement of repeating units enclosed in ( ) is random. v is an integer from 4 to 120; R ² is independently a hydrogen atom or a methyl group, and R ³ is independently a hydrogen atom, a methyl group or a phenyl group. Z ⁴ is the following formula

(Wherein, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and j', k', and l' are each independently an integer of 0 to 4, and j'+k '+l' = 1 to 10, o is an integer of 2 to 10) is a divalent alkylene ether group represented by), and m is an integer of 2 to 5.] The following general formula (6) as a part or all of (B) component according to claim 1

(Wherein, R ⁴ is a urethane bond, an ether bond, an isocyanate group, or contains a hydroxyl group and a monovalent hydrocarbon group of 1 to 20 carbon atoms group which may. R ⁵ represents a hydrogen atom, a methyl group, a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms It is a roalkyl group.)
A fluorinated acrylic composition comprising an acrylic compound represented by The following general formula (7) as a part or all of (B) component according to claim 1

(Wherein, R ⁶ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group. R ⁷ is each independently a hydrogen atom, a methyl group, a fluorine atom, or a carbon number 1 to 6 is a fluoroalkyl group.)
A fluorinated acrylic composition comprising an acrylic compound represented by The fluorinated acrylic composition according to claim 1, wherein the acrylic compound of component (B) does not contain an alkyl group substituted with a fluorine atom. A fluorinated active energy ray-curable composition comprising 0.005 to 40 parts by mass of the fluorinated acrylic composition according to claim 1 with respect to 100 parts by mass of the active energy ray-curable composition (E). The active energy ray-curable composition (E) according to claim 13,
(Ea) Acrylic compound: 100 parts by mass;
(Eb) Photoinitiator: 0.1-15 mass parts
A fluorine-containing active energy ray-curable composition comprising: The fluorine-containing active energy ray-curable composition according to claim 13, wherein a cured product having a water contact angle of 90° or more at 25°C and 40% relative humidity is provided. An article having on its surface a layer of a cured product of the fluorine-containing active energy ray-curable composition according to claim 13.